Oil-soluble hydrogenation catalyst, method for preparing the same, and use thereof

Abstract

The present application relates to an oil-soluble hydrogenation catalyst, a preparation method and application thereof, the hydrogenation catalyst comprising a metal central atom or central ion and an organic ligand coordinated with the metal central atom or central ion; the metal is one or more of group B or group VIII metals with hydrogenation performance; the organic ligand comprises a carboxylate group and a carboxylic acid group, and forms a coordination bond with the metal central atom or central ion through an oxygen atom. When the oil-soluble hydrogenation catalyst is used for oil product hydrogenation, the coordination group of the organic ligand in the oil-soluble hydrogenation catalyst forms a coordination bond with the metal central atom or central ion through an oxygen atom, which can be efficiently dispersed in the oil phase, has high hydrogenation activity in the reaction process, can obtain high raw material cracking rate and impurity atom removal rate, and can maintain low condensation rate, and finally realizes lightening and high-quality of oil product raw materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of petrochemical industry, and particularly relates to a hydrogenation catalyst and a preparation method and application thereof. BACKGROUND

[0002] With the increasing dependence on petroleum resources, efficient utilization of petroleum resources, especially efficient conversion of high-metal and high-asphaltene content inferior heavy oil into light oil and gas, is an effective way to solve the current energy problem. Hydrofining of petroleum products, including hydrodesulfurization, denitrification, and demetallization, has always been an important part of the petrochemical industry. With increasingly stringent environmental regulations and rapid economic development, there is a rapid increase in demand for light oil and gas and chemical raw materials, and it is increasingly important to develop catalysts for efficient processing of heavy feedstocks. Traditional hydrofining catalysts are fixed-bed supported catalysts, which are usually composed of active metals and supports. The active metals usually have hydrogenation activity, and the supports are alumina or mixtures thereof with other oxides (such as ZrO2, MgO, etc.), which can provide the required acidity for cracking reactions. Supported catalysts have become the most widely used catalysts in industrial applications due to their high catalytic activity, strong mechanical strength, and mature process technology. However, with the increasing deterioration of crude oil quality and the increasingly stringent requirements of environmental protection and downstream devices for oil products, supported catalysts need to be upgraded and replaced due to their low diffusion mass transfer efficiency and easy coking and deactivation. Oil-soluble catalysts used in slurry bed residue processing technology have high dispersibility, nanoscale size, and high hydrogenation activity, which can overcome steric hindrance, efficiently convert heavy components, and avoid short running cycles caused by coking and fouling. Therefore, oil-soluble catalysts are considered an effective way to hydrogenate and upgrade oil products. As the core of slurry bed processing technology, the preparation of slurry bed oil-soluble catalysts has attracted much attention.

[0003] CN112745357B discloses a method for preparing a complex containing molybdenum and iron. The method mixes a solvent, a molybdenum source, an iron source, and an oxygen-containing organic acid, and then reacts to obtain a product. The product is mixed with a solution containing an alkali source to obtain a mixture. The mixture is subjected to solid-liquid separation to obtain a liquid. The liquid is then contacted with a C6-C18 oxygen-containing organic acid at a temperature of 50-150°C, and then reacted at a temperature of 160-320°C. The resulting product is separated and purified to obtain the complex containing molybdenum and iron.

[0004] CN116020563A discloses a preparation method of a non-supported multi-metal hydrogenation catalyst. The method mixes a first metal source or a dispersion thereof with an organic ligand compound, and then reacts at a temperature T1 for a time t1. Then, the method reacts at a temperature T2 for a time t2, and then adds a second metal source or a dispersion thereof, and reacts at a temperature T2 for a time t3. The resulting liquid product is collected as a non-supported catalyst.

[0005] CN114618584A discloses a preparation method of an oil-soluble iron-based catalyst, an iron salt solution and a fatty acid salt solution are mixed, heated to react, and after standing and layering, the upper organic phase is washed and dried to obtain an oil-soluble iron-based catalyst; the iron salt is preferably ferric chloride hexahydrate, ferric nitrate nonahydrate or sulfuric acid iron monohydrate, and the fatty acid salt is preferably stearate or oleate.

[0006] However, the preparation process of the existing oil-soluble catalyst is relatively complex, and the performance and cost of the obtained catalyst still need to be improved, and the hydrogenation activity of the catalyst still needs to be improved. SUMMARY

[0007] The purpose of the present application is to provide an oil-soluble hydrogenation catalyst and its preparation method and application, in order to solve the problem that the preparation process of the existing catalyst is complex, and its hydrogenation activity needs to be further improved when used for hydrogenation treatment.

[0008] In order to achieve the above purpose, the first aspect of the present application provides an oil-soluble hydrogenation catalyst, which comprises a metal central atom or central ion and an organic ligand coordinated with the metal central atom or central ion; the general formula of the hydrogenation catalyst is: MO a [R(COOH b ) x ] c , wherein M represents a metal, R(COOH b x represents the organic ligand, the organic ligand includes a carboxylate group and a carboxylic acid group, R represents a hydrocarbon group in the organic ligand, x represents the molar ratio of the total number of the carboxylate group and the carboxylic acid group and the hydrocarbon group R, a represents the molar ratio of the non-coordinated oxygen atom connected to the metal M to the metal M, b represents the molar proportion of the carboxylic acid group in the total number of the carboxylate group and the carboxylic acid group, and c represents the molar ratio of the organic ligand to the metal M, wherein: the metal is one or more of Group B or Group VIII metals with hydrogenation performance; x is 1, 2 or 3, preferably 1 or 2; a is a positive number of 0-5, preferably a positive number of 1-3; b is a positive number of 0.01-0.99, preferably a positive number of 0.1-0.5; and c is a positive number of 0.5-10, preferably a positive number of 1-5.

[0009] ​Optionally, the content of the metal in the hydrogenation catalyst is 2-35%, preferably 8-30%, and further preferably 10-20%, based on the dry weight of the hydrogenation catalyst; the metal is one or more of Ti, V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn, preferably one or more of V, Mo, W, Fe, Co, Ni, Cu and Zn, and further preferably one or more of Fe, Ni, Mo and Zn; R is a C3-C19 hydrocarbon group, preferably a C5-C11 normal or isomeric alkyl group, a C5-C12 cycloalkyl-containing group and a C6-C12 aryl group.

[0010] The second aspect of the present application provides a method for preparing an oil-soluble hydrogenation catalyst, the method comprising:

[0011] S1, mixing a first metal source, a basic agent, water and a first organic ligand compound to perform a first complexation reaction to obtain a first mixture; the first organic ligand compound is a carboxylic acid or an acid anhydride thereof,

[0012] or, mixing a first metal source, water and a second organic ligand compound to perform a first complexation reaction to obtain a first mixture; the second organic ligand compound is a mixture of a carboxylic acid salt and a carboxylic acid or an acid anhydride thereof;

[0013] S2, performing oil-water layering and liquid separation on the first mixture to obtain a first oil-phase liquid product;

[0014] The metal in the first metal source is one or more of Group B or Group VIII metals having hydrogenation performance, and the first metal source includes one or more of metal oxides, metal hydroxides, metal oxyacids and metal inorganic salts; the basic agent includes one or more of oxides, hydroxides, carbonates, bicarbonates of alkali metals or alkaline earth metals, ammonia gas, aqueous ammonia and organic amines.

[0015] Optionally, the method further comprises: mixing the first oil-phase liquid product with a second metal source to perform a second complexation reaction to obtain a second oil-phase liquid product; the molar ratio of the first metal source to the second metal source is 1:(0.01-10) in terms of metal; the second metal source is one or more of metal oxides, metal hydroxides, metal oxyacids and metal inorganic salts, and the metal in the second metal source is one or more of Group B or Group VIII metals having hydrogenation performance and different from the metal in the first metal source.

[0016] Optionally, the Group B or Group VIII metal having hydrogenation performance is one or more of Ti, V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn, preferably one or more of V, Mo, W, Fe, Co, Ni, Cu and Zn, further preferably one or more of Fe, Ni, Mo and Zn; the hydrocarbyl group in the carboxylate salt and the carboxylic acid or its anhydride is a C3-C19 hydrocarbyl group, preferably a C5-C11 n- or iso-alkyl group, a C5-C12 cycloalkyl-containing group and a C6-C12 aryl group; the carboxylate salt is a compound formed by the carboxylic acid and the basic agent; preferably, the carboxylic acid is one or more of succinic acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, ethylbutyric acid, oleic acid, petrolic acid, salicylic acid, benzoic acid and phenylacetic acid, and the carboxylate salt is sodium ethylhexanoate, sodium ethylbutyrate, ammonium ethylhexanoate or ammonium ethylbutyrate.

[0017] Optionally, the molar ratio of the first organic ligand compound or the second organic ligand compound to the first metal source is 0.5-10, preferably 1-5; the molar ratio of the first organic ligand compound to the basic agent is 0.01-0.99, preferably 0.5-0.9; the molar ratio of the carboxylate salt to the carboxylic acid or its anhydride in the second organic ligand compound is 0.01-0.99, preferably 0.5-0.9; and the molar ratio of water to the first organic ligand compound or the second organic ligand compound is 1-20, preferably 5-10.

[0018] Optionally, the time for the oil-water layering is 1-24 h; the reaction temperature for the first complexation reaction is 50-150℃, and the reaction time is 1-8 h; and the reaction temperature for the second complexation reaction is 150-450℃, and the reaction time is 1-8 h.

[0019] The third aspect of the present application provides an oil-soluble hydrogenation catalyst prepared by the method provided in the second aspect of the present application.

[0020] The third aspect of the present application provides a hydrogenation method for oil products, which comprises:

[0021] Under the conditions of a hydrogenation reaction, contacting an oil product raw material with the hydrogenation catalyst provided in the first and third aspects of the present application; wherein the oil product raw material is one or more of benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, oil slurry, residual oil, coal tar and biomass oil.

[0022] Optionally, the conditions of the hydrogenation reaction include: the amount of the hydrogenation catalyst is 50-10000 μg / g, preferably 50-3000 μg / g, based on the weight of the oil feedstock, calculated in terms of metal; the initial hydrogen pressure is 1-20 MPa, preferably 3-15 MPa; the reaction temperature is 200-500 ℃, preferably 300-450 ℃; the liquid hourly space velocity is 0.05-5.0 h -1 , preferably 0.05-1.0 h -1 ; and the hydrogen / oil volume ratio is 100-3000, preferably 200-2000.

[0023] By the above technical solution, the oil-soluble hydrogenation catalyst has high hydrogenation activity, and when used for oil hydrogenation, the coordination group of the organic ligand in the oil-soluble hydrogenation catalyst forms a coordination bond with the metal center atom or center ion through an oxygen atom, which can be highly dispersed in the oil phase, and has high hydrogenation activity in the reaction process; high cracking rate and removal of heteroatom rate of the raw material can be obtained, and the condensation rate can be kept low, so as to finally realize the lightening and high-quality of the oil feedstock.

[0024] Other features and advantages of the present application will be described in detail in the following specific embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0025] The accompanying drawings are included to provide a further understanding of the present application, and constitute a part of the specification, and are used together with the following specific embodiments to explain the present application, but do not constitute a limitation on the present application. In the drawings:

[0026] Figure 1 is the infrared spectrum of the raw material organic ligand used in Example 1 of the present application.

[0027] Figure 2 is the infrared spectrum of the hydrogenation catalyst obtained in Example 1 of the present application.

[0028] Figure 3 is the infrared spectrum of the hydrogenation catalyst obtained in Example 2 of the present application.

[0029] Figure 4 is the infrared spectrum of the hydrogenation catalyst obtained in Example 3 of the present application.

[0030] Figure 5 is the infrared spectrum of the hydrogenation catalyst obtained in Examples 4-6 of the present application. DETAILED DESCRIPTION

[0031] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0032] The first aspect of the present application provides an oil-soluble hydrogenation catalyst, which comprises a metal central atom or central ion and an organic ligand coordinated with the metal central atom or central ion; the general formula of the hydrogenation catalyst is:

[0033] MO a [R(COOH b ) x ] c ,

[0034] wherein M represents a metal, R(COOH b ) x represents the organic ligand, the organic ligand comprises a carboxylate group and a carboxylic acid group, R represents a hydrocarbon group in the organic ligand, x represents the molar ratio of the total number of the carboxylate group and the carboxylic acid group and the hydrocarbon group R, a represents the molar ratio of the non-coordinately bonded oxygen atom connected with the metal M to the metal M, b represents the molar proportion of the carboxylic acid group in the total number of the carboxylate group and the carboxylic acid group, and c represents the molar ratio of the organic ligand to the metal M, wherein:

[0035] the metal is one or more of Group B or Group VIII metals having hydrogenation performance; R is a C3-C19 hydrocarbon group, preferably a C5-C11 normal or isomeric alkyl group, a C5-C12 cycloalkyl-containing group, and a C6-C12 aryl group; x is 1, 2, or 3, preferably 1 or 2; a is a positive number of 0-5, preferably a positive number of 1-3; b is a positive number of 0.01-0.99, preferably a positive number of 0.1-0.5; and c is a positive number of 0.5-10, preferably a positive number of 1-5.

[0036] There are two forms of coordination complexes in the present application, one is that the organic carboxylate is combined with the metal through the formation of a coordination bond between the oxygen atom and the metal, the lone pair of the oxygen atom and the d orbital of the metal atom are combined with each other, forming an organic metal complex having a stable structure, which can generally exist stably at room temperature, and when used for oil hydrogenation, the reaction is heated to a high temperature (> 300℃), and in the presence of H2 and S, it is converted into a metal sulfide active phase, which has a nanoscale size and more coordination unsaturated sites, thereby having high catalytic activity. The other is a coordination compound formed by the interaction between the H atom of the hydroxyl group -OH in the organic carboxylic acid and the O atom in the metal oxide through a secondary bond hydrogen bond, which has a low bond energy, and thus has an unstable factor, the coordination structure is easily destroyed, leading to the agglomeration between the metal oxide molecules, and thus the metal catalyst formed through this bonding form has low activity and is not convenient for long-term storage.

[0037] According to the present application, the content of the metal in the hydrogenation catalyst is 2-35%, preferably 8-30%, and further preferably 10-20%, based on the dry weight of the hydrogenation catalyst; the metal is one or more of Ti, V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn, preferably one or more of V, Mo, W, Fe, Co, Ni, Cu and Zn, and further preferably one or more of Fe, Ni, Mo and Zn; R is a C3-C19 hydrocarbon group, preferably a C5-C11 normal or isoalkyl group, a C5-C12 cycloalkyl group and a C6-C12 aryl group.

[0038] According to the present application, the infrared spectrum of the hydrogenation catalyst has characteristic peaks at least in the range of 1350-1450 cm -1 and 1500-1610 cm -1 .

[0039] In the present application, "C3-C19 hydrocarbon group" refers to a hydrocarbon group having 3-19 carbon atoms, which can be a saturated or unsaturated straight chain, branched chain or carbocyclic hydrocarbon group, including but not limited to C3-C19 normal alkyl group, C3-C19 isoalkyl group, C5-C19 cycloalkyl group and C6-C19 aryl group.

[0040] In the present application, "C5-C11 normal alkyl group" refers to 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.

[0041] In the present application, "C5-C11 isoalkyl group" refers to a branched chain alkyl group having 5-11 carbon atoms, such as iso-pentyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl, iso-decyl and iso-undecyl.

[0042] In the present application, "C5-C12 cycloalkyl group" refers to a saturated hydrocarbon group having 5-12 carbon atoms containing a saturated carbocyclic ring, such as cyclopentyl, cyclohexyl, methylcyclohexyl, decahydronaphthyl, methyldcahydronaphthyl, ethyldcahydronaphthyl and the like.

[0043] In the present application, "C6-C12 aryl group" refers to a group having 6-12 carbon atoms containing an aromatic ring, such as phenyl, naphthyl, anthryl, p-tolyl, benzyl, methylnaphthyl and the like.

[0044] According to the present application, the C3-C19 hydrocarbon group, C5-C11 normal alkyl group, C5-C11 isoalkyl group, C5-C12 cycloalkyl group and C6-C12 aryl group can be optionally substituted, for example, can be unsubstituted, or can be substituted by one or more groups selected from halogen, nitro, sulfonic acid group and the like.

[0045] According to the present application, the oil-soluble hydrogenation catalyst can be a catalyst currently used for oil hydrogenation, which can be highly dispersed in oil phase, such as oil-soluble molybdenum catalyst, oil-soluble molybdenum cobalt catalyst, oil-soluble molybdenum nickel catalyst, oil-soluble iron molybdenum catalyst, oil-soluble iron zinc catalyst, etc. In a specific embodiment of the present application, the oil-soluble catalyst can be oil-soluble catalyst such as iron naphthenate, iron carboxylate, etc.

[0046] The oil-soluble hydrogenation catalyst of the present application has high hydrogenation activity. When used for oil hydrogenation, the coordination group of the organic ligand in the oil-soluble hydrogenation catalyst forms a coordination bond with the metal center atom or center ion through an oxygen atom, which can be highly dispersed in oil phase and has high hydrogenation activity during the reaction process. High raw material cracking rate and heteroatom removal rate can be obtained, and low condensation rate can be maintained, thereby realizing the lightening and high quality of oil raw materials.

[0047] The second aspect of the present application provides a method for preparing an oil-soluble hydrogenation catalyst, which comprises:

[0048] S1, mixing a first metal source, a basic agent, water and a first organic ligand compound to perform a first complexation reaction to obtain a first mixture; the first organic ligand compound is a carboxylic acid or an acid anhydride thereof,

[0049] or, mixing a first metal source, water and a second organic ligand compound to perform a first complexation reaction to obtain a first mixture; the second organic ligand compound is a mixture of a carboxylate and a carboxylic acid or an acid anhydride thereof;

[0050] S2, oil-water layering and liquid separation of the first mixture to obtain a first oil phase liquid product;

[0051] The metal in the first metal source is one or more of Group B or Group VIII metals having hydrogenation performance, and the first metal source includes one or more of metal oxides, metal hydroxides, metal oxoacids and metal inorganic salts; the basic agent includes one or more of oxides, hydroxides, carbonates, bicarbonates of alkali metals or alkaline earth metals, ammonia, aqueous ammonia and organic amines.

[0052] In the method, the addition of the basic agent or the carboxylate, and the oil-water layering and liquid separation operation enable the carboxylate to participate in the formation of the complex compound and to be stably retained in the complex compound.

[0053] According to the present application, optionally, the method further comprises: mixing the first oil phase liquid product with a second metal source to perform a second coordination reaction, to obtain a second oil phase liquid product; the molar ratio of the first metal source to the second metal source is 1:(0.01-10) in terms of metal; the second metal source is one or more of metal oxides, metal hydroxides, metal oxoacids and metal inorganic salts, and the metal in the second metal source is one or more of Group B or Group VIII metals having hydrogenation performance and different from the metal in the first metal source.

[0054] According to the present application, optionally, the Group B and Group VIII metals having hydrogenation performance are one or more of Ti, V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn, preferably one or more of V, Mo, W, Fe, Co, Ni, Cu and Zn, and further preferably one or more of Fe, Ni, Mo and Zn; the hydrocarbon group in the carboxylate and the carboxylic acid or its anhydride is a C3-C19 hydrocarbon group, preferably a C5-C11 normal or isomeric alkyl group, a C5-C12 cycloalkyl group containing a saturated carbon ring and a C6-C12 aryl group; the carboxylate is a compound formed by the carboxylic acid and the basic agent.

[0055] According to the present application, optionally, the molar ratio of the first organic ligand compound or the second organic ligand compound to the first metal source is 0.5-10, preferably 1-5; the molar ratio of the first organic ligand compound to the basic agent is 0.01-0.99, preferably 0.5-0.9; the molar ratio of the carboxylate to the carboxylic acid or its anhydride in the second organic ligand compound is 0.01-0.99, preferably 0.5-0.9; and the molar ratio of water to the first organic ligand compound or the second organic ligand compound is 1-20, preferably 5-10.

[0056] According to the present application, optionally, the first organic ligand compound and the second organic ligand compound are each independently one or more of C4-C20 carboxylic acids or their anhydrides, preferably one or more of C4-C20 normal or isomeric alkyl carboxylic acids or their anhydrides, C6-C20 cycloalkyl carboxylic acids or their anhydrides containing a saturated carbon ring, and C7-C20 aromatic carboxylic acids or their anhydrides containing an aromatic ring; and further preferably one or more of C4-C12 normal or isomeric alkyl carboxylic acids or their anhydrides, C6-C13 cycloalkyl carboxylic acids or their anhydrides containing a saturated carbon ring, and C7-C13 aromatic carboxylic acids or their anhydrides containing an aromatic ring.

[0057] According to the application, optionally, the C4-C20 carboxylic acid refers to a monovalent carboxylic acid with carbon atom number of 4-20, which can be a saturated or unsaturated straight chain, branched chain or carbo ring monovalent carboxylic acid, including but not limited to C4-C20 n-alkyl carboxylic acid, C4-C20 iso-alkyl carboxylic acid, C6-C20 cycloalkane carboxylic acid containing saturated carbo ring and C7-C20 aromatic carboxylic acid containing aromatic ring.

[0058] According to the application, optionally, the carboxylic acid is preferably one or more of succinic acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, ethylbutyric acid, oleic acid, petrolic acid, salicylic acid, benzoic acid and phenylacetic acid; and the carboxylic acid salt is sodium ethylhexanoate, sodium ethylbutyrate, ammonium ethylhexanoate or ammonium ethylbutyrate.

[0059] According to the application, optionally, the oil-water separation time is 1-24 h; the reaction temperature of the first complexation reaction is 50-150 ℃, and the reaction time is 1-8 h; and the reaction temperature of the second complexation reaction is 150-450 ℃, and the reaction time is 1-8 h.

[0060] According to the application, optionally, there is no strict requirement for the reaction pressure and reaction atmosphere in the preparation of the hydrogenation catalyst, for example, the reaction pressure can be normal pressure, and the reaction atmosphere can be air or inert gas atmosphere.

[0061] In a specific embodiment of the application, the method for preparing the oil-soluble hydrogenation catalyst comprises: mixing a metal source, a carboxylic acid, water and an alkaline agent in a reactor, and reacting at 50-150 ℃ for 1-8 h to obtain a layered reaction product, and separating the liquid product in the oil phase to obtain a single-metal hydrogenation catalyst; in another embodiment of the application, the liquid product in the oil phase obtained in the foregoing separation is added with another metal source or several metal sources, and then reacted at 150-450 ℃ for 1-8 h to obtain a product, which is a double-metal or multi-metal hydrogenation catalyst.

[0062] In the application, the metal source is reacted with an alkaline solution, and then neutralized with a carboxylic acid, so as to finally form an organic metal complex, convert the metal into an organic phase, and highly disperse the metal in hydrocarbon compounds. Since the reaction temperature is low and the metal conversion rate is high, the generated catalyst can be highly dispersed in hydrocarbon oil, and in-situ sulfidized into a catalyst active phase in the heating process. The process for preparing the hydrogenation catalyst is simple, the raw materials are low in price and less in quantity, high-temperature treatment is not required, and the energy consumption is low. In addition, the water phase generated in the reaction can be separated and purified to obtain a large amount of salt by-products, such as ammonium nitrate, sodium sulfate and ammonium chloride, which are important chemical products.

[0063] The third aspect of the application provides a hydrogenation method for oil products, which comprises:

[0064] The oil feedstock is one or more of benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, oil slurry, residual oil, coal tar and biomass oil.

[0065] According to the present application, the conditions of the hydrogenation reaction include: the amount of the hydrogenation catalyst is 50-10000 μg / g, preferably 50-3000 μg / g, based on the weight of the oil feedstock, the amount of metal; the initial hydrogen pressure is 1-20 MPa, preferably 3-15 MPa; the reaction temperature is 200-500°C, preferably 300-450°C; the liquid hourly space velocity is 0.05-5.0 h -1 , preferably 0.05-1.0 h -1 ; and the hydrogen / oil volume ratio is 100-3000, preferably 200-2000.

[0066] The present application is further illustrated by the following examples, but the present application is not limited in any way by the examples.

[0067] The raw materials used in the examples are commercially available unless otherwise specified.

[0068] Examples 1-9

[0069] The hydrogenation catalysts in Examples 1-9 are prepared.

[0070] The raw materials, reaction conditions and test results used in Examples 1-3 are shown in Table 1. The corresponding weight of the metal source compound, water, alkaline agent and carboxylic acid is weighed according to Table 1 and added to a three-necked flask, and then the reaction is carried out under the conditions shown in Table 1. The gas produced during the reaction is separated, and after the reaction is completed, the liquid product in the flask is poured out and placed in a separatory funnel for oil-water separation. After standing for 2 h, the upper oil phase product is obtained by separation, which is a single-metal oil-soluble hydrogenation catalyst. The metal content and infrared spectrum of the product are determined, and the composition of the product is determined according to the results.

[0071] The method used in Examples 4-6 is as described above, except that after obtaining the single-metal oil-soluble hydrogenation catalyst described in Example 2, another or more metal sources as described in Table 2 are added, and the reaction is continued under the conditions shown in Table 2. The gas and liquid produced during the reaction are separated, and after the reaction is completed, the remaining liquid product in the flask is the double or multi-metal oil-soluble hydrogenation catalyst. The metal content and infrared spectrum of the product are determined, and the composition of the product is determined according to the results.

[0072] The method used in Examples 7-9 is as described above, except that the corresponding weight of the metal source compound, water and carboxylate salt is weighed according to Table 3, and then the reaction is carried out under the conditions shown in Table 3.

[0073] Table 1: Reaction raw materials, reaction conditions and results of each example

[0074]

[0075]

[0076] Table 2: Reaction raw materials, reaction conditions and results of each example

[0077]

[0078] Table 3: Reaction raw materials, reaction conditions and results of each example

[0079]

[0080]

[0081] Examples 10-12 and Comparative Example 1

[0082] The hydrogenation catalysts prepared in Examples 2, 5 and 6 were applied to the study of the hydrodesulfurization reaction of dibenzothiophene (DBT), in which decahydronaphthalene was used as the solvent, the mass fraction of DBT in 10 g of total reactants (DBT + solvent) was 10%, the reaction was carried out in a 100 mL full back-mixed high-pressure reaction kettle, the test conditions included an initial hydrogen pressure of 5 MPa, a reaction temperature of 360°C, a reaction time of 60 min, and the total amount of hydrogenation catalyst added was 5% based on the weight of the total reactants in terms of metal content. The experimental results are shown in Table 3.

[0083] Comparative Example 1 was tested according to the method of Examples 10-12, except that no hydrogenation catalyst was added. The experimental results are shown in Table 3.

[0084] Table 4: Reaction results of Examples 10-12 and Comparative Example 1

[0085]

[0086] From the results in Table 4, it can be seen that compared with the pure thermal reaction without adding catalyst, the oil-soluble hydrogenation catalysts of the present application have higher DBT conversion rate and desulfurization rate, indicating that the catalysts of the present application have catalytic hydrogenation and desulfurization activity.

[0087] Examples 13-15 and Comparative Example 2

[0088] The hydrogenation catalysts prepared in Examples 2, 4 and 5 were applied to the hydrogenation reaction of catalytic diesel oil. The catalytic diesel oil contained 0.739% of S, 554 μg / g of N, 88% of total aromatic hydrocarbons, 16.9% of monocyclic aromatic hydrocarbons, 60.8% of bicyclic aromatic hydrocarbons and 10.3% of tricyclic aromatic hydrocarbons. The reaction was carried out in a 100 mL full back-mixed high-pressure reactor. 10 g of the catalytic diesel oil was added, and 2 g of the hydrogenation catalyst was added in terms of metal content. The test conditions included an initial hydrogen pressure of 5 MPa, a reaction temperature of 360°C and a reaction time of 60 min. The experimental results are shown in Table 5.

[0089] Comparative Example 2 was tested according to the method of Examples 13-15, except that a conventional Ni-W supported catalyst (28% of Ni+W content, Al2O3, SiO2, etc. as the support) was used to replace the products prepared in Examples in an equivalent amount of metal content. The experimental results are shown in Table 5.

[0090] Table 5 Reaction results of Examples 10-12 and Comparative Example 2

[0091]

[0092] As can be seen from the results in Table 5, compared with the supported catalyst, the non-supported single-metal hydrogenation catalyst and the double-metal or multi-metal hydrogenation catalyst of the present application have lower S and N contents. In addition, the content of polycyclic aromatic hydrocarbons can be effectively reduced, which indicates that the hydrogenation catalysts of the present application have higher catalytic hydrogenation activity.

[0093] Examples 16-17 and Comparative Examples 3-4

[0094] The hydrogenation catalysts prepared in Examples 2 and 4 were applied to the hydrogenation reaction of vacuum residue. The vacuum residue contained 14% of asphaltene, 26.3% of carbon residue and 175 μg / g of heavy metals (Ni+V). 200 g of the vacuum residue was mixed with the hydrogenation catalyst in a 2 L batch high-pressure reactor, and the mixture was contacted with hydrogen under hydrogenation conditions to perform a catalytic hydro-thermal conversion test of the residue. The hydrogenation reaction conditions and the experimental results are shown in Table 6.

[0095] Comparative Example 3 was tested according to the method of Examples 16 or 17, except that the catalyst used in Comparative Example 3 was a single-metal oil-soluble molybdenum catalyst currently used in industry, and the other test conditions were the same. The experimental results are shown in Table 6.

[0096] Comparative Example 4 was tested according to Examples 16 or 17, except that the catalyst used in Comparative Example 4 was the Ni-W supported catalyst used in Comparative Example 2, and the other test conditions were the same. The experimental results are shown in Table 6. Comparative Example 3 was tested according to the method of Examples 16 or 17, except that the catalyst used in Comparative Example 3 was a single-metal oil-soluble molybdenum catalyst currently used in industry, and the other test conditions were the same. The experimental results are shown in Table 6.

[0097] Table 6 Reaction results of Examples 16-17 and Comparative Examples 3-4

[0098]

[0099] From the data of Examples 16, 17 and Comparative Examples 3, 4 in Table 6, it can be seen that the oil-soluble hydrogenation catalyst prepared by the present application not only has lower catalyst metal cost, but also can obtain higher residue cracking rate, lower condensation rate and higher distillate yield when applied to oil hydrogenation.

[0100] Example 18

[0101] The determination method of the metal content in the hydrogenation catalysts obtained in Examples 1-9 and the metal organic acid complexes of the raw materials is as follows: after the test sample is diluted 100 times with an organic solvent, the SPECTRO ARCOS SOP plasma emission spectrometer is used to determine the metal content by inductively coupled plasma emission spectrometry (ICP-OES), and the determination conditions are as follows: the light chamber is tightly filled with argon, the observation is vertical, and the wavelength range is 130 nm-770 nm.

[0102] The determination method of the infrared spectrum of the hydrogenation catalysts obtained in Examples 1-6 is as follows: the NICOLET IS50 spectrometer of Thermo Fisher Company is used to determine the infrared spectrum of the obtained solid catalyst product, and the determination conditions are as follows: the scanning wavelength is from 400-4000 cm -1 , and the scanning times are 16. The ZnSe crystal and mercury cadmium telluride infrared detector are used together to measure the attenuated total reflection ratio (ATR) of the sample, and the resolution is 4 cm -1 .

[0103] Figure 1 The infrared absorption spectrum of the organic ligand compound ethylhexanoic acid in Example 1 is shown in the figure, and it can be seen from the figure that there is a C-O characteristic peak of carboxylic acid at 1701.88 cm -1 , and there is a C-H characteristic peak of CH3 at 1460 cm -1 . Figure 2 The infrared absorption spectrum of the organic acid complexed with Zn in Example 1 is shown in the figure, and it can be seen from the figure that zinc iso-octanoate mainly has two structures, respectively at 1629.21 cm -1 and 1548.00 cm -1 , which are the coordination peaks of carboxylate. The characteristic peaks at these two places are respectively different from the coordination peak of carboxylate at 1427.06 cm -1 by 202.15 cm -1 and 120.94 cm -1 , respectively, indicating that they are monodentate and bidentate coordination forms, respectively, and there is a carboxylic acid peak at 1706.42 cm -1The CO characteristic peak at this location is basically the same as that of the carboxylic acid of ethylhexanoic acid, indicating that the carboxylic acid is in a free state. Figure 3 The image shows the infrared absorption spectrum of the organic acid complexed with Fe in Example 2. An interaction exists between the unreacted organic acid and the coordinated Fe metal, causing the characteristic peak of free carboxylic acid (CO) to shift blue to 1691.55 cm⁻¹. -1 The resulting ferrous isooctanoate also has two coordination structures, located at 1587.31 cm⁻¹. -1 and 1541.18cm -1 The coordination peaks of the carboxylate are generated, and the characteristic peaks at these two locations are similar to those at 1421.90 cm⁻¹. -1 The coordination peaks of the carboxylates differ by 165.41 cm⁻¹. -1 and 119.28cm -1 This indicates monodentate and bidentate coordination forms, respectively. Furthermore, the catalysts prepared in Examples 4-6 using ferric isooctanoate with different metal sources demonstrate this (e.g.) Figure 5 As shown in the figure, the original coordination structure of iron isooctanoate was altered. After the addition of Mo metal, the main product still mainly coordinates with Fe and carboxylate, and the concentrations at 1611.28 cm⁻¹ are as follows. -1 and 1565.35cm -1 The coordination peaks of the carboxylate are generated, and the characteristic peaks at these two locations are similar to those at 1406.50 cm⁻¹. -1 The coordination peaks of the carboxylates differ by 204.78 cm⁻¹. -1 and 159.85cm -1 This indicates that both are monodentate coordination mechanisms, but their coordination numbers differ. In the Fe-Zn bimetallic and Fe-Zn-Ni trimetallic catalysts, the monodentate and bidentate coordination structures of Zn and the carboxylate group remain essentially unchanged (characteristic peak positions are 1621.23-1625.46 cm⁻¹, respectively). -1 1548.48-1549.23cm -1 Additionally, Fe exhibits monodentate coordination with carboxylate ions (characteristic peak positions are 1593.76-1601.92 cm⁻¹). -1 No obvious characteristic peaks indicating coordination between Ni and carboxylate groups were observed. (Comparison) Figure 3 and Figure 4 It can be seen that choosing carboxylic acids with different hydrocarbon groups has virtually no effect on the position of the coordination peak.

[0104] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0105] It should be further noted that each of the various technical features described in the above embodiments can be combined with any other technical features in any suitable manner, and the present application shall be deemed to disclose all possible combinations thereof, without causing unnecessary repetition.

[0106] Furthermore, any combination of the various embodiments of the present application can be made, as long as it does not deviate from the spirit of the present application, and it shall be deemed to be disclosed by the present application.

Claims

1. An oil-soluble hydrogenation catalyst, characterized in that, The hydrogenation catalyst comprises a metal central atom or central ion and an organic ligand coordinated to the metal central atom or central ion; the general formula of the hydrogenation catalyst is: MO a [R(COOH b ) x ] c , Where M represents a metal, R(COOH) b ) x The organic ligand represents the organic ligand comprising a carboxyl group and a carboxylic acid group; R represents the hydrocarbon group in the organic ligand; x represents the molar ratio of the total number of the carboxyl group and the carboxylic acid group to the hydrocarbon group R; a represents the molar ratio of the noncoordinate bonded oxygen atom connected to the metal M to the metal M; b represents the molar ratio of the carboxylic acid group to the total number of the carboxyl group and the carboxylic acid group; and c represents the molar ratio of the organic ligand to the metal M, wherein: The metal is one or more of Group B or Group VIII metals with hydrogenation properties; x is 1, 2, or 3; a is a positive number between 1 and 5; b is a positive number between 0.1 and 0.5; c is a positive number between 0.5 and 10.

2. The hydrogenation catalyst according to claim 1, wherein, x is 1 or 2; a is a positive number from 1 to 3; c is a positive number from 1 to 5.

3. The hydrogenation catalyst according to claim 1, wherein, Based on the dry weight of the hydrogenation catalyst, the content of the metal in the hydrogenation catalyst is 2-35%; the metal is one or more selected from Ti, V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn; R is a C3-C19 hydrocarbon group.

4. The hydrogenation catalyst according to claim 3, wherein, Based on the dry weight of the hydrogenation catalyst, the content of the metal in the hydrogenation catalyst is 8-30%; the metal is one or more selected from V, Mo, W, Fe, Co, Ni, Cu and Zn; R is a C5-C11 normal or isomeric alkyl group, a C5-C12 cycloalkyl group, or a C6-C12 aryl group.

5. The hydrogenation catalyst according to claim 4, wherein, Based on the dry weight of the hydrogenation catalyst, the content of the metal in the hydrogenation catalyst is 10-20%; the metal is one or more of Fe, Ni, Mo and Zn.

6. A method for preparing an oil-soluble hydrogenation catalyst, characterized in that, The method includes: S1. A first metal source, an alkaline agent, water, and a first organic ligand compound are mixed to undergo a first coordination reaction to obtain a first mixture; the first organic ligand compound is a carboxylic acid or its anhydride. or, A first metal source, water, and a second organic ligand compound are mixed to carry out a first coordination reaction to obtain a first mixture; the second organic ligand compound is a mixture of a carboxylate and a carboxylic acid or its anhydride; S2. The first mixture is subjected to oil-water separation and liquid separation to obtain a first oil phase liquid product; The first oil phase liquid product is mixed with the second metal source to carry out a second coordination reaction to obtain the second oil phase liquid product; the molar ratio of the first metal source to the second metal source is 1:(0.01-10) based on metal content. The molar ratio of the first organic ligand compound or the second organic ligand compound to the first metal source is 0.5-10; The molar ratio of the first organic ligand compound to the basic agent is 0.01-0.99; In the second organic ligand compound, the molar ratio of the carboxylate to the carboxylic acid or its anhydride is 0.01-0.99; The oil-water separation time is 1-24 hours; The reaction temperature of the first coordination reaction is 50-150℃, and the reaction time is 1-8h; The reaction temperature for the second coordination reaction is 150-450℃, and the reaction time is 1-8h. The metal in the first metal source is one or more of Group B or Group VIII metals with hydrogenation properties, and the first metal source includes one or more of metal oxides, metal hydroxides, metal oxyacids and metal inorganic salts. The alkaline agent includes one or more of the following: oxides of alkali metals or alkaline earth metals, hydroxides, carbonates, bicarbonates, ammonia, ammonia water, and organic amines.

7. The method according to claim 6, wherein, The second metal source is one or more of metal oxides, metal hydroxides, metal oxyacids, and metal inorganic salts. The metal in the second metal source is one or more of Group B or Group VIII metals with hydrogenation properties and is different from the metal in the first metal source.

8. The method according to claim 6 or 7, wherein, The group B or group VIII metal with hydrogenation properties is one or more of Ti, V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn, and the carboxylate and the carboxylic acid or its anhydride have a C3-C19 hydrocarbon group. The carboxylate is a compound formed by the carboxylic acid and the alkaline agent; The carboxylic acid is one or more selected from succinic acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, ethylbutyric acid, oleic acid, petroleum ether, salicylic acid, benzoic acid, and phenylacetic acid, and the carboxylate salt is sodium ethylhexanoate, sodium ethylbutyrate, ammonium ethylhexanoate, or ammonium ethylbutyrate.

9. The method according to claim 8, wherein, The group B or group VIII metal with hydrogenation properties is one or more of V, Mo, W, Fe, Co, Ni, Cu, and Zn; the carboxylate and the carboxylic acid or its anhydride have hydrocarbon groups of C5-C11 normal or isoalkyl, C5-C12 cycloalkyl, and C6-C12 aryl.

10. The method according to claim 9, wherein, The group B or group VIII metal with hydrogenation properties is one or more of Fe, Ni, Mo and Zn.

11. The method according to claim 6, wherein, The molar ratio of the first organic ligand compound or the second organic ligand compound to the first metal source is 1-5; The molar ratio of the first organic ligand compound to the basic agent is 0.5-0.9; In the second organic ligand compound, the molar ratio of the carboxylate to the carboxylic acid or its anhydride is 0.5-0.9; The molar ratio of water to the first organic ligand compound or the second organic ligand compound is 1-20.

12. The method according to claim 11, wherein, The molar ratio of water to the first organic ligand compound or the second organic ligand compound is 5-10.

13. The oil-soluble hydrogenation catalyst prepared by the method according to any one of claims 6-12.

14. A method for hydrogenating oil products, characterized in that, The method includes: Under hydrogenation reaction conditions, the oil feedstock is brought into contact with the hydrogenation catalyst described in any one of claims 1-5 and 13; The oil raw materials are one or more of the following: benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, oil slurry, residual oil, coal tar, and biomass oil.

15. The method according to claim 14, wherein, The conditions for the hydrogenation reaction include: Based on the weight of the oil feedstock, and calculated as metal, the amount of the hydrogenation catalyst is 50-10000 μg / g; the initial hydrogen pressure is 1-20 MPa; the reaction temperature is 200-500℃; and the liquid hourly space velocity is 0.05-5.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-3000.

16. The method according to claim 15, wherein, Based on the weight of the oil feedstock, and calculated as metal, the amount of the hydrogenation catalyst is 50-3000 μg / g; the initial hydrogen pressure is 3-15 MPa; the reaction temperature is 300-450℃; and the liquid hourly space velocity is 0.05-1.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 200-2000.

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