Hydrogenation catalysts, their preparation methods and applications

Abstract

This invention relates to the field of hydrogenation technology, and discloses a hydrogenation catalyst, its preparation method, and its application. The method includes: reacting an acidic solution containing aluminum and titanium with an alkaline solution containing aluminum to form a gel, obtaining a solid gel product; aging the solid gel product in the presence of a precipitant to obtain an aging product; subjecting the aging product to hydrothermal treatment, followed by a first drying, to obtain titanium-containing pseudoboehmite, wherein the hydrothermal treatment temperature is higher than the aging reaction temperature; optionally shaping the titanium-containing pseudoboehmite, followed by a second drying and a first calcination, to obtain a titanium oxide-alumina composite oxide support; introducing an active component and an additive onto the titanium oxide-alumina composite oxide support, followed by a third drying and a second calcination. This method avoids using organic titanium-containing reagents to prepare a catalyst with a low titanium oxide content and a specific crystal structure in an alumina-titanium oxide composite oxide support, thereby improving the catalyst's reactivity.

Description

Technical Field

[0001] This invention relates to the technical field of hydrogenation, specifically to a hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] With the continuous deterioration and increasing heaviness of petroleum resources, the market demand for diversified and lightweight petrochemical products is growing. Based on the compositional characteristics of petroleum products, hydrogenation to achieve hydrogen saturation of polycyclic aromatic hydrocarbons, gums, and asphaltenes, while removing heteroatoms and preserving alkyl side chains as intact as possible, is the general direction for improving petroleum properties. Among these, the catalyst is the core of hydrogenation technology. The development of new catalytic materials is fundamental to improving catalyst performance. Support materials need to have suitable pore sizes to provide diffusion channels for reactant molecules, while also possessing a large specific surface area to promote the dispersion of active metals on the support surface. Hydrogenation catalysts using TiO2 as a support have exhibited excellent reaction performance during use; however, due to the limitations of TiO2's pore structure and thermal stability, it has not been widely applied in the field of hydrogenation catalysts. The titanium oxide-alumina composite oxide support obtained by combining titanium oxide and alumina can effectively overcome the limitations of TiO2 itself, while also overcoming the problem of difficult reduction of metals supported on alumina, improving the utilization rate of active metals and enhancing the hydrogenation activity of the catalyst.

[0003] Patent application CN113649016A discloses a method for preparing a hydrogenation catalyst. This method involves mixing alumina, metatitanic acid, and a solvent, followed by high-energy ball milling and molding, and then drying and calcining to obtain a titanium oxide-alumina support. The titanium oxide-alumina composite support is then impregnated with a solution containing molybdenum and cobalt or nickel, followed by drying and calcination to obtain the hydrogenation catalyst. The hydrogenation catalyst prepared by this method exhibits advantages such as high low-temperature activity, and good hydrogenation activity and stability at high space velocities.

[0004] Patent application CN109833891A discloses a heavy distillate oil hydrotreating catalyst and its application using mesoporous TiO2-Al2O3 as a support. A mesoporous alumina precursor is prepared using a template-directed method. Titanium oxide, titanium isopropoxide, or tetrabutyl titanate is then introduced into the precursor solution. After crystallization and drying, a mesoporous TiO2-Al2O3 precursor is obtained. This precursor is mixed with alumina, an extrusion aid, and phosphate, extruded into strips, and then dried and calcined to obtain a phosphorus-modified TiO2-Al2O3 support. The catalyst active components include Group VIB metal oxides, Group VIII oxides, and Group VA oxides. This method can prepare a mesoporous TiO2-Al2O3 support, effectively improving the catalyst's desulfurization and denitrification capabilities.

[0005] Patent application CN1344586A discloses a supported nano-TiO2 composite support and its preparation method. This method involves preparing a titanium sol by mixing tetrabutyl titanate with ethanol, water, and nitric acid. The titanium sol is then added to a slurry prepared by mixing boehmite with water or anhydrous ethanol. The sample is dried and calcined sequentially at 200, 300, 400, and 500 °C for 2 hours. This method can support nano-TiO2 on macroporous alumina. XRD results show that the nano-TiO2 has anatase crystal structure. Loading active components onto this support can effectively improve the hydrorefining catalytic activity of the catalyst.

[0006] The above methods are complex and discontinuous in preparing the titanium oxide-alumina composite oxide support for hydrogenation catalysts. The methods for introducing TiO2 mostly involve titanium-containing organic reagents, which are costly and unsuitable for the industrial production of hydrogenation catalysts. Furthermore, the hydrogenation catalysts produced cannot simultaneously meet the requirements of hydrodesulfurization and aromatic hydrogenation saturation reactions. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems existing in the prior art and provide a hydrogenation catalyst, its preparation method, and its application. This method can prepare an alumina-titanium oxide composite oxide support with low titanium oxide content and a specific crystal form as a hydrogenation catalyst support without using organic titanium-containing reagents. This is more conducive to the industrial production of hydrogenation catalysts and improves the desulfurization reaction activity and aromatic hydrogenation saturation performance of the catalyst.

[0008] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a hydrogenation catalyst, wherein the method includes the following steps:

[0009] (1) A gelling reaction is carried out between an acidic solution containing aluminum and titanium and an alkaline solution containing aluminum to obtain a solid gelling product;

[0010] (2) In the presence of a precipitant, the solid gelling product obtained in step (1) is subjected to an aging reaction to obtain an aging reaction product.

[0011] (3) The aging reaction product obtained in step (2) is subjected to hydrothermal treatment and then subjected to first drying to obtain titanium-containing pseudoboehmite. The temperature of hydrothermal treatment is higher than the temperature of aging reaction.

[0012] (4) The titanium-containing pseudoboehmite obtained in step (3) is optionally shaped, and then subjected to a second drying and a first calcination to obtain a titanium oxide-alumina composite oxide carrier.

[0013] (5) The active component and the auxiliary agent are introduced onto the titanium oxide-alumina composite oxide support obtained in step (4), and then a third drying and a second calcination are performed to obtain a hydrogenation catalyst. The active component is selected from at least one group VIII metal and at least one group VIB metal, and the auxiliary agent is selected from at least one group VA element.

[0014] The second aspect of the present invention provides a hydrogenation catalyst prepared by the preparation method described in the first aspect.

[0015] The third aspect of this invention provides the application of the hydrogenation catalyst described in the second aspect in hydrodesulfurization reactions or aromatic hydrogenation saturation reactions.

[0016] The method provided by this invention uses a combination of co-precipitation and hydrothermal methods to prepare an alumina-titanium oxide composite oxide support with low titanium oxide content and a specific crystal form as a hydrogenation catalyst support without using organic titanium-containing reagents. This method is more conducive to the industrial production of hydrogenation catalysts and improves the hydrodesulfurization performance of the catalysts.

[0017] The method provided by this invention is simple, uses inexpensive and readily available raw materials, has easily controllable operating conditions, and allows for adjustable product properties.

[0018] The method provided by this invention introduces active components and additives onto an alumina-titanium oxide composite oxide support. The three work synergistically to improve the reaction activity of the catalyst, which is more conducive to the hydrogenation reaction of aromatics and difficult-to-remove sulfides, and improves the conversion rate of the reaction feedstock. The catalyst has both good hydrodesulfurization activity and aromatic hydrogenation saturation performance. Attached Figure Description

[0019] Figure 1 These are the XRD patterns of the alumina-titanium oxide composite oxide supports prepared in Example 1 and Comparative Example 1;

[0020] Figure 2 The images show the infrared skeletons of the alumina-titanium oxide composite oxide carriers prepared in Example 1 and Comparative Example 1. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] The first aspect of this invention provides a method for preparing a hydrogenation catalyst, wherein the method includes the following steps:

[0023] (1) A gelling reaction is carried out between an acidic solution containing aluminum and titanium and an alkaline solution containing aluminum to obtain a solid gelling product;

[0024] (2) In the presence of a precipitant, the solid gelling product obtained in step (1) is subjected to an aging reaction to obtain an aging reaction product.

[0025] (3) The aging reaction product obtained in step (2) is subjected to hydrothermal treatment and then subjected to first drying to obtain titanium-containing pseudoboehmite. The temperature of hydrothermal treatment is higher than the temperature of aging reaction.

[0026] (4) The titanium-containing pseudoboehmite obtained in step (3) is optionally shaped, and then subjected to a second drying and a first calcination to obtain a titanium oxide-alumina composite oxide carrier.

[0027] (5) The active component and the auxiliary agent are introduced onto the titanium oxide-alumina composite oxide support obtained in step (4), and then a third drying and a second calcination are performed to obtain a hydrogenation catalyst. The active component is selected from at least one group VIII metal and at least one group VIB metal, and the auxiliary agent is selected from at least one group VA element.

[0028] In this invention, there are no particular limitations on the preparation method of the acidic solution containing aluminum and titanium, as long as the titanium-containing compound can be dissolved in an aluminum solution to obtain the acidic solution. Preferably, in step (1), the acidic solution containing aluminum and titanium is prepared by dissolving the titanium-containing compound in an acidic aluminum solution.

[0029] In this invention, there is no particular limitation on the type of titanium-containing compound, as long as it meets the requirements of the gelation reaction. Preferably, the titanium-containing compound is titanium oxysulfate and / or titanium sulfate. By selecting titanium-containing compounds within the above range to prepare an acidic solution containing titanium and aluminum for the gelation reaction, the use of organic titanium reagents is avoided, ensuring that the entire preparation process is simple and environmentally friendly.

[0030] In this invention, there is no particular limitation on the type of acidic aluminum solution. Preferably, the acidic aluminum solution is selected from at least one of aluminum sulfate solution, aluminum nitrate solution, and aluminum chloride solution.

[0031] In this invention, there is no particular limitation on the type of aluminum-containing alkaline solution, as long as the gelation reaction is achieved. Preferably, in step (1), the aluminum-containing alkaline solution is a sodium aluminate solution and / or a potassium aluminate solution.

[0032] In this invention, the ratio of titanium to aluminum is controlled by adjusting the concentration of the acidic solution containing aluminum and titanium, thereby controlling the titanium content to prepare alumina-titanium oxide composite oxides in different ranges to meet different application scenarios. Preferably, in step (1), the concentration of the acidic solution containing aluminum and titanium, calculated as alumina, is 35-120 g / L, for example, it can be 35 g / L, 40 g / L, 45 g / L, 50 g / L, 55 g / L, 60 g / L, 65 g / L, 70 g / L, 75 g / L, 80 g / L, 85 g / L, 90 g / L, 95 g / L, 100 g / L, 110 g / L, 115 g / L, 120 g / L, or any value between any two groups.

[0033] Preferably, in step (1), the concentration of the acidic solution containing aluminum and titanium, calculated as titanium oxide, is 5-80 g / L, for example, it can be 5 g / L, 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, 50 g / L, 55 g / L, 60 g / L, 65 g / L, 70 g / L, 75 g / L, 80 g / L, or any value between any two groups.

[0034] In this invention, there is no particular limitation on the concentration of the aluminum-containing alkaline solution, as long as it meets the requirements of the gelation reaction. Preferably, in step (1), the concentration of the aluminum-containing alkaline solution, calculated as alumina, is 20-300 g / L, for example, it can be 20 g / L, 30 g / L, 40 g / L, 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L, 100 g / L, 110 g / L, 120 g / L, 130 g / L, 140 g / L, 150 g / L, 160 g / L, 170 g / L, 180 g / L, 190 g / L, 200 g / L, 210 g / L, 220 g / L, 230 g / L, 240 g / L, 250 g / L, 260 g / L, 270 g / L, 280 g / L, 290 g / L, 300 g / L, or any value between any two groups.

[0035] In this invention, the method of gelation reaction is not particularly limited and can be any method conventionally defined in the art. Preferably, in step (1), the gelation reaction is carried out continuously or intermittently, preferably continuously. On the one hand, carrying out the gelation reaction continuously is more conducive to controlling the pH of the gelation reaction process, effectively improving the quality of the alumina-titanium oxide composite oxide. On the other hand, continuous operation can increase the throughput per unit time and improve production efficiency.

[0036] The present invention does not particularly limit the equipment used for the gelation reaction, and any conventional choice in the art can be used. Specifically, for example, it can be carried out in a gelation tank.

[0037] According to a preferred embodiment of the present invention, the continuous gelation reaction process of the present invention includes: adding a certain amount of deionized water to the gelation tank in advance, and introducing an acidic solution containing aluminum and titanium and an alkaline solution containing aluminum from the top of the gelation tank, so that the acidic solution containing aluminum and titanium and the alkaline solution containing aluminum are mixed and contacted to carry out the gelation reaction, and the slurry generated by the gelation reaction flows out of the gelation tank continuously, while controlling the liquid level in the gelation tank to remain constant.

[0038] In this invention, the conditions for the gelation reaction are relatively flexible. Preferably, in step (1), the conditions for the gelation reaction include: a temperature of 50-70°C and a pH value of 4-7. Under this preferred method, it is more beneficial to improve the quality of the alumina-titanium oxide composite oxide. In this invention, the pH value should not be too high during the gelation reaction, as an excessively high pH will result in low pore volume and specific surface area of ​​the titanium-aluminum composite oxide product; the pH value should also not be too low, because a lower pH value will easily lead to a large difference in the formation rate of hydrated oxides of aluminum and titanium, which is not conducive to the uniform dispersion of titanium in alumina. In this invention, there is no particular limitation on the method of pH control. For example, the flow rates of the acidic solution containing aluminum and titanium and the precipitant can be adjusted. In this invention, there is no particular limitation on the flow rates of the acidic solution containing aluminum and titanium and the precipitant, as long as the pH value of the gelation reaction is met.

[0039] In this invention, the pH value of the reaction system is adjusted by adding a precipitant, so that the slurry obtained from the solid gelling product in step (1) undergoes an aging reaction. This invention allows for a wide range of precipitant types. Preferably, in step (2), the precipitant is selected from alkali metal compounds, and more preferably from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. In this invention, there is no particular limitation on the amount of precipitant used; the limitation is that it meets the pH value required for the aging reaction. Those skilled in the art can select the appropriate precipitant based on actual needs.

[0040] In this invention, the selection range of conditions for the aging reaction is relatively wide. Preferably, in step (2), the conditions for the aging reaction include: a temperature of 60-98℃, a time of 4-9h, and a pH value of 7-11;

[0041] More preferably, in step (2), the aging reaction conditions include: a temperature of 70-95℃, a time of 5-8h, and a pH value of 7.5-10. By controlling the aging reaction conditions, the pore structure of the alumina-titanium oxide composite oxide is regulated, thereby improving the quality of the alumina-titanium oxide composite oxide.

[0042] In this invention, preferably, after the aging treatment, step (2) further includes solid-liquid separation of the aging product to obtain a solid aging product. In this invention, the solid-liquid separation is a conventional operation in the art, specifically, for example, it can be at least one of sedimentation, filtration and centrifugation, which can be selected by those skilled in the art according to actual needs.

[0043] In this invention, preferably, the hydrothermal treatment temperature is 10-100°C higher than the aging reaction temperature, more preferably 10-80°C higher, and even more preferably 20-70°C higher. For example, it can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, or any value between any two groups. By controlling the temperatures of the aging reaction and the hydrothermal treatment, the pore concentration of the alumina-titanium oxide composite oxide can be increased, while obtaining the anatase crystal form. When the temperature difference between the two is not within the above-mentioned preferred range, the alumina-titanium oxide composite oxide grain size is larger, affecting the specific surface area and most probable pore size of the composite oxide material.

[0044] In this invention, preferably, step (3) further includes washing the solid aging product before hydrothermal treatment. In this invention, the washing operation is a conventional operation in the art, requiring only a reduction in the content of impurity ions (e.g., residual sodium and sulfate) in the solid aging product, for example, such that the sodium oxide content in the obtained alumina-titanium oxide composite oxide is less than 0.1% by weight, preferably less than 0.06% by weight, and more preferably 0.01-0.05% by weight.

[0045] In this invention, preferably, step (3) includes: adding water (preferably deionized water) to the solid aging product after aging treatment, pulping it, and then performing hydrothermal treatment. In this invention, the amount of water used is such that the concentration of the slurry obtained after pulping, based on the weight of oxides (alumina + titanium oxide), is 50-180 g / L, preferably 70-150 g / L.

[0046] Preferably, in this invention, the method does not use organic titanium-containing reagents. This invention prepares alumina-titanium oxide composite oxide materials via co-precipitation and hydrothermal treatment. The reaction process is simple, easy to operate, uses inexpensive and readily available raw materials, requires no organic reagents, and the production process is environmentally friendly.

[0047] Provided that the temperature of the hydrothermal treatment is higher than the temperature of the aging reaction, the selection range of the hydrothermal treatment conditions is relatively wide, in order to further optimize the pore structure characteristics of the alumina-titanium oxide composite oxide. Preferably, in step (3), the hydrothermal treatment conditions include: temperature 100-180℃, time 2-9h. In this invention, the hydrothermal treatment can change the existence state of titanium dioxide on alumina. The co-precipitation method combined with the hydrothermal method not only improves the pore concentration of the alumina-titanium oxide composite oxide, making the most probable pore size fall within a suitable range, but also allows the titanium dioxide dispersed in the alumina framework to aggregate to form anatase, thus obtaining anatase-γ-Al2O3 support when the titanium dioxide content is low.

[0048] In this invention, the selection range for the first drying conditions is relatively wide. Preferably, the first drying conditions include a temperature of 60-200℃, more preferably 100-160℃.

[0049] In this invention, the molding method described in step (4) is not particularly limited. Preferably, the molding in step (4) includes: mixing the titanium-containing pseudoboehmite obtained in step (3) with optionally an extrusion aid, an adhesive, and water, molding, and then performing a second drying and calcination to obtain a titanium oxide-alumina composite oxide carrier. In this invention, the extrusion aid used in the molding process is an extrusion aid conventionally defined in the art, such as guar gum powder or cellulose. In this invention, the adhesive used in the molding process is an adhesive conventionally defined in the art, such as nitric acid, acetic acid, or citric acid. In this invention, the amount of extrusion aid, adhesive, and water used in the molding process is not particularly limited, and those skilled in the art can select according to actual needs. In this invention, the second drying is a conventional method, such as drying in an oven, a mesh belt kiln, or a fluidized bed. When drying is performed by heating, the preferred second drying temperature is 50-200°C, and the preferred second drying time is 0.5-6 hours. More preferably, the preferred second drying temperature is 60-150°C, and the preferred second drying time is 2-4 hours. In this invention, the calcination method and conditions are the conventional methods and conditions used in the preparation of catalyst supports, such as calcination using a mesh belt kiln, a vertical furnace, and a converter. Preferably, in step (4), the conditions for the first calcination include: a temperature of 300-800℃ and a time of 1-6h; more preferably, in step (4), the conditions for the first calcination include: a temperature of 400-600℃ and a time of 2-4h.

[0050] In this invention, preferably, the amounts of the acidic solution containing aluminum and titanium and the alkaline solution containing aluminum are such that, based on the total amount of the alumina-titanium oxide composite oxide carrier, the content of alumina is 70-99% by weight, preferably 75-95% by weight, and the content of titanium oxide is 1-30% by weight, preferably 4-25% by weight. It should be noted that a small amount of impurities may exist in the alumina-titanium oxide composite oxide carrier; therefore, when impurities are present, the sum of the contents of alumina, titanium oxide, and the impurities must equal 100%. In this invention, the type of impurities is not specifically limited; for example, it can be SO3, Na2O, etc.

[0051] In this invention, the composition of the alumina-titanium oxide composite oxide carrier was determined by measuring the characteristic spectral lines of each element using a Rigaku Electric Co., Ltd. 3271 X-ray fluorescence spectrometer, and the elemental content of the alumina-titanium oxide composite oxide carrier was semi-quantitatively analyzed using the external standard method.

[0052] In this invention, preferably, the titanium oxide is anatase and the alumina is γ-crystalline. Using the method of this invention, anatase-structured alumina-titanium oxide composite oxide carrier can be prepared without organic titanium reagents and with low titanium content.

[0053] In this invention, the crystal structure of the alumina-titanium oxide composite oxide was determined using a Philips XPERT series X-ray powder diffractometer.

[0054] The alumina-titanium oxide composite oxide support provided by this invention has a high pore concentration, which is beneficial for hydrogenation reactions. Preferably, the pore volume of the alumina-titanium oxide composite oxide support is 0.4-1 mL / g, and the specific surface area is 150-400 m². 2 / g, with a most probable pore size of 5-13nm; more preferably, the alumina-titanium oxide composite oxide support has a pore volume of 0.6-0.8mL / g and a specific surface area of ​​200-300m². 2 / g, with a most probable pore size of 7-12nm.

[0055] In this invention, the pore structure characteristics of the alumina-titanium oxide composite oxide were determined by N2 adsorption-desorption characterization using a Micromeritics ASAP2420 adsorption instrument.

[0056] In this invention, preferably, in step (5), the active component is selected from cobalt and / or nickel, as well as molybdenum and / or tungsten.

[0057] In this invention, preferably, the active components are provided by precursors of each active component, more preferably by soluble compounds of each active component, and even more preferably by at least one of nickel nitrate, nickel acetate, nickel sulfate, basic nickel carbonate, nickel chloride, cobalt sulfate and cobalt nitrate, and at least one of sodium molybdate, ammonium paramolybdate, molybdenum oxide, sodium tungstate, ammonium tungstate and ammonium metatungstate.

[0058] In this invention, preferably, in step (5), the auxiliary agent is phosphorus.

[0059] In this invention, preferably, the adjuvant is provided by a compound containing adjuvant elements, and more preferably by at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, and potassium phosphate.

[0060] In this invention, there are no particular limitations on the introduction of the active components and promoters. Provided that the selected Group VIB and at least one Group VIII metal and / or at least one Group VA component are sufficiently supported on the titanium oxide-alumina composite oxide support, any known method for preparing hydrogenation catalysts can be used, such as impregnation or co-precipitation, with impregnation being preferred. According to a specific embodiment of the invention, a solution containing Group VIII and Group VIB active components and promoters is contacted with the alumina-titanium oxide composite oxide support, followed by a third drying and a second calcination to obtain the hydrogenation catalyst. In this invention, the conditions for the third drying are those commonly used for preparing such catalysts, such as a drying temperature of 80-200°C, preferably 100-200°C, and a drying time of 1-24 hours, preferably 2-12 hours. In this invention, the selection range of the conditions for the second roasting is relatively wide. Preferably, in step (5), the conditions for the second roasting include: a temperature of 250-600℃ and a time of 1-6h; more preferably, in step (5), the conditions for the second roasting include: a temperature of 300-500℃ and a time of 2-4h.

[0061] In this invention, the amounts of the titanium dioxide-alumina composite oxide support, active component, and additives are such that, based on the total amount of the hydrogenation catalyst, the content of the Group VIII metals (calculated as oxides) is 0.5-10% by weight, preferably 1.5-5% by weight, the content of the Group VIB metals is 5-35% by weight, preferably 6-30% by weight, and the content of the Group VA elements (calculated as oxides) is 1-6% by weight, preferably 2-5% by weight.

[0062] In this invention, the content of each component in the hydrogenation catalyst was determined by measuring the characteristic spectral lines of each element using a Rigaku Electric Co., Ltd. 3271 X-ray fluorescence spectrometer, and the elemental content of the alumina-titanium oxide composite oxide was determined by semi-quantitative analysis using the external standard method.

[0063] The second aspect of the present invention provides a hydrogenation catalyst prepared by the preparation method described in the first aspect.

[0064] In this invention, preferably, the hydrogenation catalyst has a pore volume of 0.4-0.7 mL / g and a specific surface area of ​​170-220 m². 2 / g, with a most probable pore size of 7-11nm.

[0065] In this invention, the pore structure characteristics of the hydrogenation catalyst were determined by N2 adsorption-desorption characterization using a Micromeritics ASAP 2420 adsorption instrument.

[0066] The third aspect of this invention provides the application of the hydrogenation catalyst described in the second aspect in hydrodesulfurization reactions or aromatic hydrogenation saturation reactions.

[0067] The hydrogenation catalyst provided by this invention has both desulfurization reaction activity and aromatic hydrogenation saturation performance.

[0068] The hydrodesulfurization reaction conditions for recalcitrant sulfides provided by this invention are conventionally defined in the art. Preferably, the hydrodesulfurization reaction conditions are: reaction temperature 240-360℃, more preferably 260-300℃; reaction pressure 3-6 MPa, more preferably 4-5 MPa; volume hourly space velocity 10-80 h⁻¹. -1 Preferably 20-60h -1 The hydrogen-to-oil volume ratio is 200-1000, preferably 300-600.

[0069] The reaction conditions for aromatic hydrocarbon hydrogenation saturation provided by this invention are those conventionally defined in the art. Preferably, the conditions for the aromatic hydrocarbon hydrogenation reaction are: reaction temperature 200-320℃, preferably 240-300℃; reaction pressure 3-6 MPa, preferably 4-5 MPa; and volume hourly space velocity 10-80 h⁻¹. -1 Preferably 20-60h -1 The hydrogen-to-oil volume ratio is 200-1000, preferably 300-600.

[0070] In this invention, the hydrogenation reaction apparatus can be carried out in any reactor that allows the feedstock oil to contact and react with the aforementioned hydrogenation catalyst under hydrogenation reaction conditions, for example, in the micro fixed-bed reactor.

[0071] In this invention, according to conventional methods in the art, before using the hydrogenation catalyst for hydrodesulfurization reaction or aromatic hydrogenation saturation reaction, it can usually be pre-sulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials in the presence of hydrogen at a temperature of 70-360°C. The pre-sulfurization treatment can be carried out outside the equipment or in situ inside the equipment. This invention does not particularly limit the specific operation method of pre-sulfurization, and those skilled in the art can choose according to actual needs.

[0072] The present invention will be described in detail below through embodiments. Unless otherwise specified, all raw materials used in the following embodiments are commercially available products.

[0073] The composition of the alumina-titanium oxide composite oxide carrier was determined by measuring the characteristic spectral lines of each element using a Rigaku Electric Co., Ltd. 3271 X-ray fluorescence spectrometer. The elemental content of the titanium-aluminum composite oxide was semi-quantitatively analyzed using the external standard method, yielding the composition of Al2O3, TiO2, SO3, Na2O, etc. in the sample.

[0074] The N2 adsorption-desorption characterization method is as follows: N2 adsorption-desorption characterization is performed on a Micromeritics ASAP 2420 adsorption instrument. Before the test, about 0.3g of alumina-titanium oxide composite oxide support is pretreated at 350℃ under vacuum for 10 hours.

[0075] The crystal form characterization method for alumina-titanium oxide composite oxides was as follows: A certain amount of alumina-titanium oxide composite oxide support was ground into powder and pressed into sheets. The crystal form of the sample was determined using a Philips XPERT series X-ray powder diffractometer. The test conditions were: Cu Kα rays (Kα = 0.154 nm), operating current 30 mA, operating voltage 40 kV, Ni filter, and scanning range 2θ = 5°-70°.

[0076] The infrared skeleton characterization method for the alumina-titanium oxide composite oxide support was as follows: A certain amount of alumina-titanium oxide composite oxide support was ground into powder, KBr was added, and it was pressed into a sheet. The characterization was performed using a Nicolet 6700 infrared spectrometer manufactured by Thermo Fisher Scientific with a resolution of 4 cm⁻¹. -1 Scanning range 4000-400cm -1 The infrared spectrum of the alumina-titanium oxide composite oxide was obtained by scanning 32 times and using the single-point attenuation total reflection method.

[0077] The radial crushing strength test method for alumina-titanium oxide composite oxide carrier is as follows: a 5mm carrier is placed horizontally between the two platforms of the particle strength tester, and a load is applied evenly to it until the carrier is destroyed. The applied pressure when the particles are crushed is recorded.

[0078] Example 1

[0079] (1) Add 3L of deionized water to the gelling tank in advance, add titanium oxysulfate to aluminum sulfate solution to prepare an acidic solution containing aluminum and titanium, and pass the acidic solution containing aluminum and titanium and sodium aluminate solution from the top of the gelling tank to mix the acidic solution containing aluminum and titanium and sodium aluminate solution in the gelling tank to carry out the gelling reaction. The slurry after the gelling reaction flows out from the overflow pipe of the gelling tank. The liquid level in the gelling tank remains unchanged. When the pre-added deionized water is replaced by the slurry after the gelling reaction, the slurry collection begins, and then the filter cake (solid gelling product) is obtained by filtration.

[0080] The concentration of sodium aluminate solution (calculated as alumina) was 200 g / L, and the flow rate was 42 g / min. The concentration of titanium oxide in the acidic solution containing aluminum and titanium was 12.89 g / L, and the concentration of alumina was 58 g / L. By adjusting the flow rate of the acidic solution containing aluminum and titanium to 115-125 g / min, the pH value of the gelation reaction was approximately 6.3, and the temperature of the gelation reaction was 60℃.

[0081] (2) The gelation reaction product was aged by adding sodium carbonate solution to adjust the pH of the aging treatment. The aging conditions were pH 9.0, temperature 90℃, and time 6h.

[0082] (3) The aged mixture was filtered and washed sequentially to remove residual sodium and sulfate. The resulting filter cake (solid aged product) was then added to deionized water and slurried. The concentration of the resulting slurry was 130 g / L based on the weight of the titanium dioxide-alumina composite oxide. The resulting slurry was subjected to hydrothermal treatment at 150°C for 4 hours. After hydrothermal treatment, titanium-containing pseudoboehmite A1 was obtained by spray drying.

[0083] (4) Take 100g of titanium-containing pseudoboehmite A1 and 3g of guar gum powder and mix them evenly. At room temperature, mix the mixture with 85ml of nitric acid aqueous solution with a volume concentration of 1.65%. Continue to knead the mixture into a plastic body on a twin-screw extruder and then extrude it into a butterfly strip with a diameter of 1.4 mm. After drying the wet strip at 120℃ for 4 hours, it is calcined at 550℃ for 3 hours to obtain carrier Z1. The composition and properties of carrier Z1 are shown in Table 1.

[0084] (5) Take 10g of support and impregnate it for 2 hours with a mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid with a MoO3 content of 278 g / L, a NiO content of 67.1 g / L and a P2O5 content of 57.5 g / L. Dry it at 120℃ for 2 hours and calcine it at 400℃ for 3 hours to obtain catalyst C1.

[0085] from Figure 1It can be seen that in Example 1, titanium oxide exhibits anatase crystal form (titanium oxide shows diffraction peaks at 25.3°, 48.1°, 54°, and 55.1°, indicating that titanium oxide exhibits anatase crystal form), while aluminum oxide exhibits γ-Al2O3 crystal form (aluminum oxide shows diffraction peaks at 36°, 45°, and 67°, indicating that aluminum oxide exhibits γ-Al2O3 crystal form). Figure 2 The results of infrared skeleton analysis for Example 1 and Comparative Example 1 are shown, where 1100cm -1 The peak at this location represents a characteristic peak of the Al-O bond. From... Figure 2 It can be seen that the characteristic vibration peak of the Al-O bond in Example 1 disappeared, indicating that the Ti part in Example 1 replaced the Al in the alumina structure, affecting the chemical environment around the Al atoms, and thus affecting the reaction activity of the catalyst prepared with the alumina-titanium oxide composite oxide support.

[0086] Comparative Example 1

[0087] This comparative example uses the preparation method described in the existing technical document (“Effects of the addition of titania onthethermal characterization of alumina-supported palladium”, Journal of Molecular Catalysis A, 2002, 180, 285-291) to prepare titanium dioxide-alumina composite oxide. 20 g of γ-Al₂O₃ (Sinopec Changling Catalyst Co., Ltd.) and 7.74 g of isopropyl titanate were dissolved in propanol, and the solution was measured to 15 mL and stirred thoroughly. Subsequently, γ-Al₂O₃ was dispersed in the above isopropyl titanate solution in isopropanol, dried overnight at 110 °C, and then calcined at 550 °C for 3 hours to obtain the alumina-titanium dioxide composite oxide support DS1.

[0088] from Figure 1 It can be seen that the titanium oxide in the composite oxide carrier prepared by this method is in the anatase crystal form, and the aluminum oxide is in the γ-Al2O3 crystal form as in Example 1. Figure 2 Infrared skeleton analysis results show that, compared with pure alumina support, 1100 cm -1 The characteristic peaks of the Al-O bonds did not change, indicating that the method of impregnation with organic matter does not affect the framework structure of alumina.

[0089] Take 20g of support DS1, impregnate it for 2 hours with 14.8 mL of a mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid with a MoO3 content of 248 g / L, a NiO content of 59.87 g / L and a P2O5 content of 51.32 g / L, dry it at 120℃ for 2 hours, and calcine it at 400℃ for 3 hours to obtain catalyst DC1.

[0090] Example 2

[0091] Following the method of Example 1, in step (1), the concentration of titanium oxide in the acidic solution containing aluminum and titanium was 20.67 g / L, the concentration of aluminum oxide was 45.76 g / L, and the flow rate was 110-120 g / min. The remaining conditions were the same as in Example 1.

[0092] (2) Same as Example 1.

[0093] (3) The aged mixture was filtered and washed in sequence to remove residual sodium and sulfate. Then the resulting filter cake (solid aged product) was added to deionized water to make a slurry. The concentration of the slurry was 130 g / L based on the weight of the titanium dioxide-alumina composite oxide. The slurry was hydrothermally treated at 150°C for 4 h, filtered, and dried at 120°C for 6 h to obtain titanium-containing pseudoboehmite A2.

[0094] (4) Take 100g of titanium-containing boehmite A2 and 3g of guar gum powder and mix them evenly. At room temperature, mix the mixture with 105ml of 1% nitric acid aqueous solution and continue to knead it into a plastic body on a twin-screw extruder. Then, extrude it into a butterfly-shaped strip with a diameter of 1.4 mm. After drying the wet strip at 120℃ for 4 hours, it is calcined at 600℃ for 3 hours to obtain carrier Z2. The composition and properties of carrier Z2 are shown in Table 1. In Example 2, the alumina is the same as in Example 1, exhibiting the γ-Al2O3 crystal form.

[0095] (5) Take 20g of support and impregnate it for 2 hours with 13.8 mL of a mixed solution of ammonium molybdate, cobalt nitrate and phosphoric acid with MoO3 content of 193.12 g / L, CoO content of 45.24 g / L and P2O5 content of 52.19 g / L. Dry it at 120℃ for 2 hours and calcine it at 400℃ for 3 hours to obtain catalyst C2.

[0096] Example 3

[0097] According to the method of Example 2, steps (1) and (2) are the same as in Example 2;

[0098] (3) The aged mixture was filtered and washed in sequence to remove residual sodium and sulfate. Then the resulting filter cake (solid aged product) was added to deionized water and slurried. The concentration of the slurry was 130 g / L based on the weight of titanium oxide-alumina composite oxide. The slurry was hydrothermally treated at 130°C for 4 h, filtered, and dried at 120°C for 6 h to obtain titanium-containing pseudoboehmite A3.

[0099] (4) Take 100g of titanium-containing boehmite A3 and 3g of guar gum powder and mix them evenly. At room temperature, mix the mixture with 105ml of 2% nitric acid aqueous solution and continue to knead it into a plastic body on a twin-screw extruder. Then, extrude it into a butterfly-shaped strip with a diameter of 1.4 mm. After drying the wet strip at 120℃ for 4 hours, calcine it at 600℃ for 3 hours to obtain carrier Z3. The composition and properties of carrier Z3 are shown in Table 1. In Example 3, the alumina is the same as in Example 1, exhibiting the γ-Al2O3 crystal form.

[0100] (5) Take 20g of support and impregnate it for 2 hours with 14.4 mL of a mixed solution of ammonium molybdate, cobalt nitrate and phosphoric acid with MoO3 content of 185.07 g / L, CoO content of 43.35 g / L and P2O5 content of 50.02 g / L. Dry it at 120℃ for 2 hours and calcine it at 400℃ for 3 hours to obtain catalyst C3.

[0101] Example 4

[0102] According to the method of Example 2, steps (1) and (2) are the same as in Example 2;

[0103] (3) The aged mixture was filtered and washed in sequence to remove residual sodium and sulfate. Then the resulting filter cake (solid aged product) was added to deionized water to make a slurry. The concentration of the slurry was 130 g / L based on the weight of the titanium oxide-alumina composite oxide. The slurry was hydrothermally treated at 110 °C for 4 h to obtain titanium-containing pseudoboehmite A4.

[0104] (4) Take 100g of titanium-containing pseudoboehmite A4 and 3g of guar gum powder and mix them evenly. At room temperature, mix the mixture with 105ml of 2.5% nitric acid aqueous solution and continue to knead it into a plastic body on a twin-screw extruder. Then, extrude it into a butterfly-shaped strip with a diameter of 1.4 mm. After drying the wet strip at 120℃ for 4 hours, calcine it at 600℃ for 3 hours to obtain carrier Z4. The composition and properties of carrier Z4 are shown in Table 1. In Example 4, the alumina is the same as in Example 1, exhibiting the γ-Al2O3 crystal form.

[0105] (5) Take 20g of support and impregnate it for 2 hours with 14.8 mL of a mixed solution of ammonium molybdate, cobalt nitrate and phosphoric acid with MoO3 content of 180.07 g / L, CoO content of 42.18 g / L and P2O5 content of 48.67 g / L. Dry it at 120℃ for 2 hours and calcine it at 400℃ for 3 hours to obtain catalyst C4.

[0106] Example 5

[0107] Following the method of Example 2, steps (1) and (3) are the same as in Example 2, except that the aging treatment temperature in step (2) is 60°C. The composition and properties of carrier Z5 are shown in Table 1.

[0108] (4) Take 100g of titanium-containing pseudoboehmite A5 and 3g of guar gum powder and mix them evenly. At room temperature, mix the mixture with 70ml of nitric acid aqueous solution with a volume concentration of 2% and continue to knead it into a plastic body on a twin-screw extruder. Then, extrude it into a butterfly strip with a diameter of 1.4 mm. After drying the wet strip at 120℃ for 4 hours, it is calcined at 600℃ for 3 hours to obtain carrier Z5. The composition and properties of carrier Z5 are shown in Table 1.

[0109] In Example 5, the alumina was in the same γ-Al2O3 crystal form as in Example 1.

[0110] (5) Take 20g of support Z5, impregnate it for 2 hours with 11.6 ml of a mixed solution of ammonium molybdate, cobalt nitrate and phosphoric acid with MoO3 content of 229.7 g / L, CoO content of 53.81 g / L and P2O5 content of 62.09 g / L, dry it at 120℃ for 2 hours, and calcine it at 400℃ for 3 hours to obtain catalyst C5.

[0111] Example 6

[0112] Following the method of Example 1, in step (1), the concentration of titanium oxide in the acidic solution containing aluminum and titanium was 31.75 g / L, and the concentration of aluminum oxide was 46.64 g / L. The remaining conditions were the same as in Example 1.

[0113] (2) Same as Example 1.

[0114] (3) The aged mixture was filtered and washed in sequence to remove residual sodium and sulfate. Then the resulting filter cake (solid aged product) was added to deionized water and slurried. The concentration of the slurry was 130 g / L based on the weight of titanium oxide-alumina composite oxide. The slurry was hydrothermally treated at 120°C for 4 h, filtered, and dried at 120°C for 6 h to obtain titanium-containing pseudoboehmite A6.

[0115] (4) Take 100g of titanium-containing pseudoboehmite A6 and 3g of guar gum powder and mix them evenly. At room temperature, mix the mixture with 80ml of 2% nitric acid aqueous solution and continue to knead it into a plastic body on a twin-screw extruder. Then, extrude it into a butterfly strip with a diameter of 1.4 mm. After drying the wet strip at 120℃ for 4 hours, it is calcined at 600℃ for 3 hours to obtain carrier Z6. The composition and properties of carrier Z6 are shown in Table 1.

[0116] In Example 6, the alumina was in the same γ-Al2O3 crystal form as in Example 1.

[0117] (5) Take 20g of support and impregnate it for 2 hours with 12.4 mL of a mixed solution of ammonium molybdate, cobalt nitrate and phosphoric acid with MoO3 content of 296 g / L, NiO content of 71.46 g / L and P2O5 content of 61.25 g / L. Dry it at 120℃ for 2 hours and calcine it at 400℃ for 3 hours to obtain catalyst C6.

[0118] Example 7

[0119] (1) The method of Example 1 is different except that in step (1), an acidic solution containing aluminum and titanium with different titanium oxide contents is used. Specifically, the titanium oxide concentration is 6.11 g / L, the aluminum oxide concentration is 58 g / L, and the flow rate is 120-130 g / min.

[0120] (2) The gelation reaction product is subjected to aging treatment. The aging treatment conditions are pH 8.0, temperature 70℃, and time 8h. The concentration of the aging mixture is 70g / L based on titanium oxide-alumina.

[0121] (3) The aged mixture was filtered and washed sequentially to remove residual sodium and sulfate. The resulting filter cake (solid aged product) was then added to deionized water and slurried. The concentration of the resulting slurry was 130 g / L (calculated as titanium dioxide-alumina). The resulting slurry was subjected to hydrothermal treatment at 170°C for 4 hours. After hydrothermal treatment, the mixture was spray-dried and then calcined at 600°C for 3 hours to obtain titanium-containing pseudoboehmite A7.

[0122] (4) Take 100g of titanium-containing boehmite A7 and 3g of guar gum powder and mix them evenly. At room temperature, mix the mixture with 90ml of 2.5% nitric acid aqueous solution and continue to knead it into a plastic body on a twin-screw extruder. Then, extrude it into a butterfly-shaped strip with a diameter of 1.4 mm. After drying the wet strip at 120℃ for 4 hours, calcine it at 550℃ for 3 hours to obtain carrier Z7. The composition and properties of carrier Z7 are shown in Table 1. In Example 7, the alumina is the same as in Example 1, exhibiting the γ-Al2O3 crystal form.

[0123] (5) Take 20g of support and impregnate it for 2 hours with a mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid with a MoO3 content of 254.92 g / L, a NiO content of 61.53 g / L and a P2O5 content of 52.74 g / L. Dry it at 120℃ for 2 hours and calcine it at 500℃ for 3 hours to obtain catalyst C7.

[0124] Comparative Example 2

[0125] Following the method of Comparative Example 1, 20 g of γ-Al₂O₃ (Sinopec Changling Catalyst Co., Ltd.) was taken, and 15.48 g of isopropyl titanate was dissolved in propanol, and the volume was measured to 15 mL and stirred thoroughly. Then, γ-Al₂O₃ was dispersed in the above isopropyl titanate isopropyl alcohol solution, dried at 110 °C overnight, and calcined at 550 °C for 3 hours to obtain alumina-titanium oxide composite oxide support DS2.

[0126] Take 20g of support DS2 and impregnate it for 2 hours with 14 mL of a mixed solution of molybdenum oxide, basic nickel carbonate and phosphoric acid with a MoO3 content of 190.4 g / L, a CoO content of 44.6 g / L and a P2O5 content of 51.45 g / L. Then dry it at 120℃ for 2 hours and calcine it at 400℃ for 3 hours to obtain catalyst D2.

[0127] Comparative Example 3

[0128] This embodiment uses the titration precipitation method described in patent application CN111050904A to prepare a titanium oxide-alumina composite oxide support. Sodium aluminate was diluted in water, and aluminum sulfate and titanium oxysulfate were added under vigorous stirring and heating at 60°C, resulting in a final pH of 6.5. The pH was adjusted to 7.2 using NaOH, and the mixture was aged at 60°C for 1 hour with stirring. The filter cake was re-slurryed with water, adjusted to pH 10 with ammonia, and aged at 95°C for 1 hour with stirring. The slurry was then filtered and washed with water to remove excess ammonia, dried, extruded, and calcined at below 650°C for 1 hour with a steam flow rate of 10 mL / min and 25% (volume ratio) of steam to obtain the alumina-titanium oxide composite oxide support DS3. The composition and properties of the alumina-titanium oxide composite oxide support DS3 are shown in Table 1.

[0129] The remaining steps are the same as in Example 1, and catalyst D3 is obtained.

[0130] The composition and properties of the catalysts prepared in the above embodiments and comparative examples are shown in Table 2.

[0131] Table 1

[0132]

[0133] Note: Trace amounts of impurities exist during the carrier synthesis and analysis process.

[0134] The results in Table 1 show that Examples 1-7 prepared using the method described in this invention all exhibit the anatase-γ-Al₂O₃ crystal form. When the preparation conditions are within the preferred range described in this invention, the alumina-titanium oxide composite oxide support possesses a superior specific surface area and most probable pore size, and exhibits high support strength. Compared to the comparative examples, the method described in this invention provides inexpensive and readily available raw materials for preparing alumina-titanium oxide composite oxide materials, and the preparation process is simple and short, allowing for the acquisition of composite oxide materials with low titanium content and the anatase-γ-Al₂O₃ crystal form.

[0135] Table 2

[0136]

[0137] As can be seen from the results in Table 2, when the preparation conditions are within the preferred range described in this invention, the catalyst with alumina-titanium oxide composite oxide as the support has a better specific surface area and most probable pore size.

[0138] Test Example 1

[0139] The catalysts prepared in the above examples and comparative examples were used in a fixed-bed continuous flow microreactor, using a n-decane solution containing 0.45% 4,6-DMDBT (mass fraction) and 0.45% decahydronaphthalene (mass fraction) as feedstock. Before the reaction, the catalyst needed to be pre-sulfurized. The sulfidation oil was a cyclohexane solution containing 5% CS2 (mass fraction), the sulfidation temperature was 360°C, the hydrogen flow rate was 365 mL / min, the sulfidation oil flow rate was 0.4 mL / min, and the sulfidation pressure was 4 MPa. After sulfidation, the reaction oil was switched to the reaction oil. The reaction conditions for 4,6-DMDBT were: reaction temperature 280°C, reaction pressure 4 MPa, hydrogen flow rate 100 mL / min, reaction oil flow rate 0.2 mL / min, and volumetric hourly space velocity (VHSV) 40 h⁻¹. -1 After the system stabilized, the product condensate was collected, and the product composition was analyzed by GC-MS. The reaction results are shown in Table 3.

[0140] Test Example 2

[0141] The catalysts prepared in the above examples and comparative examples were used in a fixed-bed continuous flow microreactor. A n-decane solution containing 1% decahydronaphthalene (mass fraction) and 1% pyrene (mass fraction) was used as the feedstock. Before the reaction, the catalyst underwent pre-sulfurization. The pre-sulfurization oil was a cyclohexane solution containing 5% CS2 (mass fraction). The pre-sulfurization temperature was 360°C, the hydrogen flow rate was 365 mL / min, the pre-sulfurization oil flow rate was 0.4 mL / min, and the pre-sulfurization pressure was 4 MPa. After pre-sulfurization, the reaction oil was switched to the reaction oil. The reaction conditions for pyrene were: reaction temperature 240°C, reaction pressure 4 MPa, hydrogen flow rate 100 mL / min, reaction oil flow rate 0.2 mL / min, and volumetric hourly space velocity (VHSV) 40 h⁻¹.-1 After the system stabilized, the product condensate was collected, and the product composition was analyzed by GC-MS. The reaction results are shown in Table 3.

[0142] Calculate the conversion rate x of the reactants using the following formula:

[0143]

[0144] Where a is the mass fraction of 4,6-DMDBT or pyrene in the product, and b is the mass fraction of 4,6-DMDBT or pyrene in the raw material.

[0145] Table 3

[0146]

[0147]

[0148] Based on the table above and the data from the examples, it can be seen that, under the premise of the same TiO2 content, when the alumina-titanium oxide composite oxide material prepared by the method provided in this invention is used as a catalyst support to prepare a catalyst, the catalyst has good reactivity and good aromatic hydrogenation saturation performance while maintaining high hydrodesulfurization activity.

[0149] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a hydrogenation catalyst, characterized in that, The method includes the following steps: (1) A gelling reaction is carried out between an acidic solution containing aluminum and titanium and an alkaline solution containing aluminum to obtain a solid gelling product; (2) In the presence of a precipitant, the solid gelling product obtained in step (1) is subjected to an aging reaction to obtain an aging reaction product; (3) The aging reaction product obtained in step (2) is subjected to hydrothermal treatment and then first drying to obtain titanium-containing pseudoboehmite. The temperature of hydrothermal treatment is higher than the temperature of aging reaction. (4) The titanium-containing pseudoboehmite obtained in step (3) is optionally shaped, and then subjected to a second drying and a first calcination to obtain a titanium oxide-alumina composite oxide carrier. (5) The active component and the auxiliary agent are introduced onto the titanium oxide-alumina composite oxide support obtained in step (4), and then a third drying and a second calcination are performed to obtain a hydrogenation catalyst. The active component is selected from at least one of Group VIII metals and at least one of Group VIB metals, and the auxiliary agent is selected from at least one of Group VA elements. In step (2), the conditions for the aging reaction include: a temperature of 70-95℃, a time of 5-8h, and a pH value of 7.5-10; In step (3), the conditions for hydrothermal treatment include: temperature 100-180℃ and time 2-9h; In step (4), the titanium oxide is anatase and the aluminum oxide is γ-crystalline.

2. The method according to claim 1, wherein, In step (1), the acidic solution containing aluminum and titanium is prepared by dissolving a titanium-containing compound in an acidic aluminum solution.

3. The method according to claim 2, wherein, In step (1), the titanium-containing compound is titanium oxysulfate and / or titanium sulfate.

4. The method according to claim 2, wherein, In step (1), the acidic aluminum solution is selected from at least one of aluminum sulfate solution, aluminum nitrate solution and aluminum chloride solution.

5. The method according to claim 1, wherein, In step (1), the aluminum-containing alkaline solution is a sodium aluminate solution and / or a potassium aluminate solution.

6. The method according to claim 1, wherein, In step (1), the concentration of the acidic solution containing aluminum and titanium, calculated as aluminum oxide, is 35-120 g / L.

7. The method according to claim 6, wherein, In step (1), the concentration of the acidic solution containing aluminum and titanium, calculated as titanium oxide, is 5-80 g / L.

8. The method according to claim 1, wherein, In step (1), the concentration of the aluminum-containing alkaline solution, calculated as alumina, is 20-300 g / L.

9. The method according to claim 1 or 2, wherein, In step (1), the gelation reaction is carried out continuously or intermittently.

10. The method according to claim 9, wherein, In step (1), the gelation reaction is carried out continuously.

11. The method according to claim 1, wherein, In step (1), the conditions for the gelation reaction include: a temperature of 50-70℃ and a pH value of 4-7.

12. The method according to claim 1, wherein, In step (2), the precipitant is selected from compounds containing alkali metals.

13. The method according to claim 12, wherein, In step (2), the alkali metal-containing compound is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

14. The method according to claim 1, wherein, In step (3), the temperature of the hydrothermal treatment is 10-100°C higher than the temperature of the aging reaction.

15. The method according to claim 14, wherein the temperature of the hydrothermal treatment is 10-80°C higher than the temperature of the aging reaction.

16. The method according to claim 15, wherein the temperature of the hydrothermal treatment is 20-70°C higher than the temperature of the aging reaction.

17. The method according to claim 1, wherein, The method for preparing the hydrogenation catalyst does not use organic titanium-containing reagents.

18. The method according to claim 1, wherein, In step (4), the conditions for the first roasting include: a temperature of 300-800℃ and a time of 1-6h.

19. The method according to claim 18, wherein, In step (4), the conditions for the first roasting include: a temperature of 400-600℃ and a time of 2-4h.

20. The method according to claim 1, wherein, In step (4), the amounts of the acidic solution containing aluminum and titanium and the alkaline solution containing aluminum are such that, based on the total amount of the titanium oxide-alumina composite oxide carrier, the content of aluminum oxide is 70-99% by weight and the content of titanium oxide is 1-30% by weight.

21. The method according to claim 20, wherein, based on the total amount of the titanium dioxide-alumina composite oxide carrier, the content of alumina is 75-96% by weight and the content of titanium dioxide is 4-25% by weight.

22. The method according to claim 1, wherein, In step (4), the pore volume of the titanium dioxide-alumina composite oxide support is 0.4-1 mL / g, and the specific surface area is 150-400 m². 2 / g, with a most probable pore size of 5-13nm.

23. The method according to claim 22, wherein, The titanium dioxide-alumina composite oxide carrier has a pore volume of 0.6-0.8 mL / g and a specific surface area of ​​200-300 m². 2 / g, with a most probable pore size of 7-12nm.

24. The method according to claim 1, wherein, In step (5), the active component is selected from cobalt and / or nickel, as well as molybdenum and / or tungsten.

25. The method according to claim 1, wherein, In step (5), the auxiliary agent is phosphorus.

26. The method according to claim 1, wherein, In step (5), the conditions for the second roasting include: a temperature of 200-700℃ and a time of 1-6h.

27. The method according to claim 26, wherein, In step (5), the conditions for the second roasting include: a temperature of 300-500℃ and a time of 2-4h.

28. The method according to claim 1, wherein, In step (5), the amounts of the titanium dioxide-alumina composite oxide support, active component and additives are such that, based on the total amount of hydrogenation catalyst, the content of the Group VIII metals in the oxide is 0.5-10% by weight, the content of the Group VIB metals in the oxide is 5-35% by weight, and the content of the Group VA elements in the oxide is 1-6% by weight.

29. The method according to claim 28, wherein, In step (5), the content of the group VIII metals, calculated as oxides, is 1.5-5% by weight, the content of the group VIB metals, calculated as oxides, is 6-30% by weight, and the content of the group VA elements, calculated as oxides, is 2-5% by weight.

30. The hydrogenation catalyst prepared by the method according to any one of claims 1-29.

31. The application of the hydrogenation catalyst according to claim 30 in hydrodesulfurization reaction or aromatic hydrogenation saturation reaction.

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