Hydrogenation catalyst and preparation method therefor and use thereof, and hydrogenation method

Abstract

Disclosed are a hydrogenation catalyst and a preparation method therefor and the use thereof, and a hydrogenation method. The hydrogenation catalyst comprises a carrier, metallic molybdenum, organic nickel and an organometallic additive, wherein the metallic additive element is a species, the ksp value of a sulfide of which is less than the ksp of α-NiS. The hydrogenation catalyst not only has strong hydrogenation activity in the absence of sulfidation, but also has good stability as compared to conventional noble metals and nickel-based catalysts during the treatment of low-sulfur raw materials.

Description

Hydrogenation catalysts, their preparation methods and applications, and hydrogenation methods

[0001] Cross-references to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202510212596.X, filed on February 25, 2025, and Chinese Patent Application No. 202510212594.0, filed on February 25, 2025, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to hydrogenation catalysts, their preparation methods and applications, and hydrogenation methods, specifically to hydrogenation catalysts that do not require sulfidation, their preparation methods and applications, and hydrogenation methods. Background Technology

[0004] Currently, distillate oil hydrotreating catalysts primarily use sulfide-treated Group VIB and VIII metals as the active phase. Although sulfide-treated active phases possess high hydrotreating capacity, their application has certain limitations: First, to maintain stable catalytic activity, a certain concentration of hydrogen sulfide is required in the feedstock and reaction atmosphere to maintain the structural stability of the active phase. Therefore, when processing increasingly more sulfur-free or low-sulfur feedstocks, sulfide-treated catalysts require the addition or blending of sulfur, thus limiting their application. Second, sulfide-treated catalysts require sulfidation during startup and regeneration after use, which is not only cumbersome and corrodes equipment but also generates large amounts of sulfur-containing waste, requiring significant costs for its disposal. To address these issues, researchers have attempted to prepare sulfur-free active phases for hydrotreating oil products.

[0005] CN201010114256.7 discloses a hydrorefining catalyst, obtained by impregnating a support in an impregnation solution, followed by aging, drying, and activation. The catalyst contains 5-25% molybdenum oxide, 1-6% cobalt oxide, 0-15% tungsten oxide, 0-4% nickel oxide, and 0-4.5% alkali metal oxides, and uses ammonia and a polyamine complexing agent. The catalyst exhibits excellent hydrodesulfurization and deolefinization effects, and superior anti-coking properties. However, the catalyst needs to be sulfided before use, and a certain concentration of hydrogen sulfide needs to be maintained in the reaction atmosphere during use.

[0006] CN202280014020.7 discloses a catalyst for the hydrotreating of heavy petroleum fractions and its application. The catalyst comprises group VIB metal oxides, group VIII metal oxides, and group VA oxides; by weight percentage, the catalyst support includes mesoporous TiO2-Al2O3 and alumina; the catalyst exhibits good hydrodesulfurization and hydronitrogenation activity for heavy petroleum fractions. However, the catalyst requires sulfidation before use, and a high concentration of hydrogen sulfide is required in the reaction atmosphere during use.

[0007] CN201310250257.8 discloses a method for preparing a catalyst support for the hydrotreating of wax oil. The method uses a silica-alumina-phosphorus-alumina composite molecular sieve and supports it with Group VIB and Group VIII metal oxides to prepare the catalyst. During the hydrotreating of wax oil, the catalyst exhibits excellent aromatic ring hydrogenation saturation performance and CS / CN bond cleavage ability, making it suitable for pretreatment of feedstocks in catalytic cracking and hydrocracking. However, the catalyst needs to be sulfided before use, and a high concentration of hydrogen sulfide is required in the reaction atmosphere to maintain the sulfided state of the active phase during stable operation.

[0008] CN201611056149.7 discloses a method for preparing a wax oil hydrogenation catalyst. First, an aqueous solution of ammonium metatungstate, ammonium paramolybdate or ammonium tetramolybdate, nickel nitrate, and orthophosphoric acid is prepared as a co-impregnation solution. A support prepared by the co-impregnation solution is then impregnated in a single step at room temperature. The impregnated support is first dried at room temperature, and then heated and dried under a steam atmosphere to obtain the catalyst. The catalyst exhibits a uniform distribution of active components, a large pore volume and specific surface area, and high desulfurization and denitrification activity. However, the catalyst requires pre-sulfurization treatment before use, and during use, a high concentration of hydrogen sulfide must be maintained in the reaction atmosphere to preserve the catalyst's sulfidated state.

[0009] In existing technologies, the active component of hydrogenation catalysts is generally a metal sulfide, which usually needs to be pre-sulfurized, especially when processing low-sulfur feedstock oil. In order to maintain hydrogenation activity, sulfur replenishment is required. Summary of the Invention

[0010] To address the shortcomings of existing technologies, this invention provides a hydrogenation catalyst, its preparation method, its application, and a hydrogenation method. This hydrogenation catalyst not only exhibits strong hydrogenation activity without the need for sulfidation, but also demonstrates better stability compared to conventional noble metal and nickel-based catalysts when processing low-sulfur feedstocks.

[0011] The first aspect of this invention provides a hydrogenation catalyst, the hydrogenation catalyst comprising a support, metallic molybdenum, organonickel, and an organometallic auxiliary, wherein the auxiliary element is a sulfide k. sp k values ​​less than α-NiS sp (i.e., 3.2 × 10)-19 ) species. In this invention, sulfide k sp The value refers to the concentration product of a metal sulfide in water at 25°C, k. sp =[M n+ ][S 2- ], where [M n+ [S] represents the concentration of metal ions in a saturated solution. 2- ] is S 2- The concentration of ions in a saturated solution.

[0012] According to a preferred embodiment of the present invention, the metal additive element is a sulfide k sp Value in 1×10 -20 Up to 1×10 -40 Among the species, preferably, the metal additive element includes one or more elements selected from zinc, copper, cadmium, lead, and tin.

[0013] In this invention, the selection of the aforementioned metal additive elements is based on the low solubility product characteristics of their sulfides. As an example, the following provides the solubility product constants of some preferred metal elements and their sulfides at 25°C to illustrate the preferred scope of this invention, such as the k-solubility product constant of ZnS. sp =1.6×10 -22 k of CuS sp =6.3×10 -36 CdS's k sp =8.0×10 -27 PbS's k sp =1.0×10 -28 SnS's k sp =1.0×10 -25 .

[0014] In this invention, any catalyst that meets the aforementioned requirements can achieve the purpose of this invention. According to a preferred embodiment of this invention, the mass content of organic groups in the catalyst is 4%-20%, preferably 6%-18%. Using the aforementioned preferred content of organic groups can achieve high complexation and uniform distribution of metal-organic compounds.

[0015] In this invention, the range of organic groups in the catalyst is relatively wide, as illustrated below, but this does not limit the scope of the invention. The organic groups are organic acid radicals and / or organic complexing agents. In this invention, the organic complexing agent may also be referred to as an organic complex, and in previous documents, it was simply called an organic complex.

[0016] In this invention, the range of selectable organic acid radicals is relatively wide, for example, they are dicarboxylic or higher acid radicals. According to a preferred embodiment of this invention, the organic acid radical is one or more of the following: malonate, methylmalonate, dimethylmalonate, diethylene glycol, citrate, oxalate, ethylenediaminetetramethylenephosphonate, salicylate, benzoate, tartrate, glycolate, and gluconate; preferably selected from one or more of the following: malonate, methylmalonate, dimethylmalonate, diethylene glycol, citrate, salicylate, benzoate, and tartrate.

[0017] In this invention, the range of possible organic complexing agents is relatively wide, for example, organic substances with complexing and dissolving effects. According to a preferred embodiment of this invention, the organic complexing agent is one or more of acetylacetone, EDTA, NTA, and ethylenediamine.

[0018] According to a preferred embodiment of the present invention, the organic group is selected from one or more of tartrate, acetylacetone, citrate, glycolate, and gluconate.

[0019] According to a preferred embodiment of the present invention, the catalyst further contains free organic matter, the organic groups of which may be the same as or different from the organic groups of the organonitrile and / or organometallic auxiliaries, preferably the same. For example, it may be an organic acid corresponding to the aforementioned organic acid anion and / or the aforementioned organic complexing agent.

[0020] In this invention, the content of each component can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention.

[0021] According to a preferred embodiment of the present invention, based on the weight of the hydrogenation catalyst, the organonitrile contains 0.1%-4.0% by mass, preferably 0.2%-3.0%, and more preferably 0.5%-2.0% by mass of nickel element.

[0022] According to a preferred embodiment of the present invention, based on the weight of the hydrogenation catalyst, the mass content of the organometallic auxiliary, calculated as metal auxiliary element, is 0.05%-2.5%, preferably 0.1%-2.0%, and more preferably 0.2%-1.5%.

[0023] According to a preferred embodiment of the present invention, based on the weight of the hydrogenation catalyst, the mass content of metallic molybdenum, calculated as molybdenum element, is 3.0%-25%, preferably 4.0%-20%, more preferably 4.0%-18%, further preferably 5.0%-18.0%, and even more preferably 5.0%-15.0%.

[0024] According to a preferred embodiment of the present invention, the carrier mass content is 40%-85%, preferably 45%-80%, and more preferably 50%-75%.

[0025] In the hydrogenation catalyst of this invention, metallic molybdenum can exist in the form of molybdenum salt, molybdenum oxide, or elemental molybdenum.

[0026] This invention provides a hydrogenation catalyst, comprising an active metal oxide and a metal promoter oxide, wherein the active metal oxide comprises molybdenum oxide and nickel oxide, and the metal promoter element is a sulfide (k). sp k values ​​less than α-NiS sp (i.e., 3.2 × 10) -19 The catalyst of the species has the following XPS properties: the peak area of ​​the Ni element 3 / 2p orbitals in the range of 855-less than 860 eV accounts for 25%-85% of the total peak area of ​​the Ni element 3 / 2p orbitals, preferably 30%-80%, more preferably 40%-70%, and even more preferably 45%-70%; and the ratio of the peak area in the range of 855-less than 860 eV to the peak area in the range of 860-865 eV is between 0.4 and 1.7, preferably between 0.7 and 1.7, more preferably between 0.7 and 1.3, and even more preferably between 0.8 and 1.3.

[0027] According to a preferred embodiment of the present invention, the metal additive element is a sulfide k sp Value in 1×10 -20 Up to 1×10 -40 Among the species, preferably, the metal additive element includes one or more elements selected from zinc, copper, cadmium, lead, and tin.

[0028] In this invention, the selection of the aforementioned metal additive elements is based on the low solubility product characteristics of their sulfides. As an example, the following provides the solubility product constants of some preferred metal elements and their sulfides at 25°C to illustrate the preferred scope of this invention, such as the k-solubility product constant of ZnS. sp =1.6×10 -22 k of CuS sp =6.3×10 -36 CdS's k sp =8.0×10 -27 PbS's k sp =1.0×10 -28 SnS's k sp =1.0×10 -25 .

[0029] In this invention, the content of each component can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention.

[0030] According to a preferred embodiment of the present invention, the molybdenum oxide content is 5.0%-35% by weight of the catalyst, more preferably 5.0%-30%, even more preferably 10%-30%, even more preferably 10%-28%, even more preferably 12-28%, and even more preferably 12-26%.

[0031] According to a preferred embodiment of the present invention, the nickel oxide content is 1.0%-7.0% by weight of the catalyst, preferably 1.0%-6.0%, preferably 2.0%-6.0%, preferably 2.0%-5.0%, more preferably 2.5%-5.5%, and even more preferably 2.5%-4.5%.

[0032] According to a preferred embodiment of the present invention, the mass content of the metal auxiliary oxide is 0.2%-4.0%, preferably 0.3%-3.5%, more preferably 0.3%-2.5%, further preferably 0.5%-3.0%, and even more preferably 0.5%-2.0%, based on the weight of the catalyst.

[0033] According to a preferred embodiment of the present invention, the carrier mass content is 40%-90%, preferably 50%-87%, and more preferably 55%-85%, based on the weight of the catalyst.

[0034] In the hydrogenation catalyst of the present invention, the support has no special requirements and can be any commonly used support, such as an inorganic refractory oxide. The inorganic refractory oxide can be one or more of alumina, amorphous silica-alumina, macroporous silica, and titanium-silicon composite materials, preferably γ-alumina.

[0035] In the hydrogenation catalyst of this invention, the support may be doped with a small amount of one or more doping elements selected from heteroatoms such as silicon, phosphorus, boron, magnesium, and fluorine to improve the support performance. The content of the doping element does not exceed 5.0% of the total mass of the support, and is preferably silicon and / or phosphorus. The heteroatoms can be incorporated using existing technologies, either during the preparation of the support or after the support is prepared.

[0036] In the hydrogenation catalyst of this invention, the properties of the support are not particularly required; for example, it can have the following properties: pore volume of 0.6-1.3 cm³. 3 / g, with a preferred pore volume of 0.7-1.2cm³. 3 / g, specific surface area is 180-340m² 2 / g, preferably 210-310m 2 / g.

[0037] According to one embodiment of the present invention, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:

[0038] (1) A molybdenum source is introduced onto the carrier, followed by drying and calcination;

[0039] (2) The product of step (1) is introduced into an organonitrile source and an organometallic additive source, and then dried. The metal additive element is a sulfide K. sp k values ​​less than α-NiS sp (i.e., 3.2 × 10) -19 ) species.

[0040] According to a preferred embodiment of the present invention, the metal additive element is a sulfide k sp Value in 1×10 -20 Up to 1×10 -40 Among the species, preferably, the metal additive element includes one or more elements selected from zinc, copper, cadmium, lead, and tin.

[0041] In this invention, the selection of the aforementioned metal additive elements is based on the low solubility product characteristics of their sulfides. As an example, the following provides the solubility product constants of some preferred metal elements and their sulfides at 25°C to illustrate the preferred scope of this invention, such as the k-solubility product constant of ZnS. sp =1.6×10 -22 k of CuS sp =6.3×10 -36 CdS's k sp =8.0×10 -27 PbS's k sp =1.0×10 -28 SnS's k sp =1.0×10 -25 .

[0042] In this invention, the amount of each component can be selected within a wide range. According to a preferred embodiment of this invention, the amount of organonitrile source and organometallic auxiliary source is such that the mass content of organic groups in the catalyst is 4%-20%, preferably 6%-18%.

[0043] In this invention, the amount of each component can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention.

[0044] According to a preferred embodiment of the present invention, the amount of each raw material is such that, based on the weight of the hydrogenation catalyst, the mass content of organonickel, calculated as nickel element, is 0.1%-4.0%, preferably 0.2%-3.0%, and more preferably 0.5%-2.0%.

[0045] According to a preferred embodiment of the present invention, the amount of each raw material is such that, based on the weight of the hydrogenation catalyst, the mass content of the organometallic auxiliary agent, calculated as a metal auxiliary element, is 0.05%-2.5%, preferably 0.1%-2.0%, and more preferably 0.2%-1.5%.

[0046] According to a preferred embodiment of the present invention, the amount of each raw material is such that, based on the weight of the hydrogenation catalyst, the mass content of metallic molybdenum, calculated as molybdenum element, is 3.0%-25%, preferably 3.0%-20%, more preferably 4.0%-20%, more preferably 4.0%-18%, further preferably 5.0%-18.0%, and even more preferably 5.0%-15.0%.

[0047] According to a preferred embodiment of the present invention, the amount of each raw material is such that, based on the weight of the hydrogenation catalyst, the carrier mass content is 40%-85%, preferably 45%-80%, and more preferably 50%-75%.

[0048] In this invention, there are no special requirements for the way the molybdenum source is introduced in step (1). For example, impregnation loading, co-precipitation loading, etc. can be used. Impregnation loading is used as an example in this invention. There are no special requirements for the solvent used in the impregnation process. According to a preferred embodiment of this invention, the solvent used for impregnation is one or more of ammonia, tartaric acid, citric acid, water, ethanol, acetone, and toluene.

[0049] In this invention, there are no special requirements for the drying and calcination conditions in step (1). The following is an illustrative description, but it does not limit the scope of this invention.

[0050] For example, drying conditions include: a temperature of 100-180℃, preferably 120-160℃; and a time of 2-20 hours, preferably 4-16 hours.

[0051] For example, roasting conditions include: a temperature of 380-600℃, preferably 400-550℃; and a time of 2-12 hours, preferably 3-10 hours.

[0052] According to the present invention, the organonitrile source and organometallic auxiliary source introduced in step (2) can be introduced separately or simultaneously, preferably simultaneously; more preferably, when introduced simultaneously, the organic groups, such as organic acid radicals or organic complexing agents, corresponding to the organonitrile source and organometallic auxiliary source are the same.

[0053] According to the present invention, the introduction of the organonitrile source and organometallic auxiliary source in step (2) can be achieved by impregnation, such as stepwise impregnation or co-impregnation, with co-impregnation being preferred. A wide range of solvents can be selected for impregnation, such as one or more of tartaric acid, citric acid, water, ethanol, acetone, and toluene.

[0054] According to a preferred embodiment of the present invention, during the co-impregnation process, the molar concentration of the organonitrile source, calculated as nickel element, is 0.1-2.0 mol / L, preferably 0.2-1.5 mol / L, and the molar concentration of the organometallic auxiliary source, calculated as metal auxiliary element, is 0.05-1.0 mol / L, preferably 0.1-0.5 mol / L. The impregnation can be performed multiple times as needed.

[0055] In this invention, the organic groups corresponding to the organonitrile source and the organometallic auxiliary source can be the same or different, but preferably the same.

[0056] In this invention, the range of organic groups corresponding to the organonitrile source and the organometallic auxiliary source is relatively wide, such as organic acid radicals and / or organic complexing agents.

[0057] In this invention, the range of organic acid radicals is relatively wide, for example, they are dibasic or higher acid radicals, preferably one or more of the following: malonate, methylmalonate, dimethylmalonate, diethylene glycol, citrate, oxalate, ethylenediaminetetramethylenephosphonate, salicylate, benzoate, tartrate, glycolate, and gluconate; more preferably, they are selected from one or more of the following: malonate, citrate, methylmalonate, dimethylmalonate, diethylene glycol, salicylate, benzoate, and tartrate.

[0058] In this invention, the organic complexing agent can be selected from a wide range, for example, organic compounds with complexing and dissolving effects, preferably one or more of acetylacetone, EDTA, NTA, and ethylenediamine. The organic acid anion or organic complexing agent corresponding to the organonitrile and organometallic auxiliaries can be the same or different, but it is preferred to use the same organic acid anion or organic complexing agent.

[0059] According to a preferred embodiment of the present invention, preferably, the organic groups of the organonitrile source and the organometallic auxiliary source are each selected from one or more of tartrate, acetylacetone, citrate, glycolate, and gluconate.

[0060] In this invention, the drying conditions in step (2) can be selected from a wide range, as illustrated below, but this does not limit the scope of the invention.

[0061] For example, in step (2), the drying conditions include: a temperature of 80-180℃, preferably 100-160℃, and a time determined according to the temperature, for example, a general time of 1-10 hours, preferably 2-8 hours.

[0062] This invention also provides a method for preparing a hydrogenation catalyst, the method comprising:

[0063] The product prepared according to the aforementioned method is used as a precursor, which is then calcined.

[0064] The range of optional roasting conditions is quite wide, as illustrated below, but this does not limit the scope of the invention.

[0065] According to a preferred embodiment of the present invention, the roasting conditions preferably include: a temperature of 380-600℃, preferably 400-550℃; and a time of 2-12 hours, preferably 3-10 hours.

[0066] Specifically, the present invention also provides a method for preparing a hydrogenation catalyst, the method comprising:

[0067] (1) A molybdenum source is introduced onto the carrier, followed by drying and calcination;

[0068] (2) The product of step (1) is introduced into an organonitrile source and an organometallic additive source, and then dried and calcined. The metal additive element is a sulfide with a K content of 100%. sp k values ​​less than α-NiS sp (i.e., 3.2 × 10) -19 ) species.

[0069] According to a preferred embodiment of the present invention, the metal additive element is a sulfide k sp Value in 1×10 -20 Up to 1×10 -40 Among the species, preferably, the metal additive element includes one or more elements selected from zinc, copper, cadmium, lead, and tin.

[0070] In this invention, the selection of the aforementioned metal additive elements is based on the low solubility product characteristics of their sulfides. As an example, the following provides the solubility product constants of some preferred metal elements and their sulfides at 25°C to illustrate the preferred scope of this invention, such as the k-solubility product constant of ZnS. sp =1.6×10 -22 k of CuS sp =6.3×10 -36 CdS's k sp =8.0×10 -27 PbS's k sp =1.0×10 -28 SnS's k sp =1.0×10 -25 .

[0071] The hydrogenation method involves performing steps (1) and (2) according to the aforementioned method of the present invention, and calcining the product of step (2) as a precursor to obtain a calcined catalyst. Specifically, the product prepared according to the aforementioned method of the present invention is used as a precursor, and then the precursor is calcined.

[0072] In this invention, the range of optional calcination conditions in step (2) is relatively wide. The following is an illustrative description, but it does not limit the scope of this invention.

[0073] For example, in step (2), the roasting conditions include: a temperature of 380-600℃, preferably 400-550℃; and a roasting time determined according to the temperature, for example, 2-12 hours, preferably 3-10 hours.

[0074] The fifth aspect of the present invention provides a catalyst prepared by the method of the present invention.

[0075] The sixth aspect of the present invention provides the application of the hydrogenation catalyst described herein as a catalyst for hydrogenation under sulfur-free conditions.

[0076] The seventh aspect of the present invention provides a method for hydrogenating low-sulfur feedstock, the method comprising: introducing low-sulfur feedstock into a reduced hydrogenation catalyst to carry out a hydrogenation reaction, wherein the hydrogenation catalyst includes the hydrogenation catalyst described in the present invention.

[0077] The present invention does not have specific requirements for the sulfur content of the low-sulfur feedstock oil. For example, the low-sulfur feedstock oil is a feedstock with a sulfur content of 0-50000ppm, preferably 500-20000ppm, and the nitrogen content of the low-sulfur feedstock oil is 0-4000ppm, preferably 20-1000ppm.

[0078] The present invention does not have special requirements on the source of the low-sulfur feedstock oil, such as one or more of the following: low-sulfur wax oil, coal-based liquefied oil, biomass feedstock, and coal chemical synthesis feedstock.

[0079] In this invention, the hydrogenation reaction conditions can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention.

[0080] For example, hydrogenation reaction conditions may include: a reaction temperature of 200-400℃, preferably 220-380℃, a hydrogen pressure of 2.0-18.0 MPa, preferably 4.0-16.0 MPa, and a liquid hourly space velocity of 0.2-3.0 h⁻¹. -1 Preferably 0.3-2.0h -1 The hydrogen-to-oil ratio is 200:1-1500:1, preferably 400:1-1200:1.

[0081] In this invention, there are no special requirements for reduction, and conventional reduction techniques can be used as a reference. The following is an illustrative description, but it does not limit the scope of this invention. For example, the reduction adopts hydrogen activation treatment. The specific method is as follows: the treatment temperature is 120-320℃, preferably 160-280℃, the hydrogen pressure is 1.0-20.0MPa, preferably 2.0-15.0MPa, and the treatment time is 2.0-20.0 hours, preferably 4.0-16.0 hours.

[0082] Compared with the prior art, the present invention has the following advantages:

[0083] 1. The hydrogenation catalyst has good activity and stability, and in particular, it can be used without sulfidation treatment.

[0084] 2. The hydrogenation catalyst is highly adaptable to the sulfur content of the feedstock, and can process both conventional sulfur-containing feedstocks and low-sulfur feedstocks. Moreover, the catalyst has strong long-term stability.

[0085] 3. In the hydrogenation process of low-sulfur feedstock, no sulfidation treatment is required before use. The reactants can be directly introduced to carry out the reaction, which greatly simplifies the start-up process. Detailed Implementation

[0086] The present invention will be further described below with reference to the embodiments, but the following embodiments do not constitute a limitation of the present invention. Unless otherwise specified, the percentage content of the materials mentioned herein is a mass percentage content.

[0087] The alumina in the embodiments and comparative examples of this invention was prepared by the following method:

[0088] 6000.0 g of alumina dry adhesive powder was weighed, and 200.0 g of acetic acid, 200.0 g of citric acid, 300.0 g of polyethylene glycol, 100.0 g of ammonium bicarbonate, 100.0 g of urea, 120.0 g of cyanine powder, and 500.0 g of cellulose were added and mixed evenly. Then, 4000.0 g of an aqueous solution containing 1.0% nitric acid was added, and the mixture was compacted for 15.0 min. The mixture was then extruded into strips using a 2.0 mm diameter four-leaf clover-shaped perforated plate. After drying at 140℃ for 4.0 h and calcining at 600℃ for 4.0 h, the resulting carrier was designated S-0-1. The pore properties of the S-0-1 carrier were determined as follows: specific surface area of ​​281 m². 2 / g, pore volume 1.08cm 3 / g.

[0089] 6000.0 g of alumina dry adhesive powder was weighed, and 200.0 g of acetic acid, 300.0 g of citric acid, 200.0 g of polyethylene glycol, 200.0 g of urea, 200.0 g of guar gum powder, and 200.0 g of cellulose were added and mixed evenly. Then, 4000.0 g of an aqueous solution containing 2.0% nitric acid was added, and the mixture was kneaded for 20.0 min. The mixture was then extruded into strips using a 2.0 mm diameter four-leaf clover-shaped perforated plate. After drying at 180℃ for 3.0 h and calcining at 600℃ for 5.0 h, the resulting carrier was designated S-0-2. The pore properties of the S-0-2 carrier were determined as follows: specific surface area of ​​276 m². 2 / g, pore volume 1.15cm 3 / g.

[0090] In this invention, the XPS device used is the ESCALAB-Xi X-ray photoelectron spectrometer manufactured by Thermo Fisher Scientific, and its characterization parameters are shown in the table.

[0091] In this invention, sulfide k sp The value refers to the concentration product of metal sulfides in water at 25°C, k. sp =[M n+ ][S 2- ], where [M n+ [S] represents the concentration of metal ions in a saturated solution. 2- ] is S 2- The concentration of ions in a saturated solution.

[0092] In this invention, the composition of each component of the catalyst is obtained by ICP (metal) and TG-GC (organic compounds).

[0093] XPS analysis and characterization methods

[0094] Example 1

[0095] (1) Weigh 18.0g of ammonium heptamolybdate tetrahydrate, dissolve it in 130ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-1 and impregnate it in the molybdenum solution. After impregnation, dry the solid at 120°C for 6.0 hours and calcine it at 450°C for 4.0 hours to obtain the intermediate.

[0096] (2) Weigh 8.0g nickel tartrate, 3.0g copper tartrate, and 6.0g tartaric acid, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours. The resulting catalyst is called Cat-1.

[0097] Example 2

[0098] (1) Weigh 24.0g of ammonium heptamolybdate tetrahydrate, dissolve it in 130ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-1 and impregnate it in the molybdenum solution. After impregnation, dry the solid at 120°C for 6.0 hours and calcine it at 450°C for 4.0 hours to obtain the intermediate.

[0099] (2) Weigh 14.0g nickel acetylacetone, 4.0g copper acetylacetone and 12.0g acetylacetone, dissolve them in a 1:1 mixture of deionized water and ethanol, and bring the volume to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours. The resulting catalyst is called Cat-2.

[0100] Example 3

[0101] (1) Weigh 27.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-1, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0102] (2) Weigh 14.0g nickel citrate, 6.0g zinc citrate, and 12.0g citric acid, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours. The resulting catalyst is called Cat-3.

[0103] Example 4

[0104] (1) Weigh 35.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-1 and immerse it in the molybdenum solution, dry it at 120℃ for 6.0 hours, and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0105] (2) Weigh 20.0g nickel gluconate, 10.0g zinc gluconate and 4.0g gluconic acid, dissolve them in deionized water and make up to 110ml to obtain an organic source solution;

[0106] The intermediate was impregnated with an organic source solution, and after impregnation, the solid was dried at 120°C for 6.0 hours. The resulting catalyst was designated Cat-4.

[0107] Example 5

[0108] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-1, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0109] (2) Weigh 12.0g nickel citrate, 3.0g cadmium citrate, and 12.0g citric acid, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours. The resulting catalyst is called Cat-5.

[0110] Example 6

[0111] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-1, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0112] (2) Weigh 8.0g nickel citrate, 2.0g zinc citrate, and 1.0g citric acid, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours. The resulting catalyst is named Cat-6.

[0113] Example 7

[0114] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-1, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0115] (2) Weigh 12.0g nickel oxalate, 4.0g zinc oxalate, 8.0g oxalic acid, and 20.0g ammonia water with a mass fraction of 20%, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours. The resulting catalyst is called Cat-7.

[0116] Example 8

[0117] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-1, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0118] (2) Weigh 12.0g nickel acetylacetonate, 4.0g copper tartrate, and 8.0g methylmalonic acid, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours. The resulting catalyst is called Cat-8.

[0119] Comparative Example 1

[0120] The preparation of the intermediate is the same as in Example 3.

[0121] Weigh 15.0g of nickel nitrate hexahydrate and 10.0g of citric acid, dissolve them in deionized water, and make up to 110ml to obtain an impregnation solution; impregnate the intermediate with the impregnation solution, and after impregnation, dry the solid at 120℃ for 6.0 hours. The resulting catalyst is denoted as DCT-1.

[0122] Comparative Example 2

[0123] The preparation of the intermediate is the same as in Example 3.

[0124] Weigh 10.0g nickel citrate and 10.0g citric acid, dissolve them in deionized water, and bring the volume to 110ml to obtain the impregnation solution.

[0125] The intermediate was impregnated with an impregnation solution. After impregnation, the solid was dried at 120°C for 6.0 hours. The resulting catalyst was designated as DCT-1.

[0126] Comparative Example 3

[0127] The preparation of the intermediate is the same as in Example 3.

[0128] Weigh 10.0g nickel citrate, 5.0g zinc nitrate hexahydrate, and 10.0g citric acid, dissolve them in deionized water, and bring the volume to 110ml to obtain the impregnation solution.

[0129] The intermediate was impregnated with an impregnation solution. After impregnation, the solid was dried at 120°C for 6.0 hours. The resulting catalyst was designated as DCT-3.

[0130] Comparative Example 4

[0131] The preparation of the intermediate is the same as in Example 3.

[0132] Weigh 15.0g of nickel nitrate hexahydrate, 4.0g of zinc citrate, and 10.0g of citric acid, dissolve them in deionized water, and bring the volume to 110ml to obtain the impregnation solution.

[0133] The intermediate was impregnated with an impregnation solution. After impregnation, the solid was dried at 120°C for 6.0 hours. The resulting catalyst was designated as DCT-4.

[0134] The composition of the catalyst is shown in Table 1:

[0135] Table 1

[0136] Test Example 1

[0137] The catalysts prepared in Examples 1-8 and Comparative Examples 1-4 were placed in reaction tubes, and the reaction tubes were sealed at 200°C and 16.0 MPa hydrogen pressure for 10.0 hours. VGO feedstock (properties shown in Table 2) was then introduced into the reaction tubes, maintaining the reaction pressure at 16.0 MPa, controlling the reaction temperature at 375°C, and the liquid hourly space velocity at 1.0 h⁻¹. -1 The hydrogen-to-oil ratio was 1200:1. After 1000 hours of reaction, the composition and properties of the sample were analyzed, and the results are shown in Table 3.

[0138] Table 2 Evaluation of the properties of conventional oils

[0139] Table 3 Catalyst Evaluation Results

[0140] Test Example 2

[0141] The catalysts from Examples 1-8 and Comparative Examples 1-4 were placed in reaction tubes, and the reaction tubes were sealed at 200°C and 16.0 MPa hydrogen pressure for 10.0 hours. Then, low-sulfur wax oil (properties of the feedstock are shown in Table 4) was introduced into the reaction tubes, maintaining the reaction pressure at 16.0 MPa, controlling the reaction temperature at 375°C, and the liquid hourly space velocity at 1.0 h⁻¹. -1 The hydrogen-to-oil ratio was 1200:1. After 1000 hours of reaction, the composition and properties of the sample were analyzed, and the results are shown in Table 5.

[0142] Table 4. Evaluation of the properties of low-sulfur wax oils

[0143] Table 5 Catalyst Evaluation Results

[0144] The evaluation results show that the catalyst provided by this invention exhibits good hydrodenitrification and hydrodesulfurization performance when treating conventional wax oil and low-sulfur wax oil without the need for sulfidation, and the catalyst stability can reach more than 1000 hours.

[0145] Example 1'

[0146] (1) Weigh 20.0g of ammonium heptamolybdate tetrahydrate, dissolve it in 140ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-2 and impregnate it in the molybdenum solution. After impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0147] (2) Weigh 10.0g nickel tartrate, 3.0g copper tartrate, and 6.0g tartaric acid, dissolve them in deionized water, and make up to 120ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours to obtain the catalyst intermediate.

[0148] (3) The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was denoted as Cat-1'.

[0149] Example 2'

[0150] (1) Weigh 25.0g of ammonium heptamolybdate tetrahydrate, dissolve it in 140ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-2 and impregnate it in the molybdenum solution. After impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0151] (2) Weigh 15.0g nickel acetylacetone and 5.0g copper acetylacetone, dissolve them in a 1:1 mixture of deionized water and ethanol, and bring the volume up to 120ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours to obtain the catalyst intermediate.

[0152] (3) The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was denoted as Cat-2'.

[0153] Example 3'

[0154] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-2, impregnate S-0-2 with the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine at 450℃ for 4.0 hours to obtain the intermediate.

[0155] (2) Weigh 15.0g nickel citrate, 5.0g zinc citrate, and 12.0g citric acid, dissolve them in deionized water, and make up to 120ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours to obtain the catalyst intermediate.

[0156] (3) The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was denoted as Cat-3'.

[0157] Example 4'

[0158] (1) Weigh 35.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-2 and impregnate it in the molybdenum solution. After impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0159] (2) Weigh 18.0g of nickel glycolate and 13.0g of zinc gluconate, dissolve them in deionized water, and make up to 120ml to obtain an organic source solution;

[0160] The intermediate was impregnated with an organic source solution, and after impregnation, the solid was dried at 120°C for 6.0 hours to obtain the catalyst intermediate.

[0161] (3) The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was denoted as Cat-4'.

[0162] Example 5'

[0163] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-2, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0164] (2) Weigh 12.0g nickel citrate, 3.0g cadmium citrate, and 12.0g citric acid, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours to obtain the catalyst intermediate.

[0165] (3) The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was denoted as Cat-5'.

[0166] Example 6'

[0167] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-2, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0168] (2) Weigh 8.0g nickel citrate, 2.0g zinc citrate, and 1.0g citric acid, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours to obtain the catalyst intermediate.

[0169] (3) The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was denoted as Cat-6'.

[0170] Example 7'

[0171] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-2, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0172] (2) Weigh 12.0g nickel oxalate, 4.0g zinc oxalate, 8.0g oxalic acid, and 20.0g ammonia water with a mass fraction of 20%, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours to obtain the catalyst intermediate.

[0173] (3) The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was denoted as Cat-7'.

[0174] Example 8'

[0175] (1) Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia water with a mass fraction of 20%, dissolve them in 120ml of deionized water to prepare a molybdenum solution; weigh 100.0g of carrier S-0-2, impregnate it in the molybdenum solution, and after impregnation, dry the solid at 120℃ for 6.0 hours and calcine it at 450℃ for 4.0 hours to obtain the intermediate.

[0176] (2) Weigh 12.0g nickel acetylacetonate, 4.0g copper tartrate, and 8.0g methylmalonic acid, dissolve them in deionized water, and make up to 110ml to obtain an organic source solution; impregnate the intermediate with the organic source solution, and after impregnation, dry the solid at 120℃ for 6.0 hours to obtain the catalyst intermediate.

[0177] (3) The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was denoted as Cat-8'.

[0178] Comparative Example 1'

[0179] The preparation of the intermediate is the same as in Example 3'.

[0180] Weigh 23.0g of nickel nitrate hexahydrate and 12.0g of citric acid, dissolve them in deionized water, and make up to 110ml to obtain an impregnation solution; impregnate the intermediate with the impregnation solution, and after impregnation, dry the solid at 120℃ for 6.0 hours to obtain the catalyst intermediate.

[0181] The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was designated as DCT-1'.

[0182] Comparative Example 2'

[0183] The preparation of the intermediate is the same as in Example 3'.

[0184] Weigh 15.0g of nickel citrate and 12.0g of citric acid, dissolve them in deionized water, and make up to 110ml to obtain the impregnation solution.

[0185] The intermediate was impregnated with an impregnation solution, and after impregnation, the solid was dried at 120°C for 6.0 hours to obtain the catalyst intermediate.

[0186] The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was designated as DCT-2'.

[0187] Comparative Example 3'

[0188] The preparation of the intermediate is the same as in Example 3'.

[0189] Weigh 15.0g nickel citrate, 8.0g zinc nitrate hexahydrate, and 12.0g citric acid, dissolve them in deionized water, and dilute to 110ml to obtain a molybdenum solution.

[0190] The intermediate was impregnated with a molybdenum solution, and after impregnation, the solid was dried at 120°C for 6.0 hours to obtain the catalyst intermediate.

[0191] The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was designated as DCT-3'.

[0192] Comparative Example 4'

[0193] The preparation of the intermediate is the same as in Example 3'.

[0194] Weigh 23.0g of nickel nitrate hexahydrate, 5.0g of zinc citrate, and 12.0g of citric acid, dissolve them in deionized water, and bring the volume to 110ml to obtain the impregnation solution.

[0195] The intermediate was impregnated with an impregnation solution and dried at 120°C for 6.0 hours to obtain the catalyst intermediate.

[0196] The catalyst intermediate was calcined at 450°C for 6.0 hours, and the resulting catalyst was designated as DCT-4'.

[0197] Table 6 Catalyst Composition

[0198] XPS analysis was performed on catalysts Cat-1', Cat-2', Cat-3', Cat-4', Cat-5', Cat-6', Cat-7', Cat-8', DCT-1', DCT-2', DCT-3', and DCT-4'. The ratio of the characteristic peaks of the 3 / 2p orbitals of Ni in the 855-857 eV and 858-860 eV ranges is shown in Table 7.

[0199] Table 7. Ni peaks and proportions in XPS catalyst

[0200] Test Example 3

[0201] Cat-1', Cat-2', Cat-3', Cat-4', Cat-5', Cat-6', Cat-7', Cat-8', DCT-1', DCT-2', DCT-3', and DCT-4' were placed in a reaction tube and subjected to a reaction at 340°C, 6.0 MPa, and a hydrogen flow rate of 5.0 ml / min·g. 催化剂 The catalyst was activated under the following conditions. Then, coal liquefaction oil (raw material properties are shown in Table 8) was introduced into the reaction tube. The reaction pressure was set to 17.0 MPa, the reaction temperature was controlled at 375℃, and the liquid hourly space velocity was 0.8 h⁻¹. -1 The hydrogen-to-oil ratio was 1200:1. After 1000 hours of reaction, the composition and properties of the sample were analyzed, and the results are shown in Table 9.

[0202] Table 8 Evaluation of Raw Material Properties

[0203] Table 9 Properties of the generated oil samples

[0204] The evaluation results show that the calcined catalyst provided by this invention has higher and more stable performance in hydrogenating saturated aromatics and hydrogenating nitrogen removal when processing low-sulfur coal liquefaction oil.

Claims

1. A hydrogenation catalyst, said hydrogenation catalyst comprising a support, metallic molybdenum, organonickel, and an organometallic promoter, wherein, The metal additive element is a sulfide, k. sp k values ​​less than α-NiS sp Species.

2. The catalyst according to claim 1, wherein, In the catalyst, The organic group content is 4%-20% by mass, preferably 6%-18%; and / or The metal additive element is sulfide K. sp Value in 1×10 -20 -1×10 -40 Among the species, preferably, the metal additive element includes one or more elements selected from zinc, copper, cadmium, lead, and tin.

3. The catalyst according to claim 1 or 2, wherein, The organic groups are organic acid radicals and / or organic complexing agents; Preferably, The organic acid anion is a dicarboxylic acid anion or an acid anion with two or more components, preferably one or more of the following: malonate, methylmalonate, dimethylmalonate, diethylene glycol, citrate, oxalate, ethylenediaminetetramethylenephosphonate, salicylate, benzoate, tartrate, glycolate, and gluconate; and / or The organic complexing agent is one or more of acetylacetone, EDTA, NTA, and ethylenediamine. More preferably, the organic group is selected from one or more of tartrate, acetylacetone, citrate, glycolate, and gluconate; and / or The catalyst also contains free organic matter, the organic groups of which may be the same as or different from the organic groups of the organonitrile and / or organometallic auxiliaries, preferably the same.

4. The catalyst according to any one of claims 1-3, wherein, Based on the weight of the hydrogenation catalyst, The organonitrile contains 0.1%-4.0% by mass of nickel, preferably 0.2%-3.0%, more preferably 0.5%-2.0%; and / or The organometallic additive, based on the mass content of the metal additive element, is 0.05%-2.5%, preferably 0.1%-2.0%, more preferably 0.2%-1.5%; and / or The molybdenum metal, based on elemental molybdenum, contains 3.0%-25% by mass, preferably 4.0%-20%, more preferably 5.0%-18.0%; and / or The carrier mass content is 40%-85%, preferably 45%-80%, and more preferably 50%-75%; and / or Molybdenum exists as molybdenum salts, molybdenum oxide, or elemental molybdenum.

5. A hydrogenation catalyst, characterized in that: The catalyst comprises an active metal oxide and a metal auxiliary oxide, wherein the active metal oxide comprises molybdenum oxide and nickel oxide, and the metal auxiliary element is a sulfide. sp k values ​​less than α-NiS sp The catalyst of the species has the following XPS properties: the peak area of ​​the Ni element 3 / 2p orbitals in the range of 855-less than 860 eV accounts for 25%-85% of the total peak area of ​​the Ni element 3 / 2p orbitals, preferably 30%-80%, more preferably 40%-70%, and even more preferably 45%-70%; and the ratio of the peak area in the range of 855-less than 860 eV to the peak area in the range of 860-865 eV is between 0.4 and 1.7, preferably between 0.7 and 1.7, and even more preferably between 0.8 and 1.

3.

6. The catalyst according to claim 5, wherein, The metal additive element is a sulfide, k. sp Value in 1×10 -20 -1×10 -40 Among the species, preferably, the metal additive element includes one or more elements selected from zinc, copper, cadmium, lead, and tin; and / or Based on the weight of the catalyst, The molybdenum oxide content is 5.0%-35% by mass, preferably 10%-30%, more preferably 12-28%; and / or The nickel oxide content is 1.0%-7.0% by mass, preferably 2.0%-6.0%, more preferably 2.5%-5.5%; and / or The mass content of the metal auxiliary oxide is 0.2%-4.0%, preferably 0.3%-3.5%, more preferably 0.5%-3.0%; and / or The carrier content is 40%-90%, preferably 50%-87%, and more preferably 55%-85%.

7. The catalyst according to any one of claims 1-6, wherein, The carrier is an inorganic refractory oxide, preferably... The inorganic refractory oxide is one or more of alumina, amorphous aluminum silica, macroporous silica, and titanium-silicon composite materials, preferably γ-alumina; and / or The carrier contains one or more doping elements selected from silicon, phosphorus, boron, magnesium, and fluorine; preferably, the content of the doping element does not exceed 5.0% of the total mass of the carrier; and / or The carrier has the following properties: pore volume of 0.6-1.3 cm³. 3 / g, with a preferred pore volume of 0.7-1.2cm³. 3 / g; specific surface area is 180-340m² 2 / g, preferably 210-310m 2 / g.

8. A method for preparing a hydrogenation catalyst, characterized in that, The method includes: (1) A molybdenum source is introduced onto the carrier, followed by drying and calcination; (2) The product of step (1) is introduced into an organonitrile source and an organometallic additive source, and then dried. The metal additive element is a sulfide K. sp k values ​​less than α-NiS sp Species.

9. The method according to claim 8, wherein, The amount of organonitrile source and organometallic auxiliary source used is such that the mass content of organic groups in the catalyst is 4%-20%, preferably 6%-18%. The metal additive element is a sulfide, k. sp Value in 1×10 -20 -1×10 -40 Among the species, preferably, the metal additive element includes one or more elements selected from zinc, copper, cadmium, lead, and tin.

10. The method according to claim 8 or 9, wherein, The amounts of each raw material used are such that, based on the weight of the hydrogenation catalyst, The organonitrile contains 0.1%-4.0% by mass of nickel, preferably 0.2%-3.0%, more preferably 0.5%-2.0%; and / or The organometallic additive, based on the mass content of the metal additive element, is 0.05%-2.5%, preferably 0.1%-2.0%, more preferably 0.2%-1.5%; and / or The molybdenum metal, based on elemental molybdenum, contains 3.0%-25% by mass, preferably 4.0%-20%, more preferably 5.0%-18.0%; and / or The carrier mass content is 40%-85%, preferably 45%-80%, and more preferably 50%-75%.

11. The method according to any one of claims 8-10, wherein, In step (1), a molybdenum source is introduced using an impregnation loading method. Preferably, the solvent used for impregnation is one or more of ammonia, tartaric acid, citric acid, water, ethanol, acetone, and toluene; and / or The drying conditions include: a temperature of 100-180℃, preferably 120-160℃; and a time of 2-20 hours, preferably 4-16 hours. The roasting conditions include: a temperature of 380-600℃, preferably 400-550℃; and a time of 2-12 hours, preferably 3-10 hours.

12. The method according to any one of claims 8-11, wherein, In step (2), The co-impregnation loading method was used to introduce organonickel sources and organometallic additive sources; Preferably, The solvent used for impregnation is one or more of tartaric acid, citric acid, water, ethanol, acetone, and toluene; and / or During the co-impregnation loading process, the molar concentration of the organonitrile source, calculated as nickel element, is 0.1-2.0 mol / L, preferably 0.2-1.5 mol / L, and the molar concentration of the organometallic auxiliary source, calculated as metal auxiliary element, is 0.05-1.0 mol / L, preferably 0.1-0.5 mol / L. and / or The organic nickel source and the organometallic auxiliary source may correspond to the same or different organic groups, preferably the same; and / or The organic groups of the organonitrile source and the organometallic auxiliary source are organic acid radicals and / or organic complexing agents, respectively. Preferably, The organic acid radical is a dicarboxylic acid radical or a higher-order acid radical, preferably one or more of the following: malonate, methylmalonate, dimethylmalonate, diethylene glycol, citrate, oxalate, ethylenediaminetetramethylenephosphonate, salicylate, benzoate, tartrate, glycolate, and gluconate; and / or the organic complexing agent is one or more of the following: acetylacetone, EDTA, NTA, and ethylenediamine. Preferably, the organic groups of the organonitrile source and the organometallic auxiliary source are each selected from one or more of tartrate, acetylacetone, citrate, glycolate, and gluconate. and / or The drying conditions include: a temperature of 80-180℃, preferably 100-160℃; and a drying time of 1-10 hours, preferably 2-8 hours.

13. A method for preparing a hydrogenation catalyst, characterized in that, The method includes: The product prepared according to any one of claims 8-12 is used as a precursor, and then the precursor is calcined. Preferably, the roasting conditions include: a temperature of 380-600℃, more preferably 400-550℃; and a time of 2-12 hours, more preferably 3-10 hours.

14. The catalyst prepared by the method according to any one of claims 8-13.

15. The application of the hydrogenation catalyst according to any one of claims 1-7 and 14 as a catalyst for hydrogenation under sulfur-free conditions.

16. A method for hydrogenating a low-sulfur feedstock, the method comprising: The hydrogenation reaction is carried out by introducing low-sulfur feedstock into the reduced hydrogenation catalyst, characterized in that the hydrogenation catalyst comprises any one of the hydrogenation catalysts described in claims 1-7 and 14.

17. The method according to claim 16, wherein, The low-sulfur feedstock oil is a feedstock with a sulfur content between 0-5000 ppm; and / or The low-sulfur feedstock oil is one or more of the following: low-sulfur wax oil, coal-based liquefied oil, biomass feedstock, and coal chemical synthetic feedstock. and / or The conditions for hydrogenation reaction include: Temperature 200-400℃, preferably 220-380℃; and / or The hydrogen pressure is 2.0-18.0 MPa, preferably 4.0-16.0 MPa; and / or The liquid hourly space velocity is 0.2-3.0 h⁻¹. -1 Preferably 0.3-2.0h -1 ; and / or The hydrogen-to-oil ratio is 200:1-1500:1, preferably 400:1-1200:1.

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