Oil-soluble hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention relates to an oil-soluble hydrogenation catalyst as well as a preparation method and application thereof. The hydrogenation catalyst comprises a metal central atom or a central ion and an organic ligand coordinated with the metal central atom or the central ion, the metal is one or more of B group metal or VIII group metal with hydrogenation performance; the organic ligand comprises a carboxylate radical group and a carboxylic acid group, and forms a coordinate bond with the metal central atom or the central ion through an oxygen atom. When the oil-soluble hydrogenation catalyst is used for hydrogenation of oil products, coordination groups of organic ligands in the oil-soluble hydrogenation catalyst and metal central atoms or central ions form coordination bonds through oxygen atoms, the oil-soluble hydrogenation catalyst can be efficiently dispersed in an oil phase, and the oil-soluble hydrogenation catalyst has high hydrogenation activity in the reaction process; according to the present invention, the high raw material cracking rate and the high heteroatom removal rate can be obtained, the low condensation rate can be maintained, and the light weight and the high quality of the oil product raw material can be ultimately achieved.

Description

Technical Field

[0001] The present invention belongs to the field of petrochemical industry, and in particular, relates to a hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] As the dependence on oil resources increases, the efficient use of oil resources, especially the efficient conversion of low-quality heavy oil with high metal and high asphaltene content into light oil and gas, is an effective way to solve the current energy problem. Hydrofining of petroleum products, including hydrodesulfurization, denitrogenation, and demetallization, has always been an important part of the petrochemical industry. With the increasingly stringent environmental regulations and the rapid economic development, the demand for light oil and gas and chemical raw materials has increased rapidly, and it is becoming increasingly important to develop catalysts that can efficiently process heavy raw materials. Traditional hydrofining catalysts are fixed-bed supported catalysts, which are usually composed of active metals and carriers. The active metals usually have hydrogenation activity, and the carrier is alumina or a mixture of alumina and other oxides (such as ZrO2, MgO, etc.), which can provide the required acidity for cracking reactions. Supported catalysts have become the catalysts with the largest number of industrial applications and the widest range due to their high catalytic activity, strong mechanical strength and mature process technology. However, as the quality of crude oil deteriorates, environmental protection and downstream equipment have stricter requirements on oil raw materials. Supported catalysts are in urgent need of upgrading and replacement due to their low diffusion and mass transfer efficiency and catalysts’ easy coking and deactivation. The oil-soluble catalysts used in the slurry bed residual oil processing technology have the characteristics of high dispersibility, nano-size and high hydrogenation activity. They can overcome steric hindrance, efficiently convert heavy components, and avoid problems such as short operating cycle caused by coking and fouling. Therefore, they are regarded as an effective way to hydrogenate and upgrade raw 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 comprises reacting a solvent, a molybdenum source, an iron source and an oxygen-containing organic acid, mixing the obtained product with a solution containing an alkali source to obtain a mixture, performing solid-liquid separation, contacting the obtained liquid with a C6-C18 oxygen-containing organic acid at 50-150°C for reaction, and then reacting at 160-320°C. The obtained product is separated and purified to obtain the complex containing molybdenum and iron.

[0004] CN116020563A discloses a method for preparing a non-supported multi-metal hydrogenation catalyst, which comprises mixing a first metal source or a dispersion thereof with an organic ligand compound, reacting the mixture at a temperature T1 for a time t1, and then reacting the mixture at a temperature T2 for a time t2; then adding a second metal source or a dispersion thereof, reacting the mixture at a temperature T2 for a time t3, and collecting the resulting liquid product as a non-supported catalyst.

[0005] CN114618584A discloses a method for preparing an oil-soluble iron-based catalyst, comprising mixing an iron salt solution and a fatty acid salt solution, heating the mixture for reaction, standing the mixture for stratification, washing the upper organic phase, and drying the mixture to obtain an oil-soluble iron-based catalyst; the iron salt is preferably ferric chloride hexahydrate, ferric nitrate nonahydrate, or ferric sulfate monohydrate, and the fatty acid salt is preferably stearate or oleate.

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

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

[0008] In order to achieve the above object, the present invention provides an oil-soluble hydrogenation catalyst in a first aspect, which comprises a metal central atom or a central ion and an organic ligand coordinated with the metal central atom or the central ion; the general formula of the hydrogenation catalyst is: MO a [R(COOH b ) x ] c , where M represents metal, R(COOH b ) x represents the organic ligand, the organic ligand includes a carboxylate 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 carboxylate group and the carboxylic acid group to the hydrocarbon group R, a represents the molar ratio of the non-coordinated bonded oxygen atoms 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 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; c is a positive number of 0.5-10, preferably a positive number of 1-5.

[0009] Optionally, based on the dry weight of the hydrogenation catalyst, the content of the metal in the hydrogenation catalyst is 2-35%, preferably 8-30%, and more preferably 10-20%; 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 more 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 group and a C6-C12 aromatic group.

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

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

[0012] Alternatively, a first metal source, water and a second organic ligand compound are mixed to perform a first coordination reaction to obtain a first mixed material; the second organic ligand compound is a mixture of a carboxylate and a carboxylic acid or an anhydride thereof;

[0013] S2, performing oil-water separation and liquid separation on the first mixed material 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 with hydrogenation properties, and the first metal source includes one or more of metal oxides, metal hydroxides, metal oxygen-containing acids and metal inorganic salts; the alkaline agent includes one or more of alkali metal or alkaline earth metal oxides, hydroxides, carbonates, bicarbonates, ammonia, ammonia water and organic amines.

[0015] Optionally, the method also includes: mixing the first oil phase liquid product with a second metal source for 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 oxygen-containing acids and metal inorganic salts, and 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.

[0016] Optionally, the Group B or Group VIII metal with 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, and further preferably one or more of Fe, Ni, Mo and Zn; the hydrocarbon groups in the carboxylate and the carboxylic acid or its anhydride are C3-C19 hydrocarbon groups, preferably C5-C11 normal or isomeric alkyl groups, C5-C12 cycloalkyl groups and C6-C12 aromatic groups; the carboxylate is a compound formed by the carboxylic acid and the alkaline 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, petroleum acid, salicylic acid, benzoic acid and phenylacetic acid, and the carboxylate 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 alkaline agent is 0.01-0.99, preferably 0.5-0.9; in the second organic ligand compound, the molar ratio of carboxylate to carboxylic acid or its anhydride is 0.01-0.99, preferably 0.5-0.9; 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 oil-water separation time is 1-24 hours; the reaction temperature of the first complex reaction is 50-150°C, and the reaction time is 1-8 hours; the reaction temperature of the second complex reaction is 150-450°C, and the reaction time is 1-8 hours.

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

[0020] A third aspect of the present invention provides a method for hydrogenating oil products, the method comprising:

[0021] Under hydrogenation reaction conditions, the oil feedstock is contacted with the hydrogenation catalyst provided by the first and third aspects of the present invention; wherein the oil feedstock is one or more of benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, slurry oil, residual oil, coal tar and biomass oil.

[0022] Optionally, the conditions of the hydrogenation reaction include: based on the weight of the oil product raw material, the amount of the hydrogenation catalyst is 50-10000 μg / g, preferably 50-3000 μg / g in terms 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 0.05-5.0h -1 , preferably 0.05-1.0h -1 ; The volume ratio of hydrogen to oil is 100-3000, preferably 200-2000.

[0023] Through the above technical scheme, the oil-soluble hydrogenation catalyst of the present invention has a high hydrogenation activity. When used for oil hydrogenation, the coordinating group of the organic ligand in the oil-soluble hydrogenation catalyst forms a coordination bond with the metal central atom or central ion through the oxygen atom, and the oil-soluble hydrogenation catalyst can be efficiently dispersed in the oil phase. During the reaction, the oil-soluble hydrogenation catalyst has a high hydrogenation activity; a high raw material cracking rate and a heteroatom removal rate can be obtained, and a low condensation rate can be maintained, and finally the oil raw material can be lightened and improved in quality.

[0024] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

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

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

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

[0031] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

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

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

[0034] Where M represents metal, R(COOH b ) x represents the organic ligand, the organic ligand includes a carboxylate 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 carboxylate group and the carboxylic acid group to the hydrocarbon group R, a represents the molar ratio of the non-coordinated bonded oxygen atoms 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 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 metals of Group B or Group VIII with hydrogenation performance; R is a C3-C19 hydrocarbon group, preferably a C5-C11 normal or isomeric alkyl group, a C5-C12 cycloalkyl group and a C6-C12 aromatic 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; c is a positive number of 0.5-10, preferably a positive number of 1-5.

[0036] There are two forms of coordination complexation in the present invention. One is that the organic carboxylate radical forms a coordination bond with the metal through the oxygen atom, and the lone electron pair of the oxygen atom is combined with the d orbital of the metal atom to form an organic metal complex with a stable structure. The complex can usually exist stably at room temperature. When used for oil hydrogenation, when the reaction temperature rises to a higher temperature (>300°C), it is converted into a metal sulfide active phase in the presence of H2 and S. Because it has a nanometer size and more coordinated unsaturated sites, it has a higher catalytic activity. The other is that the H atom of the hydroxyl group -OH in the organic carboxylic acid interacts with the O atom in the metal oxide due to its obvious electron-deficient characteristics, and the coordination compound is formed by the secondary bond hydrogen bond. Since the hydrogen bond has a lower bond energy, it has an unstable factor, and the coordination structure is easily destroyed, resulting in bonding and agglomeration between metal oxide molecules. Therefore, the metal catalyst formed by this bonding form has a lower activity and is not convenient for long-term storage.

[0037] According to the present invention, optionally, based on the dry weight of the hydrogenation catalyst, the content of the metal in the hydrogenation catalyst is 2-35%, preferably 8-30%, and more preferably 10-20%; 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 more 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 group and a C6-C12 aromatic group.

[0038] According to the present invention, optionally, the infrared spectrum of the hydrogenation catalyst is at least in the range of 1350-1450 cm -1 and 1500-1610cm -1 There is a characteristic peak at the position.

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

[0040] In the present invention, "C5-C11 normal alkyl" refers to a straight-chain alkyl group having 5 to 11 carbon atoms, such as n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-undecyl.

[0041] In the present invention, "C5-C11 isomeric alkyl" refers to a branched alkyl group having 5 to 11 carbon atoms, such as isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, and isoundecyl.

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

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

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

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

[0046] The oil-soluble hydrogenation catalyst of the present invention 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 central atom or central ion through the oxygen atom, and the oil-soluble hydrogenation catalyst can be efficiently dispersed in the oil phase. During the reaction, the oil-soluble hydrogenation catalyst has high hydrogenation activity. A high raw material cracking rate and heteroatom removal rate can be obtained, and a low condensation rate can be maintained, thereby ultimately achieving lightness and high quality of the oil raw material.

[0047] A second aspect of the present invention provides a method for preparing an oil-soluble hydrogenation catalyst, the method comprising:

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

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

[0050] S2, performing oil-water separation and liquid separation on the first mixed material 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 with hydrogenation properties, and the first metal source includes one or more of metal oxides, metal hydroxides, metal oxygen-containing acids and metal inorganic salts; the alkaline agent includes one or more of alkali metal or alkaline earth metal oxides, hydroxides, carbonates, bicarbonates, ammonia, ammonia water and organic amines.

[0052] In the method, by adding an alkaline agent or a carboxylate and adopting the oil-water layer separation and liquid separation operation, the carboxylate radical participates in the formation of the coordination compound and is stably retained in the coordination compound.

[0053] According to the present invention, optionally, the method further includes: mixing the first oil phase liquid product with a second metal source for a second coordination reaction to obtain a second oil phase liquid product; in terms of metal, the molar ratio of the first metal source to the second metal source is 1:(0.01-10); the second metal source is one or more of metal oxides, metal hydroxides, metal oxygen-containing acids 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 properties and is different from the metal in the first metal source.

[0054] According to the present invention, optionally, the Group B and Group VIII metals with 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 groups in the carboxylate and the carboxylic acid or its anhydride are C3-C19 hydrocarbon groups, preferably C5-C11 normal or isomeric alkyl groups, C5-C12 cycloalkyl groups and C6-C12 aromatic groups; the carboxylate is a compound formed by the carboxylic acid and the alkaline agent.

[0055] According to the present invention, 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 alkaline agent is 0.01-0.99, preferably 0.5-0.9; in the second organic ligand compound, the molar ratio of carboxylate to carboxylic acid or its anhydride is 0.01-0.99, preferably 0.5-0.9; 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 invention, optionally, the first organic ligand compound and the second organic ligand compound are each independently a C4-C20 carboxylic acid or anhydride thereof, preferably one or more of a C4-C20 normal or isomeric alkyl carboxylic acid or anhydride thereof, a C6-C20 cycloalkane carboxylic acid containing a saturated carbon ring or anhydride thereof, and a C7-C20 aromatic carboxylic acid containing an aromatic ring or anhydride thereof; further preferably one or more of a C4-C12 normal or isomeric alkyl carboxylic acid or anhydride thereof, a C6-C13 cycloalkane carboxylic acid containing a saturated carbon ring or anhydride thereof, and a C7-C13 aromatic carboxylic acid containing an aromatic ring or anhydride thereof.

[0057] According to the present invention, optionally, C4-C20 carboxylic acid refers to a monocarboxylic acid having 4-20 carbon atoms, and the carboxylic acid may be a saturated or unsaturated straight chain, branched chain or monocarboxylic acid having a carbon ring, including but not limited to C4-C20 normal alkyl carboxylic acids, C4-C20 isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbon rings, and C7-C20 aromatic carboxylic acids containing aromatic rings.

[0058] According to the present invention, 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, petroleum acid, salicylic acid, benzoic acid and phenylacetic acid; the carboxylate is sodium ethylhexanoate, sodium ethylbutyrate, ammonium ethylhexanoate or ammonium ethylbutyrate.

[0059] According to the present invention, optionally, the oil-water separation time is 1-24h; the reaction temperature of the first complex reaction is 50-150°C, and the reaction time is 1-8h; the reaction temperature of the second complex reaction is 150-450°C, and the reaction time is 1-8h.

[0060] According to the present invention, optionally, there are no strict requirements on the reaction pressure and reaction atmosphere when preparing the hydrogenation catalyst. For example, the reaction pressure can be normal pressure, and the reaction atmosphere can be air or an inert gas atmosphere.

[0061] In a specific embodiment of the present invention, a method for preparing an oil-soluble hydrogenation catalyst comprises: adding a metal source, a carboxylic acid, water and an alkaline agent into a reactor and mixing them, reacting them at 50-150°C for 1-8h to obtain a layered reaction product, and separating the liquids to obtain an oil phase liquid product, which is a single metal hydrogenation catalyst; in another embodiment of the present invention, the oil phase liquid product obtained by the previous separation is added with another or several metal sources, and the product obtained by reacting them at 150-450°C for 1-8h is a dual or multi-metal hydrogenation catalyst.

[0062] In the present invention, a metal source is reacted with an alkali solution, and then a neutralization reaction occurs with a carboxylic acid, and finally an organic metal complex is formed, so that the metal is converted into an organic phase, so that it can be highly dispersed in hydrocarbon compounds. Since the reaction temperature is low and the metal conversion rate is high, the generated catalyst can be efficiently dispersed in hydrocarbon oil products, and in situ sulfurized into a catalyst active phase during the heating process. The process of preparing the hydrogenation catalyst of the present invention is simple, the raw material price is low, the required raw materials are small, high-temperature treatment is not required, and the energy consumption is low. In addition, the aqueous phase produced by the reaction can be separated and purified to obtain a large amount of salt by-products, such as ammonium nitrate, sodium sulfate, ammonium chloride, etc., which are all important chemical products.

[0063] A third aspect of the present invention provides a method for hydrogenating oil products, the method comprising:

[0064] Under hydrogenation reaction conditions, the oil feedstock is contacted with the hydrogenation catalyst provided by the first and third aspects of the present invention; wherein the oil feedstock is one or more of benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, slurry oil, residual oil, coal tar and biomass oil.

[0065] According to the present invention, optionally, the conditions of the hydrogenation reaction include: based on the weight of the oil raw material, the amount of the hydrogenation catalyst is 50-10000 μg / g, preferably 50-3000 μg / g in terms 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 0.05-5.0h -1 , preferably 0.05-1.0h -1 ; The volume ratio of hydrogen to oil is 100-3000, preferably 200-2000.

[0066] The present invention is further illustrated by the following examples, but the present invention is not limited thereto.

[0067] Unless otherwise specified, the raw materials used in the examples can be obtained through commercial sources.

[0068] Examples 1-9

[0069] Examples 1-9 prepare hydrogenation catalysts.

[0070] The raw materials, reaction conditions and test results used in Examples 1-3 are shown in Table 1. According to Table 1, the corresponding weights of metal source compounds, water, alkaline agents and carboxylic acids are weighed and added to a three-necked flask, and then reacted under the conditions shown in Table 1, and the gas generated during the reaction was separated. After the reaction, the liquid product in the flask was poured out and placed in a separating funnel for oil-water separation, and allowed to stand for 2 hours. The upper oil phase product obtained by separation is a single metal oil-soluble hydrogenation catalyst. The metal content and infrared spectrum of the obtained product are measured, and the composition of the obtained product is determined based on the measured results.

[0071] The methods used in Examples 4-6 are as described above, except that after obtaining the monometallic oil-soluble hydrogenation catalyst described in Example 2, one or more other 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 generated during the reaction are separated, and after the reaction is completed, the liquid product remaining in the flask is the bi- or multi-metallic oil-soluble hydrogenation catalyst. The metal content and infrared spectrum of the product are measured, and the composition of the obtained product is determined based on the obtained results.

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

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

[0074]

[0075]

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

[0077]

[0078] Table 3 Reaction 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 hydrodesulfurization reaction of dibenzothiophene (DBT), wherein decahydronaphthalene was used as solvent, the mass fraction of dibenzothiophene in 10g of the total reactant (dibenzothiophene + solvent) was 10%, and the reaction was carried out in a 100mL fully back-mixed autoclave, and the experimental conditions included an initial hydrogen pressure of 5MPa, a reaction temperature of 360°C, a reaction time of 60min, and a total addition amount of the hydrogenation catalyst in terms of metal amount was 5% based on the weight of the total reactant. The experimental results are shown in Table 3.

[0083] Comparative Example 1 The experiment was carried out 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] It can be seen from the results in Table 4 that, compared with the pure thermal reaction without adding a catalyst, the oil-soluble hydrogenation catalyst of the present application has a higher DBT conversion rate and desulfurization rate, indicating that the catalyst of the present application has 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 hydrofining reaction of catalytic diesel, wherein the mass fraction of S element in the catalytic diesel was 0.739%, the content of N element was 554 μg / g, the total aromatic content was 88%, of which monocyclic aromatics were 16.9%, dicyclic aromatics were 60.8%, and tricyclic aromatics were 10.3%. The reaction was carried out in a 100 mL fully back-mixed autoclave, 10 g of catalytic diesel was added, and the amount of hydrogenation catalyst added was 2 g in terms of metal amount. The experimental 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 The test was carried out according to the method of Examples 13-15, except that the conventional Ni-W supported catalyst (metal Ni+W content of 28%, carrier Al2O3, SiO2, etc.) was used to replace the product prepared in the example according to the metal amount equal replacement method. The experimental results are shown in Table 5.

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

[0091]

[0092] From the results in Table 5, it can be seen that compared with the supported catalyst, the unsupported single metal hydrogenation catalyst and the bimetallic or multimetallic hydrogenation catalyst of the present application have lower S and N mass fractions, and can effectively reduce the content of polycyclic aromatic hydrocarbons while reducing the heteroatom content, indicating that the hydrogenation catalyst of the present application has higher catalytic hydrogenation activity.

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

[0094] The hydrogenation catalyst prepared in Examples 2 and 4 was applied to the hydrogenation reaction of vacuum residue, wherein the asphaltene content of the vacuum residue was 14%, the residual carbon value was 26.3%, and the heavy metal (Ni+V) content was 175 μg / g. 200 g of vacuum residue was mixed with the hydrogenation catalyst in a 2L intermittent autoclave, and contacted with hydrogen under hydrogenation conditions to carry out a residual oil catalytic hydrogenation thermal conversion test, and the reaction product was analyzed and detected. The hydrogenation reaction conditions and experimental results are shown in Table 6.

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

[0096] Comparative Example 4 was tested according to Example 16 or 17, except that the catalyst used in Comparative Example 4 was the Ni-W supported catalyst used in Comparative Example 2, and 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] By comparing the data of Examples 16 and 17 and Comparative Examples 3 and 4 in Table 6, it can be seen that the oil-soluble hydrogenation catalyst prepared by the present invention not only has a lower catalyst metal cost, but also can obtain a higher residue oil cracking rate, a lower condensation rate and a higher distillate oil yield when applied to oil hydrogenation.

[0100] Embodiment 18

[0101] Method for determining the metal content in the hydrogenation catalysts obtained in Examples 1-9 and the raw metal organic acid complexes used: After the test sample was diluted 100 times with an organic solvent, it was determined using a SPECTRO ARCOS SOP plasma emission spectrometer using inductively coupled plasma optical emission spectrometry (ICP-OES). The measurement conditions were a closed optical chamber filled with argon, vertical observation, and a wavelength range of 130nm-770nm.

[0102] Example 1-6 Infrared spectrum measurement method of the hydrogenation catalyst obtained: The infrared spectrum of the solid catalyst product obtained was measured using a NICOLET IS50 spectrometer from Thermo Fisher, under the conditions of scanning wavelength from 400 to 4000 cm -1 The number of scans is 16. ZnSe crystal and HgCdTe infrared detector are used together to measure the attenuated total reflectance (ATR) of the sample with a resolution of 4cm -1 .

[0103] Figure 1 This is the infrared absorption spectrum of the organic ligand compound ethylhexanoic acid in Example 1. It can be seen from the figure that at 1701.88 cm -1 There is a characteristic peak of CO of carboxylic acid at 1460 cm -1 There is a CH characteristic peak of CH3. Figure 2 The infrared absorption spectrum of the organic acid and Zn complex in Example 1 shows that zinc 2-ethylhexanoate has two main structures, 1629.21 cm -1 and 1548.00cm -1 The coordination peaks of carboxylate are generated. The characteristic peaks of these two locations are at 1427.06 cm -1 The coordination peaks of carboxylates differ by 202.15 cm -1 and 120.94cm -1 , indicating monodentate and bidentate coordination forms respectively, and at 1706.42 cm -1The peak at 400 nm is basically equivalent to the CO characteristic peak of the carboxylic acid of ethylhexanoic acid, indicating that the carboxylic acid is in a free state. Figure 3 This is the infrared absorption spectrum of the organic acid complexed with Fe in Example 2. There is an interaction between the unreacted organic acid and the coordinated Fe metal, which causes the characteristic peak of free carboxylic acid CO to blue-shift to 1691.55 cm -1 The generated 2-isooctanoic acid iron also has two coordination structures, at 1587.31 cm -1 and 1541.18cm -1 The coordination peaks of carboxylate are generated. The characteristic peaks of these two locations are at 1421.90 cm -1 The coordination peaks of carboxylates differ by 165.41 cm -1 and 119.28cm -1 , indicating that they are monodentate and bidentate coordination forms respectively. From the catalysts prepared by using iron isooctanoate and different metal sources in Examples 4-6, it can be seen that (such as Figure 5 The coordination structure of the original ferric isooctanoate was changed. After adding Mo metal, the main product was still mainly composed of Fe and carboxylate, with the coordinates at 1611.28 cm -1 and 1565.35cm -1 The coordination peaks of carboxylate are generated. The characteristic peaks of these two locations are at 1406.50 cm -1 The coordination peaks of carboxylates differ by 204.78 cm -1 and 159.85cm -1 , indicating that they are both monodentate coordination forms, but the coordination numbers are different. In the Fe-Zn bimetallic and Fe-Zn-Ni trimetallic catalysts, the monodentate and bidentate coordination structures of Zn and carboxylate are basically unchanged (the characteristic peak positions are 1621.23-1625.46 cm -1 、1548.48-1549.23cm -1 ), and there is also a monodentate coordination between Fe and carboxylate (characteristic peak position is 1593.76-1601.92cm -1 ), there is no obvious coordination characteristic peak structure between Ni and carboxylate. Figure 3 and Figure 4 It can be seen that choosing carboxylic acids with different hydrocarbon groups has little effect on the coordination peak position.

[0104] The preferred embodiments of the present invention are described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0105] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0106] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. An oil-soluble hydrogenation catalyst, characterized in that The hydrogenation catalyst comprises a metal central atom or a central ion and an organic ligand coordinated with the metal central atom or the central ion; the general formula of the hydrogenation catalyst is: MO a [R(COOH b ) x ] c , Where M represents metal, R(COOH b ) x represents the organic ligand, the organic ligand includes a carboxylate 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 carboxylate group and the carboxylic acid group to the hydrocarbon group R, a represents the molar ratio of the non-coordinated bonded oxygen atoms 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 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 metals of Group B or Group VIII having hydrogenation properties; x is 1, 2 or 3, preferably 1 or 2; a is a positive number between 0 and 5, preferably a positive number between 1 and 3; b is a positive number of 0.01-0.99, preferably a positive number of 0.1-0.5; c is a positive number of 0.5-10, preferably a positive number of 1-5.

2. 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%, preferably 8-30%, and more preferably 10-20%; 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 more 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 group, and a C6-C12 aryl group.

3. A method for preparing an oil-soluble hydrogenation catalyst, characterized in that: The method includes: S1, mixing a first metal source, an alkaline agent, water and a first organic ligand compound to perform a first coordination reaction to obtain a first mixed material; the first organic ligand compound is a carboxylic acid or an anhydride thereof, or, A first metal source, water and a second organic ligand compound are mixed to perform a first coordination reaction to obtain a first mixed material; the second organic ligand compound is a mixture of a carboxylate and a carboxylic acid or an anhydride thereof; S2, performing oil-water separation and liquid separation on the first mixed material to obtain a first oil phase liquid product; 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 oxygen-containing acids and metal inorganic salts; The alkaline agent includes one or more of oxides, hydroxides, carbonates, bicarbonates, ammonia gas, ammonia water and organic amines of alkali metals or alkaline earth metals.

4. The method according to claim 3, wherein: 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 oxygen-containing acids 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.

5. The method according to claim 3 or 4, wherein: The B group or VIII group metal with 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, and more 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 and a C6-C12 aryl group; The carboxylate is a compound formed by the carboxylic acid and the alkaline agent; Preferably, the carboxylic acid is one or more of succinic acid, caproic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, ethylbutyric acid, oleic acid, petroleum acid, salicylic acid, benzoic acid and phenylacetic acid, and the carboxylate is sodium ethylhexanoate, sodium ethylbutyrate, ammonium ethylhexanoate or ammonium ethylbutyrate.

6. The method according to claim 3, wherein: 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 alkaline agent is 0.01-0.99, preferably 0.5-0.9; In the second organic ligand compound, the molar ratio of carboxylate to carboxylic acid or its anhydride is 0.01-0.99, preferably 0.5-0.9; The molar ratio of water to the first organic ligand compound or the second organic ligand compound is 1-20, preferably 5-10.

7. The method according to claim 3 or 4, wherein: The oil-water separation time is 1-24h; The reaction temperature of the first complexing reaction is 50-150°C, and the reaction time is 1-8h; The reaction temperature of the second complexing reaction is 150-450° C., and the reaction time is 1-8 hours.

8. An oil-soluble hydrogenation catalyst prepared by the method described in any one of claims 3 to 7.

9. A method for hydrogenating oil products, characterized in that: The method includes: Under hydrogenation reaction conditions, contacting the oil product raw material with the hydrogenation catalyst according to any one of claims 1 to 2 and 8; The oil raw material is one or more of benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, slurry oil, residual oil, coal tar and biomass oil.

10. The method according to claim 9, wherein: The conditions of the hydrogenation reaction include: Based on the weight of the oil raw material, the amount of the hydrogenation catalyst is 50-10000 μg / g, preferably 50-3000 μg / g, in terms 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 0.05-1.0h -1 ; The volume ratio of hydrogen to oil is 100-3000, preferably 200-2000.

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