High-activity hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention discloses a high-activity hydrogenation catalyst and a preparation method and application thereof, and belongs to the technical field of catalysis, the high-activity hydrogenation catalyst comprises a modified macroporous silicon dioxide carrier precursor, and main and auxiliary metal phases and organic compounds on the precursor, the macroporous silicon dioxide carrier is modified by adding a carrier modifier and using a kneading forming mode, and the high-activity hydrogenation catalyst is obtained. The properties of channels of the hydrogenation catalyst carrier are treated, and the modifier is added to change the interaction between the catalyst carrier and the active component, so that the dispersion degree of active metal of the catalyst is improved while the properties of the carrier are changed, and the utilization rate of the metal is increased; meanwhile, diffusion of reactant molecules and product molecules can be improved through a large pore channel structure, the influence of catalyst carbon deposition on hydrogenation activity is reduced, the hydrogenation effect of the catalyst is improved, the deactivation rate of the catalyst is slowed down, the service life of the catalyst is prolonged, and the required cost is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts, and in particular to a high-activity hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] At present, with the rapid development of the national economy and sustainable development energy, the environmental problems caused by diesel vehicle exhaust emissions have become an important issue that needs to be solved urgently. People's awareness of environmental protection has gradually increased, and the automobile fuel standards of countries around the world have become more and more stringent. my country began to supply National VI standard automotive diesel nationwide on July 1, 2020. It can be seen that my country attaches more and more importance to improving the energy efficiency of clean diesel. One of the most important indicators in diesel quality upgrade is ultra-low sulfurization (S<10ppm). The hydrogenation process can effectively achieve the efficient and deep removal of sulfur compounds in automotive fuels.

[0003] The active components of hydrodesulfurization catalysts are generally transition metal elements, including Mo and W of group VIB and Co, Ni, Pt and Pd of group VIII. These metal elements have body-centered or face-centered cubic lattices or hexagonal lattices, and have unfilled d electron orbitals, and have the conditions to be hydrogenation active components in terms of both geometrical and electronic properties.

[0004] At present, most hydrorefining catalysts are composed of molybdenum or tungsten sulfides as main catalysts and nickel and cobalt sulfides as cocatalysts. The most commonly used metal component combinations are two-component Co-Mo, Ni-Mo, Ni-W, and three-component Ni-W-Mo, Co-Ni-Mo, etc. In order to promote the active metal to form a highly active hydrogenation active phase, adding organic acids, polyols, organic amines and other substances during the preparation of the impregnation solution is a common method. By changing the interaction between the carrier and the active metal, the dispersion of the active metal in the catalyst is promoted, and a highly active hydrogenation active phase is formed during the sulfidation process.

[0005] Chinese patent CN202111681472.4 introduces a diesel hydro-reforming catalyst and its preparation method and application. The components of the catalyst include active metals of Group VIB (Mo and / or W), active metals of Group VIII (Co and / or Ni), mesoporous amorphous silica-alumina, mesoporous alumina and composite mesoporous molecular sieves (composed of USY molecular sieves and MSU-1 molecular sieves). The preparation method includes mixing mesoporous amorphous silica-alumina, mesoporous alumina, composite mesoporous molecular sieves, adhesives and extrusion aids, drying and calcining to prepare a carrier after extrusion, and then impregnating the carrier with an impregnation solution containing active metals, drying and calcining, and finally obtaining a catalyst. The catalyst is suitable for the hydro-reforming of inferior high-aromatic diesel raw materials, and can overcome the defects of low octane number and high sulfur content of the existing hydrogenation catalyst when reforming high-aromatic inferior diesel, thereby producing high-octane gasoline and ultra-low sulfur diesel.

[0006] CN202211601529 provides a catalytic diesel hydrogenation catalyst and a preparation method thereof. During the carrier preparation process, a Y-type molecular sieve and a corn starch aqueous solution are processed by a ball mill to finally obtain a spherical carrier. The catalyst preparation stage involves mixing an impregnation solution containing a Group VIII metal compound, a Group VIB metal compound and a phosphorus compound, and then drying and roasting to obtain a catalyst. The active metal components in the catalyst mainly include Group VIII metals and Group VIB metals, as well as compounds of phosphorus elements. The concentrations of these elements can effectively improve the activity and stability of the catalyst within a certain range. This catalyst is suitable for diesel hydrogenation conversion processes and exhibits good performance through long-term activity evaluation. Preferred embodiments are also mentioned, including drying and roasting operations under different temperature and time conditions, and a preparation process of an organic polymer aqueous solution.

[0007] CN202211222659 discloses a method for preparing and applying a hydrogenation catalyst containing B acid. By introducing a prefabricated alumina material containing B acid, the hydrodesulfurization activity of the catalyst is significantly improved. The preparation process includes adding an impregnation liquid to a carrier, and preparing the catalyst by calcining after ultrasonic treatment and drying. The key points include: the introduction of an alumina material containing B acid improves the hydrodesulfurization activity of the catalyst, the preparation process includes the steps of impregnation, ultrasonic treatment, drying and calcination, and two catalysts, W-Ni and Co-Mo, are prepared, and their physical properties are characterized. The catalyst can be used in diesel hydrorefining and other fields.

[0008] The existing hydrogenation catalyst has the problems of fast deactivation rate, low metal utilization rate and poor metal dispersion, which lead to poor catalyst hydrogenation effect. At the same time, compared with the non-supported catalyst, the above problems do not exist, and the total metal loading can reach more than 70%. Unfortunately, unlike the supported catalyst, the pore structure of the non-supported catalyst is highly dependent on the synthesis method because it can not form an excellent pore structure through a solid carrier. The synthesis process is costly, the pore structure is poor and the stability is poor. In view of this, the present invention proposes a high-activity hydrogenation catalyst that has both advantages. The catalyst synthesis method is changed to improve the dispersion of the active metal of the catalyst and improve the utilization of the metal. At the same time, the diffusion of the reactant molecules and the product molecules can be improved through a larger pore structure, the effect of the catalyst carbon deposition on the hydrogenation activity is reduced, the hydrogenation effect of the catalyst is improved, the deactivation rate of the catalyst is slowed down, the use mission of the catalyst is extended, and the required cost is reduced. Summary of the invention

[0009] Based on previous research and existing problems, the present invention, after further research and analysis, proposes a high-activity hydrogenation catalyst and its preparation method and application, which can improve the interaction between the metal and the carrier, help the dispersion of the catalyst metal, facilitate the formation of a high-activity hydrogenation active phase, and improve the hydrogenation activity of the catalyst; it can improve the pore structure of the catalyst, facilitate molecular diffusion, improve the stability of the catalyst, and extend the service life of the catalyst.

[0010] To achieve the above object, the present invention provides the following technical solutions:

[0011] A high-activity hydrogenation catalyst comprises a main metal phase and a metal-aiding phase, and also comprises a modified macroporous silica carrier precursor and an organic compound. The modified macroporous silica carrier precursor comprises a modifier, aluminum hydroxide dry gel and macroporous silica, wherein the modifier accounts for 10wt% to 15wt% of the mass of the macroporous silica, and the mass ratio of the macroporous silica to the aluminum hydroxide dry gel is 1:1 to 4:1; the specific surface area of ​​the modified macroporous silica carrier precursor is 130 to 350m 2 / g, the pore volume is 0.5~2.5mL / g, and the pore diameter is concentrated in the range of 5~20nm.

[0012] Preferably, the atomic ratio of the main metal phase to the organic compound is 2:1 to 8:1.

[0013] Preferably, the metal phase includes Ni, Mo and W, the auxiliary metal phase includes Co, Cu or Fe, and the content of the main metal phase and the auxiliary metal phase is 20 wt% to 60 wt% based on the mass of the metal oxide.

[0014] Preferably, the metal atomic ratio of Mo to W in the main metal phase is 0.3:1 to 3:1.

[0015] The present invention also provides a method for preparing the catalyst mentioned above, the method steps are as follows:

[0016] S1. Preparing a modified macroporous silica carrier precursor: grinding and mixing macroporous silica and a carrier modifier in a certain mass ratio by a ball mill;

[0017] Adding alumina dry glue in a corresponding proportion to a peptizing agent and an extrusion aid and stirring evenly to obtain aluminum hydroxide colloid;

[0018] Mixing macroporous silica, support modifier powder and aluminum hydroxide colloid and stirring evenly;

[0019] The obtained mixture is kneaded, extruded, dried and calcined to obtain a hydrogenation catalyst carrier;

[0020] S2, adding a metal impregnation solution to the catalyst carrier in S1, and performing equal volume impregnation, pre-treating the impregnated hydrogenation catalyst in a water vapor atmosphere or an ammonia atmosphere, and taking it out at a set temperature to obtain a pre-treated hydrogenation catalyst carrier; the metal impregnation solution comprises a main metal phase metal source, an auxiliary metal phase metal source, an organic compound and water;

[0021] S3, calcining the catalyst prepared in S2 under a water vapor atmosphere to obtain a mesophase hydrogenation catalyst;

[0022] S4, calcining the intermediate phase hydrogenation catalyst in S3 for a second time under air atmosphere to obtain a final formed hydrogenation catalyst.

[0023] Preferably, in S1, the support modifier is one or more of zirconium oxide, titanium oxide or phosphorus pentoxide;

[0024] The peptizing agent is one or more of nitric acid, carbonic acid, sulfuric acid, acetic acid and tartaric acid, and the amount used is 1wt% to 3wt% by mass; the extrusion aid is sesbania powder, and the amount used is 1 to 5wt% of the mass of the catalyst carrier precursor;

[0025] The drying temperature is 80-150° C., the drying time is 2-6 hours, the calcination temperature is 300-600° C., and the calcination time is 3-9 hours.

[0026] Preferably, in S2, the organic compound is one or more of citric acid, ethylenediaminetetraacetic acid, ethylenediamine and ethylene glycol;

[0027] The treatment conditions are as follows: the gas phase atmosphere is one of water vapor or ammonia, the temperature is 100-300° C., the time is 1-6 hours, and the pressure is 0.1-2 MPa.

[0028] Preferably, in S3, the primary calcination conditions are: the gas phase atmosphere is water vapor, the calcination temperature is 300-500° C., and the calcination time is 3-8 hours.

[0029] Preferably, in S4, the secondary calcination conditions are: the gas phase atmosphere is air, the calcination temperature is 400-600° C., and the calcination time is 3-8 hours.

[0030] In addition, the present invention also proposes an application of the high-activity hydrogenation catalyst mentioned above, which can be used for the hydrogenation refining reaction of oil products such as naphtha, diesel, and wax oil.

[0031] Compared with the existing technology, the present invention provides a high-activity hydrogenation catalyst and its preparation method and application, which have the following beneficial effects:

[0032] The present invention provides a high-activity hydrogenation catalyst, which modifies a macroporous silica carrier by adding a carrier modifier and using a kneading molding method, processes the properties of the hydrogenation catalyst carrier pores, and adds a modifier to change the interaction between the catalyst carrier and the active component, improves the dispersion of the catalyst active metal while changing the carrier properties, improves the utilization rate of the metal, and can improve the diffusion of reactant molecules and product molecules through a larger pore structure, reduce the effect of catalyst carbon deposition on hydrogenation activity, improve the hydrogenation effect of the catalyst, slow down the deactivation rate of the catalyst, extend the service life of the catalyst, and reduce the required cost. The method of adding an organic compound to the impregnation liquid changes the stability of the impregnation liquid, and at the same time, the active metal of the catalyst forms a corresponding complex with the organic compound, changes the interaction between the active components, and better forms the sulfurized active components required for hydrogenation through sulfurization, thereby improving the hydrogenation activity of the catalyst. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0034] The invention provides a highly active hydrogenating agent, comprising a macroporous silica carrier precursor, and a main metal phase, a metal auxiliary phase and an organic compound supported on the precursor, wherein the main metal phase comprises Ni, Mo and W, the metal auxiliary phase comprises Co, Cu or Fe, and the content of the main metal phase and the metal auxiliary phase is 20wt% to 60wt% according to the mass of the metal oxide, and can be specifically 20, 25, 30, 35, 40, 45, 50, 55 or 60wt% in an embodiment.

[0035] In the present invention, the main metal phase includes Ni, Mo and W, and Mo and W cooperate as catalyst active centers. The metal atomic ratio of Mo and W in the main metal phase is preferably 0.3:1 to 3:1. In embodiments, it can be specifically 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1 or 3:1.

[0036] In the present invention, the auxiliary metal phase includes Co, Cu or Fe, and the metal atomic ratio of the main metal phase to the auxiliary metal phase is preferably 1:1 to 3:1. In embodiments, it may be specifically 1:1, 1.5:1, 2:1, 2.5:1 or 3:1.

[0037] In the present invention, the atomic ratio of the main metal phase to the organic compound is 2:1 to 8:1, and can be specifically 2:1, 4:1, 6:1 or 8:1 in embodiments.

[0038] The metal catalyst provided by the present invention has a rich pore structure and a large specific surface area. In the embodiment of the present invention, the specific surface area of ​​the hydrogenation catalyst carrier is 130 to 350 m 2 / g, the pore volume is 0.5~2.5mL / g, and the pore diameter is concentrated in the range of 5~20nm.

[0039] The present invention also provides a method for preparing the high-activity hydrogenation catalyst of the above technical solution, comprising the following steps:

[0040] (1) adding macroporous silica and a support modifier into a ball mill according to a certain mass ratio, and grinding the macroporous silica and the support modifier powders by the ball mill;

[0041] (2) adding aluminum hydroxide dry glue, peptizing agent, and extrusion aid and stirring evenly to obtain aluminum hydroxide colloid;

[0042] (3) Mixing macroporous silica, a carrier modifier and aluminum hydroxide colloid and stirring them uniformly; kneading the obtained mixture, kneading for 3 to 5 times and then extruding it into strips to obtain a wet-molded high-activity hydrogenation catalyst carrier precursor; drying the wet-molded high-activity hydrogenation catalyst carrier precursor and then calcining it to obtain a molded high-activity hydrogenation catalyst modified carrier.

[0043] (4) adding metal and organic compound impregnation solutions to the modified macroporous silica support for equal volume impregnation, treating the wet high-activity hydrogenation catalyst after impregnation in a water vapor atmosphere or an ammonia atmosphere, and taking it out at a set temperature to obtain a precursor of a high-activity hydrogenation catalyst; wherein the metal impregnation solution comprises a main metal phase metal source, a metal auxiliary phase metal source, an organic compound and water, the main metal phase metal source comprises a water-soluble Ni source, a water-soluble Mo source and a water-soluble W source, and the metal auxiliary phase metal source comprises a water-soluble Co source, a water-soluble Cu source or a water-soluble Fe source;

[0044] (5) calcining the precursor of the high-activity hydrogenation catalyst once in a water vapor atmosphere to obtain a mesophase hydrogenation catalyst;

[0045] (6) The mesophase hydrogenation catalyst is subjected to secondary calcination under air atmosphere to obtain a final formed hydrogenation catalyst.

[0046] In the present invention, the carrier modifier is one or more of zirconium oxide, titanium oxide or phosphorus pentoxide, and the modifier accounts for 10wt% to 15wt% of the mass of macroporous silica in the catalyst; preferably 12wt% to 14wt%, which can be specifically 12, 12.5, 13, 13.5, 14wt% in the embodiment; the peptizing agent is one or more of nitric acid, carbonic acid, sulfuric acid, acetic acid and tartaric acid, and the amount is 1wt% to 3wt%, preferably 2wt%; the extrusion aid is sesbania powder, and the amount is 1 to 5wt% of the mass of the catalyst carrier precursor, preferably 2 to 3wt%;

[0047] The drying temperature is 80-150°C, preferably 100-150°C; the drying time is 2-6 hours, preferably 4-6 hours; the calcination temperature is 300-600°C, preferably 400-550°C; the calcination time is 3-9 hours, preferably 4-6 hours.

[0048] The water-soluble W source is one or more of ammonium metatungstate and ammonium tungstate, the water-soluble Mo source is one or more of ammonium molybdate heptahydrate and ammonium molybdate tetrahydrate, the water-soluble Co source is one or more of cobalt acetate and cobalt nitrate, the water-soluble Ni source is one or more of nickel acetate and nickel nitrate, the water-soluble Cu source is one or more of copper nitrate and copper chloride, the water-soluble Fe source is one or more of ferric sulfate and ferric nitrate; the organic compound is one or more of citric acid, ethylenediaminetetraacetic acid, ethylenediamine and ethylene glycol;

[0049] In the present invention, the wet-formed high-activity hydrogenation catalyst is treated under the following treatment conditions: the gas phase atmosphere is one of water vapor or ammonia, the temperature is 100-300°C, preferably 150-200°C; the time is 1-5 hours, preferably 3-4 hours; the pressure is 0.1-2MPa, preferably 0.3-1.5MPa.

[0050] In the present invention, the wet-formed high-activity hydrogenation catalyst is calcined twice, the first calcination conditions are: the gas phase atmosphere is water vapor, the calcination temperature is 300-500°C, and the calcination time is 4-6 hours. The second calcination conditions are: the gas phase atmosphere is air, the calcination temperature is 400-600°C, and the calcination time is 4-6 hours.

[0051] It should be noted that the following embodiments and features in the embodiments may be combined with each other in the absence of conflict; and, based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in the field without making any creative work are within the scope of protection of the present disclosure.

[0052] Various aspects of the embodiments within the scope of the appended claims are described below. It should be apparent that the aspects described herein may be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on this disclosure, it should be understood by those skilled in the art that an aspect described herein may be implemented independently of any other aspect, and two or more of these aspects may be combined in various ways. For example, any number of aspects described herein may be used to implement a device and / or practice a method. In addition, other structures and / or functionality other than one or more of the aspects described herein may be used to implement this device and / or practice this method.

[0053] Example 1

[0054] 1 kg of macroporous silica and 0.120 kg of zirconium oxide were put into a ball mill respectively, and macroporous silica powder and carrier modifier powder were obtained by grinding with the ball mill respectively. 0.333 kg of alumina dry gel was weighed, and 3 wt% of the extrusion aid sesbania powder, 3 wt% of the peptizer aqueous nitric acid solution (2 wt%) and 80 wt% of deionized water were added to the alumina dry gel, and then mixed for 3 to 5 times, and extruded into shape. The molded wet catalyst carrier was dried at 120°C for 3 hours and calcined at 500°C for 5 hours to obtain a molded high-activity hydrogenation catalyst modified carrier.

[0055] Weigh 1.11 kg of nickel nitrate (Ni(NO 3 ) 2 6H 2 O), 0.34 kg ammonium molybdate ((NH 4 ) 6 Mo 7 O 24 ·4H 2 O), 0.47 kg ammonium metatungstate ((NH 4 ) 6 H 2 W 12 O 40 ·XH 2 O), 0.39 kg cobalt nitrate (Co(NO 3 ) 2 6H 2 O), 0.20kg citric acid.

[0056] First, dissolve ammonium molybdate and ammonium metatungstate with an appropriate amount of water, add citric acid and stir until completely dissolved, then add nickel nitrate and cobalt nitrate, continue stirring at room temperature until completely dissolved, and adjust the volume to 1L to obtain impregnation solution A.

[0057] Based on the mass of modified macroporous silica, 1L of impregnation solution A was added to the carrier precursor. After the impregnation, the obtained catalyst was put into a hydrothermal autoclave for hydrothermal treatment at a temperature of 150°C, a time of 4 hours, and a pressure of 1.0 MPa.

[0058] The wet-formed high-activity hydrogenation catalyst was calcined twice, and the conditions for the first calcination were: the gas phase atmosphere was water vapor, the calcination temperature was 400° C., and the calcination time was 5 hours, to obtain a mesophase high-activity hydrogenation catalyst. The mesophase high-activity hydrogenation catalyst was calcined twice, and the conditions were: the gas phase atmosphere was air, the calcination temperature was 500° C., and the calcination time was 5 hours, to obtain a formed high-activity hydrogenation catalyst, which is recorded as Example 1.

[0059] Example 2

[0060] 1 kg of macroporous silica and 0.120 kg of zirconium oxide were put into a ball mill respectively, and macroporous silica powder and carrier modifier powder were obtained by grinding with the ball mill respectively. 0.333 kg of alumina dry gel was weighed, and 3 wt% of the extrusion aid sesbania powder, 3 wt% of the peptizer aqueous nitric acid solution (2 wt%) and 80 wt% of deionized water were added to the alumina dry gel, and then mixed for 3 to 5 times, and extruded into shape. The molded wet catalyst carrier was dried at 120°C for 3 hours and calcined at 500°C for 5 hours to obtain a molded high-activity hydrogenation catalyst modified carrier.

[0061] Weigh 1.11 kg of nickel nitrate (Ni(NO 3 ) 2 6H 2 O), 0.34 kg ammonium molybdate ((NH 4 ) 6 Mo 7 O 24 ·4H 2 O), 0.47 kg ammonium metatungstate ((NH 4 ) 6 H 2 W 12 O 40 ·XH 2 O), 0.39 kg cobalt nitrate (Co(NO 3 ) 2 6H 2 O), 0.20kg citric acid.

[0062] First, dissolve ammonium molybdate and ammonium metatungstate with an appropriate amount of water, add citric acid and stir until completely dissolved, then add nickel nitrate and cobalt nitrate, continue stirring at room temperature until completely dissolved, and adjust the volume to 1L to obtain impregnation solution A.

[0063] Based on the mass of modified macroporous silica, 1L of impregnation solution A was added to the carrier precursor. After the impregnation, the obtained catalyst was treated with ammonia at a temperature of 150°C for 4 hours and a pressure of 1.0 MPa.

[0064] The wet-formed high-activity hydrogenation catalyst was calcined twice, and the conditions for the first calcination were: the gas phase atmosphere was water vapor, the calcination temperature was 400° C., and the calcination time was 5 hours, to obtain a mesophase high-activity hydrogenation catalyst. The mesophase high-activity hydrogenation catalyst was calcined twice, and the conditions were: the gas phase atmosphere was air, the calcination temperature was 500° C., and the calcination time was 5 hours, to obtain a formed high-activity hydrogenation catalyst, which is recorded as Example 2.

[0065] Example 3

[0066] 1 kg of macroporous silica and 0.120 kg of zirconium oxide were put into a ball mill respectively, and macroporous silica powder and carrier modifier powder were obtained by grinding with the ball mill respectively. 0.333 kg of alumina dry gel was weighed, and 3 wt% of the extrusion aid sesbania powder, 3 wt% of the peptizer aqueous nitric acid solution (2 wt%) and 80 wt% of deionized water were added to the alumina dry gel, and then mixed for 3 to 5 times, and extruded into shape. The molded wet catalyst carrier was dried at 120°C for 3 hours and calcined at 500°C for 5 hours to obtain a molded high-activity hydrogenation catalyst modified carrier.

[0067] Weigh 1.67 kg of nickel nitrate (Ni(NO 3 ) 2 6H 2 O), 0.50 kg ammonium molybdate ((NH 4 ) 6 Mo 7 O 24 ·4H 2 O), 0.70 kg ammonium metatungstate ((NH 4 ) 6 H 2 W 12 O 40 ·XH 2 O), 0.56 kg cobalt nitrate (Co(NO 3 ) 2 6H 2 O), 0.28kg citric acid.

[0068] First, dissolve ammonium molybdate and ammonium metatungstate with an appropriate amount of water, add citric acid and stir until completely dissolved, then add nickel nitrate and cobalt nitrate, continue stirring at room temperature until completely dissolved, and adjust the volume to 1L to obtain impregnation solution B.

[0069] Based on the mass of modified macroporous silica, 1L of impregnation solution B was added to the carrier precursor. After the impregnation, the obtained catalyst was treated with ammonia at a temperature of 150°C for 4 hours and a pressure of 1.0 MPa.

[0070] The wet-formed high-activity hydrogenation catalyst was calcined twice, and the conditions for the first calcination were: the gas phase atmosphere was water vapor, the calcination temperature was 400° C., and the calcination time was 5 hours, to obtain a mesophase high-activity hydrogenation catalyst. The mesophase high-activity hydrogenation catalyst was calcined twice, and the conditions were: the gas phase atmosphere was air, the calcination temperature was 500° C., and the calcination time was 5 hours, to obtain a formed high-activity hydrogenation catalyst, which is recorded as Example 3.

[0071] Comparative Example 1

[0072] Weigh 1 kg of macroporous silica support and 1.11 kg of nickel nitrate (Ni(NO 3 ) 2 6H 2 O), 0.34 kg ammonium molybdate ((NH 4 ) 6 Mo 7 O 24 ·4H 2 O), 0.47 kg ammonium metatungstate ((NH 4 ) 6 H 2 W 12 O 40 ·XH 2 O), 0.39 kg cobalt nitrate (Co(NO 3 ) 2 6H 2 O), 0.20kg citric acid.

[0073] First, dissolve ammonium molybdate and ammonium metatungstate with an appropriate amount of water, add citric acid and stir until completely dissolved, then add nickel nitrate and cobalt nitrate, continue stirring at room temperature until completely dissolved, and adjust the volume to 1L to obtain impregnation solution C.

[0074] The macroporous silica carrier was impregnated into the impregnation liquid C by an equal volume impregnation method, and the obtained impregnated macroporous silica carrier was dried at 120° C. for 3 hours and calcined at 500° C. for 4 hours to obtain a shaped catalyst, which is recorded as Comparative Example 1.

[0075] The catalyst properties of the embodiments of the present invention and the comparative examples were systematically evaluated:

[0076] The hydrogenation activity of Example 1, Example 2, Example 3 and Comparative Example 1 was evaluated.

[0077] The activity evaluation of the catalyst was carried out in a 100mL high-pressure hydrogenation reaction device. The catalyst was pre-sulfurized and stabilized before evaluation. The evaluation conditions of the catalyst were: reaction pressure 6MPa, hydrogen-oil volume ratio 500:1, reaction temperature 360℃, volume space velocity 2.0h 1 The properties of the feedstock oil used in the activity evaluation test are shown in Table 1.

[0078] Table 1 Properties of diesel feedstock used for evaluating catalyst activity used in the present invention

[0079] project nature <![CDATA[Density (20 °C) / (g·cm -3 )]]> 0.9166 <![CDATA[Sulfur content (μg·g -1 )]]> 3380 <![CDATA[Nitrogen content (μg·g -1 )]]> 596 IBP / 5% 215 / 230 10％ / 30％ 241 / 262 50％ / 70％ 285 / 319 90% / FBP 341 / 365

[0080] The catalyst activity results of the examples and comparative examples are shown in Table 2. The hydrodesulfurization activity and the hydrogenation saturation activity of the catalysts were compared by analyzing the sulfur content of the oil products after hydrogenation and the density of the hydrogenated products. By comparing Example 1, Example 2, Example 3, and Comparative Example 1, it was found that the catalyst provided by the present invention had higher hydrogenation and desulfurization activities than the catalyst of the comparative example; that is, the high-activity hydrogenation catalyst prepared by the present invention provided pores with larger pore sizes and uniform distribution, overcoming the disadvantage of poor dispersibility of high metal content catalysts.

[0081] Table 2 Evaluation results of catalyst reaction activity of the present invention and comparative examples

[0082]

[0083] Of course, in addition to the cases listed in the examples, other modifiers, peptizers, other metal main components, auxiliary components, organic complexing agents, Ni(Co) / (Mo+W) atomic ratio, Mo / W mass ratio, drying temperature and time, calcination temperature and time are also possible when modifying the properties of the carrier. It is just that in the cases listed in the examples, the catalytic activity is higher and the pore structure is better.

[0084] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for a person skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to replace some of the technical features therein with equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions claimed to be protected by the present invention.

Claims

1. A highly active hydrogenation catalyst comprising a main metal phase and a co-metal phase, characterized in that: The invention comprises a modified macroporous silica carrier precursor and an organic compound, wherein the modified macroporous silica carrier precursor comprises a modifier, aluminum hydroxide dry gel and macroporous silica, wherein the modifier accounts for 10wt% to 15wt% of the mass of the macroporous silica, and the mass ratio of the macroporous silica to the aluminum hydroxide dry gel is 1:1 to 4:1; the specific surface area of ​​the modified macroporous silica carrier precursor is 130 to 350m 2 / g, the pore volume is 0.5~2.5mL / g, and the pore diameter is concentrated in the range of 5~20nm.

2. A highly active hydrogenation catalyst according to claim 1, characterized in that: The atomic ratio of the main metal phase to the organic compound is 2:1 to 8:

1.

3. A highly active hydrogenation catalyst according to claim 1, characterized in that: The metal phase includes Ni, Mo and W, the auxiliary metal phase includes Co, Cu or Fe, and the content of the main metal phase and the auxiliary metal phase is 20wt% to 60wt% based on the mass of the metal oxide.

4. A highly active hydrogenation catalyst according to claim 2 or 3, characterized in that: The metal atomic ratio of Mo and W in the main metal phase is 0.3:1 to 3:

1.

5. A method for preparing a highly active hydrogenation catalyst as claimed in any one of claims 1 to 4, characterized in that: The steps are as follows: S1. Preparing a modified macroporous silica carrier precursor: grinding and mixing macroporous silica and a carrier modifier in a certain mass ratio by a ball mill; Adding corresponding proportions of aluminum hydroxide dry glue to a glue solvent and an extrusion aid and stirring evenly to obtain aluminum hydroxide colloid; Mixing macroporous silica, support modifier powder and aluminum hydroxide colloid and stirring evenly; The obtained mixture is kneaded, extruded, dried and calcined to obtain a hydrogenation catalyst carrier; S2, adding a metal impregnation solution to the catalyst carrier in S1, and performing equal volume impregnation, pre-treating the impregnated hydrogenation catalyst in a water vapor atmosphere or an ammonia atmosphere, and taking it out at a set temperature to obtain a pre-treated hydrogenation catalyst carrier; the metal impregnation solution comprises a main metal phase metal source, an auxiliary metal phase metal source, an organic compound and water; S3, calcining the catalyst prepared in S2 under a water vapor atmosphere to obtain a mesophase hydrogenation catalyst; S4, calcining the intermediate phase hydrogenation catalyst in S3 for a second time under air atmosphere to obtain a final formed hydrogenation catalyst.

6. The method for preparing a highly active hydrogenation catalyst according to claim 4, characterized in that: In S1, the support modifier is one or more of zirconium oxide, titanium oxide or phosphorus pentoxide; The peptizing agent is one or more of nitric acid, carbonic acid, sulfuric acid, acetic acid and tartaric acid, and the amount used is 1wt% to 3wt% by mass; the extrusion aid is sesbania powder, and the amount used is 1 to 5wt% of the mass of the catalyst carrier precursor; The drying temperature is 80-150° C., the drying time is 2-6 hours, the calcination temperature is 300-600° C., and the calcination time is 3-9 hours.

7. The method for preparing a highly active hydrogenation catalyst according to claim 4, characterized in that: In S2, the organic compound is one or more of citric acid, ethylenediaminetetraacetic acid, ethylenediamine and ethylene glycol; The treatment conditions are as follows: the gas phase atmosphere is one of water vapor or ammonia, the temperature is 100-300° C., the time is 1-6 hours, and the pressure is 0.1-2 MPa.

8. The method for preparing a highly active hydrogenation catalyst according to claim 4, characterized in that: In S3, the primary calcination conditions are: the gas phase atmosphere is water vapor, the calcination temperature is 300 to 500° C., and the calcination time is 3 to 8 hours.

9. The method for preparing a highly active hydrogenation catalyst according to claim 4, characterized in that: In S4, the secondary calcination conditions are: the gas phase atmosphere is air, the calcination temperature is 400-600° C., and the calcination time is 3-8 hours.

10. Use of the high-activity hydrogenation catalyst according to any one of claims 1 to 4 or the high-activity hydrogenation catalyst prepared by the method according to any one of claims 5 to 9, characterized in that: The catalyst can be used for the hydrorefining reaction of naphtha, diesel, wax oil and other oil products.

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