A hydroprocessing catalyst, its preparation method and use

Abstract

This invention provides a hydrogenation catalyst, its preparation method, and its application. The hydrogenation catalyst comprises a support and an active component and an auxiliary agent supported on the support, wherein the support is TiO₂ with an ordered mesoporous structure. 2 -Al 2 O 3 The composite oxide comprises an oxide of a Group VIB metal and an oxide of a Group VIII metal, and the auxiliary agent is an oxide of metal Ge or Ga. The hydrotreating catalyst exhibits excellent hydrodesulfurization performance and is suitable for hydrotreating petroleum distillate oils, particularly for deep hydrodesulfurization of low-quality diesel oil.

Description

A hydrogenation catalyst, its preparation method and application Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a hydrogenation catalyst containing Ge or Ga promoters, its preparation method, and its application. Background Technology

[0002] The global trend of crude oil becoming heavier and of lower quality is intensifying. High-sulfur straight-run diesel, coking diesel, and catalytic diesel are the main blending components of diesel fuel, compounded by the difficulty in deep removal of these sulfur compounds. Therefore, in order to meet production requirements, the development of more active ultra-deep hydrodesulfurization catalysts is urgently needed.

[0003] As is well known, alumina materials have attracted widespread attention from scholars both domestically and internationally due to their low cost, availability, and good formability. However, hydrodesulfurization catalysts using alumina as a support exhibit poor removal activity for sulfur-containing compounds with complex structures in tar. This is mainly due to the strong interaction (MSI) between the alumina support and the active phase, resulting in longer MoS2 lamellar lengths and lower stacking layers on the corresponding catalyst. This hinders the interaction between sulfur-containing compounds and the active phase via σ-adsorption, thus blocking the low-energy- and low-H2-consumption DDS pathway. Overcoming the drawback of excessively strong interaction between the alumina support and the active metal, achieving efficient and ultra-clean conversion of low-quality diesel fuel, and ultra-deep processing to produce high-value-added chemical raw materials, breaking through the adsorption-reaction limitations of complex-structured sulfide molecules on existing catalysts, and further developing the hydrodesulfurization mechanism of complex-structured sulfides have become key research areas both domestically and internationally. Improving the support methods for active components, screening for components with higher activity, and preparing supports with superior performance are effective ways to solve this problem. To this end, researchers both domestically and internationally have carried out a series of research studies.

[0004] CN107511178A discloses a modified alumina support and a method for preparing a hydrogenation catalyst from the modified alumina support. The modified alumina support comprises a support and a vanadium additive supported on the support, wherein the vanadium additive is distributed in the shell layer of the support. The modified alumina support is then impregnated in a second solution containing a compound with an active metal component, followed by drying and calcination to obtain the hydrogenation catalyst. The hydrogenation catalyst provided by this invention can achieve a high demetallization and desulfurization effect by controlling the stratified distribution of the active metal component along the radial direction of the hydrogenation catalyst. However, in certain hydrogenation processes, it is impossible to control the complete contact between the difficult-to-remove metal and vanadium sulfide, thus there is still a possibility of deposition at the catalyst pores, causing pore blockage and preventing the effective utilization of the active phase.

[0005] CN104209142A discloses a hydrocarbon oil desulfurization catalyst and its application method. This catalyst contains a Ga-modified USY molecular sieve and a metal oxide with sulfur adsorption function, enabling effective adsorption and desulfurization of hydrocarbon oils. It boasts advantages such as high hydrocarbon oil yield, high desulfurization rate, and high gasoline octane number. However, the Ga-modified USY molecular sieve in this catalyst uses a single modification method, and the prepared catalyst can only adsorb and remove simple compounds from hydrocarbon oils, failing to effectively remove complex sulfides from heavy oils.

[0006] CN102059121A relates to a lanthanum-modified nickel-copper octanol hydrogenation refining catalyst, its preparation, and its application. The catalyst, prepared by impregnation using γ-Al₂O₃ as a support, lanthanum as a promoter, and nickel and copper as active components, comprises 40-90% alumina, 1-40% nickel (NiO), 1-30% copper (CuO), and 0.1-10% lanthanum (La₂O₃) by mass. The catalyst exhibits excellent hydrogenation activity and selectivity. However, the use of rare earth elements as modifying materials results in high costs, limiting its industrial application.

[0007] CN102125840A discloses a catalyst for supporting Group VIII elements and alkali metals on carbon and its hydrogenation application. This invention significantly improves catalytic activity by loading active metals onto molecular sieves or activated carbon. However, while noble metals provide good catalytic performance, they are costly. Using non-noble metals results in less than ideal performance and low yields. Furthermore, loading the catalyst also presents problems such as uneven dispersion of the active metal, large particle size, and small metal surface area.

[0008] CN104248964A discloses a method for preparing a hydrodesulfurization catalyst. This method involves impregnating a prepared MoO3 / SiO2-Al2O3 mixed oxide with a Ni(H2PO2)2 solution, then obtaining a supported Ni2P-MoO3 / SiO2-Al2O3 under an argon atmosphere. Following this, in-situ sulfidation treatment using a mixture of H2S and H2 gases yields a Ni2P-MoS2 / SiO2-Al2O3 catalyst, which shows a significantly improved hydrodesulfurization activity. However, the desulfurization activity of this type of transition metal phosphide still needs further improvement and cannot yet meet the requirements of practical applications.

[0009] In summary, the main problems with current hydrodesulfurization catalysts are: single catalyst supports have structural and performance defects, making it impossible to achieve deep refining of inferior diesel fuel; the utilization rate of active metal components is low, and their prices are high, failing to overcome the adsorption-reaction limitations of complex sulfide molecules on existing catalysts. Summary of the Invention

[0010] To address the aforementioned technical problems, the present invention aims to provide a hydrotreating catalyst, its preparation method, and its application. The hydrotreating catalyst exhibits excellent hydrodesulfurization performance and is suitable for the hydrotreating process of petroleum distillate oils, particularly for the deep hydrodesulfurization process of inferior diesel oils.

[0011] This invention is achieved through the following technical solution:

[0012] A hydrogenation catalyst comprises a support and an active component and an auxiliary agent supported on the support, wherein the support is a TiO2-Al2O3 composite oxide with an ordered mesoporous structure; the active component includes an oxide of a Group VIB metal component and a Group VIII metal component, and the auxiliary agent is an oxide of metal Ge or Ga.

[0013] Preferably, the Group VIB metal component is molybdenum or tungsten; the Group VIII metal component is nickel or cobalt.

[0014] Preferably, the TiO2 content in the TiO2-Al2O3 composite oxide is 5% to 40% by mass.

[0015] Preferably, based on the catalyst, the content of the Group VIB metal component, calculated as oxide, is 5 wt% to 30 wt%, the content of the Group VIII metal component, calculated as oxide, is 0.5 wt% to 15 wt%, and the content of the auxiliary agent, calculated as oxide, is 0.5 wt% to 20 wt%.

[0016] The method for preparing the hydrogenation catalyst includes the following steps:

[0017] Step 1: Prepare an ordered mesoporous TiO2-Al2O3 composite oxide support using aluminum source, titanium source, template agent, acid and ethanol as raw materials;

[0018] Step 2: Dissolve the precursor of the active component to obtain an impregnation solution; add the impregnation solution dropwise to the surface of the TiO2-Al2O3 composite oxide support, and then dry it to obtain the TiO2-Al2O3 composite oxide support impregnated with the active component.

[0019] Step 3: Dissolve the precursor of the additive to obtain an impregnation solution; add the impregnation solution dropwise to the surface of the TiO2-Al2O3 composite oxide carrier after the active component has been impregnated, and then dry and calcine.

[0020] Preferably, in step one, the aluminum source is one or more of aluminum isopropoxide, sodium aluminate, aluminum isobutoxide, aluminum tert-butoxide, aluminum nitrate, aluminum chloride, and aluminum sulfate; the titanium source is one or more of titanium isopropoxide, tetrabutyl titanate, methyl titanate, ethyl titanate, titanium oxysulfate, titanium tetrachloride, and barium metatitanate; the acid is one or more of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid; and the template agent is one or more of P123, F127, CTAB, and CTAC.

[0021] Preferably, step one specifically includes:

[0022] (a) Dissolve the aluminum source in ethanol and stir to obtain solution A. Dissolve the template agent in ethanol and stir to obtain solution B. Add the acid dropwise to solution A to obtain solution C. Add solution C dropwise to solution B and stir to obtain solution D. Add the titanium source dropwise to solution D and stir to obtain the initial sol.

[0023] (b) The initial sol described in (a) is aged and then calcined to obtain an ordered mesoporous TiO2-Al2O3 composite oxide.

[0024] Preferably, in step two, the precursor of the active component includes a nickel-containing compound or a molybdenum-containing compound and a tungsten-containing compound or a cobalt-containing compound. The nickel-containing compound is at least one of nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, and nickel chloride. The molybdenum-containing compound is at least one of molybdenum oxide, molybdate, and paramolybdate. The molybdate is at least one of ammonium heptamolybdate tetrahydrate, molybdenum nitrate, and molybdenum sulfate. The tungsten-containing compound is at least one of tungsten oxide, ammonium metatungstate, ammonium tungstate, and ammonium paratungstate. The cobalt-containing compound is at least one of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride.

[0025] Preferably, in step three, the roasting temperature is 300℃~900℃ and the roasting time is 4~8h.

[0026] The application of the aforementioned hydrotreating catalyst in diesel hydrodesulfurization.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] This invention uses aluminum source, titanium source, template agent, acid, and ethanol as raw materials to prepare TiO2-Al2O3 composite oxide support by impregnation method. Under the premise of simple synthesis method and readily available materials, it fully utilizes the advantages of TiO2 and Al2O3 while avoiding the disadvantages of excessively strong MSI on Al2O3-based catalysts, narrow MSI controllability range, and poor TiO2 adhesion. The synthesized TiO2-Al2O3 composite oxide support has an ordered mesoporous structure. As a type of mesoporous material, ordered mesoporous materials have a large specific surface area, relatively large pore size, and regular pore structure, which can handle larger molecules or groups, making them excellent shape-selective catalysts. Especially in catalyzing reactions involving large molecules, ordered mesoporous materials exhibit excellent catalytic activity. This invention uses Ga or Ge to modify the catalyst, modulating the acidity and structural properties of the molecular sieve, thereby improving the desulfurization activity and stability of the catalyst. The following explanation uses the promoter Ge and the active component Mo as examples. Electronic structure analysis of Ge, which has a weak inert pair effect, shows that its outermost electron configuration is 3d... 10 4s 2 4p 2 Under strong oxidizing conditions (in the active phase precursor), this metal atom exists in a high oxidation state with a high coordination number, namely Ge. 4+ It exists stably and can also exist in the oxidation state with a lower coordination number, Ge, under strongly reducing conditions (catalyst sulfidation process). 2+ Stable existence. Therefore, it is foreseeable that doping with this metal at higher oxidation states can introduce acceptor levels into the band gap of the MoS2 semiconductor; while at lower oxidation states, doping with this metal can introduce donor levels into the band gap of the MoS2 semiconductor, thereby affecting the electronic structure of the active phase metal precursor and the active phase. On the other hand, during sulfidation, the oxidation state of the metal additive decreases, and the coordination number decreases accordingly, resulting in a mismatch with the coordination number of the main metal Mo. This causes a break in the MoS2 lamellar at the Ge metal additive doping site, leading to the formation of quasi-corner active sites with electronic structures and geometric structures similar to those of corner active sites. This increases the proportion of corner active sites and quasi-corner active sites without changing the number of stacked layers of the MoS2 lamellar. Therefore, this invention, by doping the catalyst with metal atoms having a weak inert pair effect, guides the formation of quasi-corner active sites with electronic structures and geometric structures similar to those of corner active sites, significantly improving the hydrodesulfurization performance of the prepared catalyst, especially in the hydrogenation process of inferior diesel.

[0029] The preparation process of this invention is simple, efficient, and highly controllable, and has good application prospects in catalysis, adsorption separation and other fields. Attached Figure Description

[0030] Figure 1 is a TEM image of the ordered mesoporous TiO2-Al2O3 composite oxide prepared in Example 3 of the present invention. Detailed Implementation

[0031] To further understand the present invention, the present invention will be described below with reference to embodiments. These descriptions are only for further explaining the features and advantages of the present invention and are not intended to limit the claims of the present invention.

[0032] The hydrotreating catalyst of the present invention comprises a support and an active component and an auxiliary agent supported on the support, wherein the support is a TiO2-Al2O3 composite oxide with an ordered mesoporous structure; the active component includes oxides of at least one Group VIB metal component and at least one Group VIII metal component, and the auxiliary agent is an oxide of metal Ge or Ga. The mass content of TiO2 in the TiO2-Al2O3 composite oxide is 5% to 40%.

[0033] The active component composition of the catalyst of the present invention, based on the catalyst, comprises, as an oxide, a Group VIB metal component of 5 wt% to 30 wt%, more preferably 10 wt% to 15 wt%, a Group VIII metal component of 0.5 wt% to 15 wt%, more preferably 1 wt% to 5 wt%, and an additive of 0.5 to 20 wt%, more preferably 0.5 to 5 wt%.

[0034] The Group VIB metal is molybdenum or tungsten, more preferably molybdenum; the Group VIII metal is nickel or cobalt, more preferably nickel.

[0035] The preparation method of the hydrogenation catalyst of the present invention includes the following steps:

[0036] Step 1: Prepare TiO2-Al2O3 composite oxide with ordered mesoporous structure using aluminum source, titanium source, template agent, acid and ethanol as raw materials;

[0037] Step 2: Dissolve the precursor of the active component to obtain an impregnation solution; add the impregnation solution dropwise to the surface of the TiO2-Al2O3 composite oxide support described in Step 1, and then dry it at a temperature of 60-120°C for 1-14 hours, preferably 4-14 hours.

[0038] Step 3: Dissolve the precursor of the additive to obtain an impregnation solution; add the impregnation solution dropwise to the surface of the TiO2-Al2O3 composite oxide carrier impregnated with the active component as described in Step 2, and then dry and calcine; wherein the drying temperature is 60-20℃, the drying time is 1-14h, more preferably 4-14h; the calcination temperature is 300℃-900℃, more preferably 500℃-800℃, and the calcination time is 4-8h, more preferably 4-6h.

[0039] In step one of this invention, the aluminum source is one or more of aluminum isopropoxide, sodium aluminate, aluminum isobutoxide, aluminum tert-butoxide, aluminum nitrate, aluminum chloride, and aluminum sulfate, preferably aluminum chloride or aluminum isopropoxide; the titanium source is one or more of titanium isopropoxide, tetrabutyl titanate, methyl titanate, ethyl titanate, titanium oxysulfate, titanium tetrachloride, and barium metatitanate, preferably tetrabutyl titanate or titanium tetrachloride. The acid is one or more of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid, preferably hydrochloric acid or nitric acid. The template agent is a mixture of one or more of P123, F127, CTAB, and CTAC, more preferably P123 or F127.

[0040] In step one of this invention, the molar ratio of aluminum source + titanium source, template agent, ethanol, and acid is (0.03-0.5):(0.001-0.005):(0.5-5):(0.03-0.3), wherein the molar ratio of titanium source to aluminum source is 1:(1-20).

[0041] Step one of the present invention specifically includes:

[0042] (a) First, dissolve the template agent in ethanol and stir, and label it as solution A; then dissolve the aluminum source in ethanol and stir, and add the acid solution dropwise, label it as solution B; add solution A to solution B and stir, then add the titanium source and stir to obtain the initial sol;

[0043] (b) The initial sol described in (a) is aged at a temperature of 50–70°C for 24–60 h, and then calcined at a temperature of 400–600°C for 2–6 h to obtain an ordered mesoporous TiO2-Al2O3 composite oxide.

[0044] In step two of this invention, the precursor of the active component includes a nickel-containing compound or a molybdenum-containing compound and a tungsten-containing compound or a cobalt-containing compound. The nickel-containing compound is at least one of nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, and nickel chloride, preferably nickel nitrate hexahydrate. The molybdenum-containing compound is at least one of molybdenum oxide, molybdate, and paramolybdate. The molybdate is ammonium heptamolybdate tetrahydrate, molybdenum nitrate, or molybdenum sulfate, preferably ammonium heptamolybdate tetrahydrate. The tungsten-containing compound is at least one of tungsten oxide, ammonium metatungstate, ammonium tungstate, and ammonium paratungstate. The cobalt-containing compound is at least one of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride.

[0045] In step three of this invention, the precursor of the additive is sodium germanate, germanium tetrachloride, or gallium nitrate, preferably sodium germanate or gallium nitrate.

[0046] The present invention also provides the application of the above-mentioned hydrotreating catalyst, namely, its application in the hydrodesulfurization of inferior diesel fuel.

[0047] The specific implementation method is as follows.

[0048] Raw material sources: Aluminum isopropoxide, tetrabutyl titanate, organic template agent P123 and ammonium heptamolybdate tetrahydrate are all from Shanghai Aladdin Biochemical Technology Co., Ltd., nitric acid and other raw materials are from Sinopharm Chemical Reagent Co., Ltd., ethanol and other raw materials are from Tianjin Fuyu Fine Chemical Co., Ltd., nickel nitrate hexahydrate is from Tianjin Oubokai Chemical Co., Ltd., and sodium germanate is from Beijing Haoke Technology Co., Ltd. All of the above raw materials are industrial products.

[0049] Analytical methods: Transmission electron microscopy images of the material were acquired using a JEOL JEM-2100 field emission transmission electron microscope to characterize the morphology of the material; the sulfur content in the generated oil was determined using a fluorescence sulfur analyzer (RPP-2000S).

[0050] Preparation of TiO2-Al2O3 composite oxide support:

[0051] Example 1

[0052] The raw materials were weighed according to the following formula: the TiO2 content in the TiO2-Al2O3 composite oxide was 5wt%. 3.95g of aluminum isopropoxide was dissolved in 20ml of ethanol and stirred for 4h, denoted as solution A; 4g of P123 was dissolved in 20ml of ethanol and stirred for 4h, denoted as solution B; 3.2ml of nitric acid was added dropwise to solution A and stirred for 15min, denoted as solution C; solution C was added dropwise to solution B and stirred for 2h, denoted as solution D; 0.22g of tetrabutyl titanate was added dropwise to solution D and stirred for 4h to obtain the initial sol; the initial sol was aged at 50℃ for 60h to obtain a pale yellow solid; the pale yellow solid was placed in a muffle furnace and heated to 450℃ at a rate of 1℃ / min and held for 6h to obtain the TiO2-Al2O3 composite oxide support.

[0053] Example 2

[0054] The raw materials were weighed according to the following formula: the TiO2 content in the TiO2-Al2O3 composite oxide was 10wt%. 3.81g of aluminum isopropoxide was dissolved in 20ml of ethanol and stirred for 4h, denoted as solution A; 4g of P123 was dissolved in 20ml of ethanol and stirred for 4h, denoted as solution B; 3.2ml of nitric acid was added dropwise to solution A and stirred for 15min, denoted as solution C; solution C was added dropwise to solution B and stirred for 2h, denoted as solution D; 0.45g of tetrabutyl titanate was added dropwise to solution D and stirred for 4h to obtain the initial sol; the initial sol was aged at 60℃ for 36h to obtain a pale yellow solid; the pale yellow solid was placed in a muffle furnace and heated to 500℃ at a rate of 1℃ / min and held for 5h to obtain the TiO2-Al2O3 composite oxide support.

[0055] Example 3

[0056] The raw materials were weighed according to the requirement that the TiO2 content in the TiO2-Al2O3 composite oxide was 20wt%. 3.52g of aluminum isopropoxide was dissolved in 20ml of ethanol and stirred for 4h, denoted as solution A; 4g of P123 was dissolved in 20ml of ethanol and stirred for 4h, denoted as solution B; 3.2ml of nitric acid was added dropwise to solution A and stirred for 15min, denoted as solution C; solution C was added dropwise to solution B and stirred for 2h, denoted as solution D; 0.94g of tetrabutyl titanate was added dropwise to solution D and stirred for 4h to obtain the initial sol; the initial sol was aged at 60℃ for 48h to obtain a pale yellow solid; the pale yellow solid was placed in a muffle furnace and heated to 550℃ at a rate of 1℃ / min and held for 4h to obtain the TiO2-Al2O3 composite oxide support.

[0057] The TEM image of the TiO2-Al2O3 composite oxide support prepared in this embodiment is shown in Figure 1.

[0058] Example 4

[0059] The raw materials were weighed according to the following formula: the TiO2 content in the TiO2-Al2O3 composite oxide was 40wt%. 2.87g of aluminum isopropoxide was dissolved in 20ml of ethanol and stirred for 4h, denoted as solution A; 4g of P123 was dissolved in 20ml of ethanol and stirred for 4h, denoted as solution B; 3.2ml of nitric acid was added dropwise to solution A and stirred for 15min, denoted as solution C; solution C was added dropwise to solution B and stirred for 2h, denoted as solution D; 2.03g of tetrabutyl titanate was added dropwise to solution D and stirred for 4h to obtain the initial sol; the initial sol was aged at 70℃ for 24h to obtain a pale yellow solid; the pale yellow solid was placed in a muffle furnace and heated to 600℃ at a rate of 1℃ / min and held for 2h to obtain the TiO2-Al2O3 composite oxide support.

[0060] Preparation of Ge-containing hydrogenation catalysts:

[0061] Example 5

[0062] The Ge-containing hydrogenation catalyst of this embodiment includes a TiO2-Al2O3 composite oxide support and Ni, Mo and Ge active components supported on the support.

[0063] The preparation methods specifically include:

[0064] Step 1: Weigh the raw materials to ensure a total NiO loading of 1 wt% and a total MoO3 loading of 15 wt% in the final catalyst, based on oxides and catalyst. Add 0.389 g of nickel nitrate hexahydrate (Ni(NO3)2·6H2O) and 1.839 g of ammonium heptamolybdate tetrahydrate (NH4)6Mo7O 24 Dissolve the TiO2-Al2O3 composite oxide carrier described in Example 3 by dissolving it in 4H2O, and then mix it to obtain an impregnation solution; weigh 8.4g of the TiO2-Al2O3 composite oxide carrier described in Example 3, and add the impregnation solution dropwise to the surface of the carrier; dry it in the dark for 12h, then dry it at 60℃ for 6h, and then dry it at 120℃ for 12h.

[0065] Step 2: Weigh the raw materials to achieve a total GeO2 loading of 1 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.1592 g of sodium germanate (Na2GeO3) to obtain an impregnation solution; weigh 9.9 g of the NiMo-impregnated TiO2-Al2O3 composite oxide support from Step 1, and add the impregnation solution dropwise to the support surface; dry in the dark for 12 h, then dry at 60 °C for 6 h, and then dry at 120 °C for 12 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min and hold for 4 h to obtain the Ge1-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0066] Example 6

[0067] The Ge-containing hydrogenation catalyst of this embodiment includes a TiO2-Al2O3 composite oxide support and Ni, Mo and Ge active components supported on the support.

[0068] The preparation methods specifically include:

[0069] Step 1: Weigh the raw materials to ensure that the total NiO loading in the final catalyst is 2 wt% and the total MoO3 loading is 14 wt%, based on oxides and catalyst. Add 0.778 g of Ni(NO3)2·6H2O and 1.716 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.4g of the TiO2-Al2O3 composite oxide carrier described in Example 3 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 8 hours, and then dry it at 120°C for 10 hours.

[0070] Step 2: Weigh the raw materials to achieve a total GeO2 loading of 1 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.1592 g of Na2GeO3 to obtain an impregnation solution; weigh 9.9 g of the NiMo-impregnated TiO2-Al2O3 composite oxide support from Step 1, and add the impregnation solution dropwise to the support surface; dry in the dark for 12 h, then dry at 60 °C for 8 h, and then dry at 120 °C for 10 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min and hold for 4 h to obtain the Ge1-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0071] Example 7

[0072] The Ge-containing hydrogenation catalyst of this embodiment includes a TiO2-Al2O3 composite oxide support and Ni, Mo and Ge active components supported on the support.

[0073] The preparation methods specifically include:

[0074] Step 1: Weigh the raw materials to achieve a total NiO loading of 3 wt% and a total MoO3 loading of 13 wt% in the final catalyst, based on oxides and catalyst. Add 1.167 g of Ni(NO3)2·6H2O and 1.594 g of (NH4)6Mo7O 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.4g of the TiO2-Al2O3 composite oxide carrier described in Example 3 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 10 hours, and then dry it at 120°C for 8 hours.

[0075] Step 2: Weigh the raw materials to achieve a total GeO2 loading of 2 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.3184 g of Na2GeO3 to obtain an impregnation solution; weigh 9.6816 g of the NiMo-impregnated TiO2-Al2O3 composite oxide support from Step 1, and add the impregnation solution dropwise to the support surface; dry in the dark for 12 h, then dry at 60 °C for 10 h, and then dry at 120 °C for 8 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min and hold for 5 h to obtain the Ge3-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0076] Example 8

[0077] The Ge-containing hydrogenation catalyst of this embodiment includes a TiO2-Al2O3 composite oxide support and Ni, Mo and Ge active components supported on the support.

[0078] The preparation methods specifically include:

[0079] Step 1: Weigh the raw materials to achieve a total NiO loading of 4 wt% and a total MoO3 loading of 12 wt% in the final catalyst, based on oxides and catalyst. Add 1.556 g of Ni(NO3)2·6H2O and 1.471 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.4g of the TiO2-Al2O3 composite oxide carrier described in Example 3 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 12 hours, and then dry it at 120°C for 6 hours.

[0080] Step 2: Weigh the raw materials to achieve a total GeO2 loading of 2 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.3184 g of Na2GeO3 to obtain an impregnation solution; weigh 9.6816 g of the NiMo-impregnated TiO2-Al2O3 composite oxide support from Step 1, and add the impregnation solution dropwise to the surface of the support; dry in the dark for 12 h, then dry at 60 °C for 12 h, and then dry at 120 °C for 6 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min and hold for 5 h to obtain the Ge4-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0081] Example 9

[0082] The Ge-containing hydrogenation catalyst of this embodiment includes a TiO2-Al2O3 composite oxide support and Ni, Mo and Ge active components supported on the support.

[0083] The preparation methods specifically include:

[0084] Step 1: Weigh the raw materials to achieve a total NiO loading of 5 wt% and a total MoO3 loading of 11 wt% in the final catalyst, based on oxides and catalyst. Add 1.945 g of Ni(NO3)2·6H2O and 1.349 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.4g of the TiO2-Al2O3 composite oxide carrier described in Example 3 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 14 hours, and then dry it at 120°C for 4 hours.

[0085] Step 2: Weigh the raw materials to achieve a total GeO2 loading of 4 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.6368 g of Na2GeO3 to obtain an impregnation solution; weigh 9.3632 g of the NiMo-impregnated TiO2-Al2O3 composite oxide support from Step 1, and add the impregnation solution dropwise to the support surface; dry in the dark for 12 h, then dry at 60 °C for 14 h, and then dry at 120 °C for 4 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min and hold for 6 h to obtain the Ge4-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0086] Example 10

[0087] The Ge-containing hydrogenation catalyst of this embodiment includes a TiO2-Al2O3 composite oxide support and Ni, Mo and Ge active components supported on the support.

[0088] The preparation methods specifically include:

[0089] Step 1: Weigh the raw materials to ensure a total NiO loading of 6 wt% and a total MoO3 loading of 10 wt% in the final catalyst, based on oxides and catalyst. Take 2.334 g of Ni(NO3)2·6H2O and 1.226 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.4g of the TiO2-Al2O3 composite oxide carrier described in Example 3 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 14 hours, and then dry it at 120°C for 4 hours.

[0090] Step 2: Weigh the raw materials to achieve a total GeO2 loading of 4 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.6368 g of Na2GeO3 to obtain an impregnation solution; weigh 9.3632 g of the NiMo-impregnated TiO2-Al2O3 composite oxide support from Step 1, and add the impregnation solution dropwise to the support surface; dry in the dark for 12 h, then dry at 60 °C for 14 h, and then dry at 120 °C for 4 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min and hold for 6 h to obtain the Ge4-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0091] Example 11

[0092] The Ge-containing hydrogenation catalyst of this embodiment includes a TiO2-Al2O3 composite oxide support and Ni, Mo and Ge active components supported on the support.

[0093] The preparation methods specifically include:

[0094] Step 1: Weigh the raw materials to achieve a total NiO loading of 4 wt% and a total MoO3 loading of 12 wt% in the final catalyst, based on oxides and catalyst. Add 1.556 g of Ni(NO3)2·6H2O and 1.471 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.4g of the TiO2-Al2O3 composite oxide carrier described in Example 3 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 12 hours, and then dry it at 120°C for 6 hours.

[0095] Step 2: Weigh the raw materials to achieve a total GeO2 loading of 1 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.1592 g of Na2GeO3 to obtain an impregnation solution; weigh 9.9 g of the NiMo-impregnated TiO2-Al2O3 composite oxide support from Step 1, and add the impregnation solution dropwise onto the support surface; dry in the dark for 12 h, then dry at 60 °C for 12 h, and then dry at 120 °C for 6 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min and hold for 5 h to obtain the Ge1-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0096] Example 12

[0097] The Ge-containing hydrogenation catalyst of this embodiment includes a TiO2-Al2O3 composite oxide support and Ni, Mo and Ge active components supported on the support.

[0098] The preparation methods specifically include:

[0099] Step 1: Weigh the raw materials to achieve a total NiO loading of 4 wt% and a total MoO3 loading of 12 wt% in the final catalyst, based on oxides and catalyst. Add 1.556 g of Ni(NO3)2·6H2O and 1.471 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.4g of the TiO2-Al2O3 composite oxide carrier described in Example 3 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 12 hours, and then dry it at 120°C for 6 hours.

[0100] Step 2: Weigh the raw materials to achieve a total GeO2 loading of 4 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.6368 g of Na2GeO3 to obtain an impregnation solution; weigh 9.3632 g of the NiMo-impregnated TiO2-Al2O3 composite oxide support from Step 1, and add the impregnation solution dropwise to the support surface; dry in the dark for 12 h, then dry at 60 °C for 12 h, and then dry at 120 °C for 6 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min and hold for 5 h to obtain the Ge4-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0101] Comparative Example 1

[0102] This comparative example provides a hydrogenation catalyst, comprising a TiO2-Al2O3 composite oxide support and Ni and Mo active components supported on the support.

[0103] The preparation methods specifically include:

[0104] The raw materials were weighed to achieve a total NiO loading of 4 wt% and a total MoO3 loading of 12 wt% in the final catalyst, based on oxides and catalyst reference. 1.556 g of Ni(NO3)2·6H2O and 1.471 g of (NH4)6Mo7O were then weighed. 24 Dissolve the material in 4H2O and mix it to obtain an impregnation solution. Weigh 8.4g of the TiO2-Al2O3 composite oxide support described in Example 3 and add the impregnation solution dropwise to the surface of the support. Dry it in the dark for 12h, then dry it at 60℃ for 12h, and then dry it at 120℃ for 6h. Finally, place it in a muffle furnace and heat it to 550℃ at a rate of 1℃ / min and hold it for 5h to obtain the NiMo / TiO2-Al2O3 hydrogenation treatment catalyst.

[0105] Application Example 1

[0106] The prepared hydrotreating catalyst was applied to the hydrodesulfurization reaction of inferior diesel oil (sulfur content 1350 μg / g) under the conditions of reaction temperature 290℃, hydrogen pressure 4MPa, hydrogen-to-oil ratio 150, and mass hourly space velocity 5.

[0107] After the hydrodesulfurization reaction, samples were taken for sulfur content determination. The sulfur content in the product oil was determined using a fluorescence sulfur analyzer (RPP-2000S), and the desulfurization rate was calculated. The results are listed in Table 1.

[0108] The catalytic activity results (Table 1) show that, compared with the catalyst without Ge promoter (Comparative Example 1), a series of Ge-modified Ge catalysts... nThe hydrodesulfurization activity of the NiMo / TiO2-Al2O3 catalyst was significantly improved, and the sulfur content of the product could be increased from 29.95 μg·g. -1 Significantly reduced to 6.44 μg·g -1 This indicates that the introduction of Ge additive can effectively improve desulfurization efficiency. Furthermore, the catalytic activity is also related to the NiO loading content. When the GeO2 loading is low (1 wt%), the catalytic activity increases with increasing NiO loading (Examples 5-8 and 11); when NiO increases to 4 wt%, the best catalytic performance is obtained, with the product sulfur content being approximately 5 times that of Comparative Example 1 and approximately 1.4 times that of the low NiO content (1 wt%, Example 5). However, excessive introduction of Ge additive and excessive loading of NiO have a negative impact on catalytic performance (Examples 10 and 9), but it is still superior to Comparative Example 1, approximately 3 times that of Comparative Example 1.

[0109] Table 1. Catalyst Hydrodesulfurization Performance Data

[0110]

[0111] Example 13

[0112] The raw materials were weighed according to a titanium source to aluminum source molar ratio of 1:19. 3.96 g of aluminum isopropoxide was dissolved in 20 ml of ethanol and stirred for 4 h. 2 ml of hydrochloric acid was added dropwise and stirred for 15 min, and this solution was labeled as solution A. 2 g of F127 was dissolved in 10 ml of ethanol and stirred for 4 h, and this solution was labeled as solution B. Solution A was added dropwise to solution B and stirred for 2 h. Then, 0.22 g of tetrabutyl titanate was added dropwise and stirred for 4 h. The resulting solution was aged at 50 °C for 60 h to obtain a pale yellow solid. The pale yellow solid was placed in a muffle furnace and heated to 500 °C at a rate of 1 °C / min and held for 6 h to obtain the TiO2-Al2O3 composite oxide support.

[0113] Example 14

[0114] The raw materials were weighed according to a titanium source to aluminum source molar ratio of 1:9. 3.81 g of aluminum isopropoxide was dissolved in 20 ml of ethanol and stirred for 4 h. 1.6 ml of hydrochloric acid was added dropwise and stirred for 15 min, resulting in solution A. 2 g of P123 was dissolved in 10 ml of ethanol and stirred for 4 h, resulting in solution B. Solution A was added dropwise to solution B and stirred for 2 h. Then, 0.45 g of tetrabutyl titanate was added dropwise and stirred for 4 h. The resulting solution was aged at 50 °C for 12 h to obtain a pale yellow solid. The pale yellow solid was placed in a muffle furnace and heated to 450 °C at a rate of 1 °C / min, and held for 4 h to obtain the TiO2-Al2O3 composite oxide support.

[0115] Example 15

[0116] The raw materials were weighed according to a titanium source to aluminum source molar ratio of 2:8. 3.52 g of aluminum isopropoxide was dissolved in 20 ml of ethanol and stirred for 4 h. Then, 3.2 ml of nitric acid was added dropwise and stirred for 15 min, and this solution was labeled as solution A. 4 g of P123 was dissolved in 20 ml of ethanol and stirred for 4 h, and this solution was labeled as solution B. Solution A was added dropwise to solution B and stirred for 2 h. Then, 0.94 g of tetrabutyl titanate was added dropwise and stirred for 4 h. The resulting solution was aged at 60 °C for 48 h to obtain a pale yellow solid. The pale yellow solid was placed in a muffle furnace and heated to 550 °C at a rate of 1 °C / min and held for 4 h to obtain the TiO2-Al2O3 composite oxide support.

[0117] Example 16

[0118] The raw materials were weighed according to a titanium source to aluminum source molar ratio of 4:6. 1.87g of aluminum chloride was dissolved in 20ml of ethanol and stirred for 4h. 3.2ml of hydrochloric acid was added dropwise and stirred for 15min, and this was recorded as solution A. 1g of F127 was dissolved in 10ml of ethanol and stirred for 4h, and this was recorded as solution B. Solution A was added dropwise to solution B and stirred for 2h. Then, 2.03g of tetrabutyl titanate was added dropwise and stirred for 4h. The resulting solution was aged at 65℃ for 48h to obtain a pale yellow solid. The pale yellow solid was placed in a muffle furnace and heated to 600℃ at a rate of 1℃ / min and held for 4h to obtain the TiO2-Al2O3 composite oxide support.

[0119] Example 17

[0120] The raw materials were weighed according to a titanium source to aluminum source molar ratio of 3:7. 2.64 g of aluminum isopropoxide was dissolved in 20 ml of ethanol and stirred for 4 h. 3.2 ml of hydrochloric acid was added dropwise and stirred for 15 min, and this solution was designated as solution A. 2 g of P123 was dissolved in 10 ml of ethanol and stirred for 4 h, and this solution was designated as solution B. Solution A was added dropwise to solution B and stirred for 2 h. Then, 1.34 g of titanium tetrachloride was added dropwise and stirred for 4 h. The resulting solution was aged at 55 °C for 24 h to obtain a pale yellow solid. The pale yellow solid was placed in a muffle furnace and heated to 450 °C at a rate of 1 °C / min and held for 5 h to obtain the TiO2-Al2O3 composite oxide support.

[0121] Weigh 20g of each of the five supports obtained in the above examples, and impregnate them with active metals Ni and Mo in equal volumes to prepare a Ga-containing hydrogenation catalyst. The specific method is as follows.

[0122] Example 18

[0123] Step 1: Based on the catalyst, weigh the raw materials with a NiO content of 1 wt% and a MoO3 content of 5 wt% (calculated as oxides). Separately weigh 0.39 g of nickel nitrate hexahydrate (Ni(NO3)2·6H2O) and 0.60 g of ammonium heptamolybdate tetrahydrate (NH4)6Mo7O. 24 Dissolve the titanium-aluminum composite oxide carrier described in Example 13 by dissolving it in 4H2O, and then mix it to obtain an impregnation solution; weigh 9.01g of the titanium-aluminum composite oxide carrier described in Example 13, and add the impregnation solution dropwise to the surface of the carrier; dry it in the dark for 12h, then dry it at 60℃ for 4h, and then dry it at 110℃ for 10h.

[0124] Step 2: Weigh the raw materials to achieve a total Ga2O3 loading of 0.5 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.14 g of gallium nitrate (Ga(NO3)3) to obtain an impregnation solution; weigh 9.86 g of the NiMo-impregnated titanium-aluminum composite oxide support from Step 1, and add the impregnation solution dropwise to the support surface; dry in the dark for 12 h, then dry at 60 °C for 4 h, and then dry at 110 °C for 10 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min, holding for 6 h to obtain Ga2O3. 0.5 -NiMo / TiO2-Al2O3 hydrogenation treatment catalyst.

[0125] Example 19

[0126] Step 1: Based on the catalyst, weigh the raw materials with a NiO content of 3 wt% and a MoO3 content of 10 wt% (calculated as oxides). Take 1.17 g of Ni(NO3)2·6H2O and 1.23 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 7.60g of the titanium-aluminum composite oxide carrier described in Example 14 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 6 hours, and then dry it at 100°C for 8 hours.

[0127] Step 2: Weigh the raw materials to achieve a total Ga2O3 loading of 2wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.54g of gallium nitrate (Ga(NO3)3) to obtain an impregnation solution; weigh 9.46g of the NiMo-impregnated titanium-aluminum composite oxide support from Step 1, and add the impregnation solution dropwise onto the support surface; dry in the dark for 12h, then at 60℃ for 6h, and then at 100℃ for 8h; finally, place it in a muffle furnace and heat it to 500℃ at a rate of 1℃ / min and hold for 4h to obtain the Ga2-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0128] Example 20

[0129] Step 1: Based on the catalyst, weigh the raw materials with a NiO content of 4 wt% and a MoO3 content of 12 wt% (based on oxides). Take 1.56 g of Ni(NO3)2·6H2O and 1.47 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.40g of the titanium-aluminum composite oxide carrier described in Example 15 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 12 hours, and then dry it at 120°C for 12 hours.

[0130] Step 2: Weigh the raw materials to achieve a total Ga2O3 loading of 1 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.27 g of gallium nitrate (Ga(NO3)3) to obtain an impregnation solution; weigh 9.73 g of the NiMo-impregnated titanium-aluminum composite oxide support from Step 1, and add the impregnation solution dropwise onto the support surface; dry in the dark for 12 h, then at 60 °C for 6 h, followed by drying at 120 °C for 6 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min, holding for 4 h to obtain the Ga1-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0131] Example 21

[0132] Step 1: Based on the catalyst, weigh the raw materials with a NiO content of 5 wt% and a MoO3 content of 15 wt% (calculated as oxides). Take 1.95 g of Ni(NO3)2·6H2O and 1.84 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 6.21g of the titanium-aluminum composite oxide carrier described in Example 16 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 8 hours, and then dry it at 120°C for 8 hours.

[0133] Step 2: Weigh the raw materials to achieve a total Ga2O3 loading of 4 wt% in the final catalyst, based on oxides and catalyst. Dissolve 1.09 g of gallium nitrate (Ga(NO3)3) to obtain an impregnation solution; weigh 8.91 g of the NiMo-impregnated titanium-aluminum composite oxide support from Step 1, and add the impregnation solution dropwise onto the support surface; dry in the dark for 12 h, then at 60 °C for 10 h, and then at 110 °C for 10 h; finally, place it in a muffle furnace and heat it to 500 °C at a rate of 1 °C / min and hold for 6 h to obtain the Ga4-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0134] Example 22

[0135] Step 1: Based on the catalyst, weigh the raw materials with a NiO content of 4 wt% and a MoO3 content of 10 wt% (calculated as oxides). Take 1.56 g of Ni(NO3)2·6H2O and 1.23 g of (NH4)6Mo7O. 24 Dissolve the substrate in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 7.21g of the titanium-aluminum composite oxide carrier described in Example 17 and add the impregnation solution dropwise to the surface of the carrier. Dry the substrate in the dark for 12 hours, then dry it at 60°C for 10 hours, and then dry it at 120°C for 10 hours.

[0136] Step 2: Weigh the raw materials to achieve a total Ga2O3 loading of 2wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.54g of gallium nitrate (Ga(NO3)3) to obtain an impregnation solution; weigh 9.46g of the NiMo-impregnated titanium-aluminum composite oxide support from Step 1, and add the impregnation solution dropwise onto the support surface; dry in the dark for 12h, then at 60℃ for 5h, followed by drying at 120℃ for 5h; finally, place it in a muffle furnace and heat it to 550℃ at a rate of 1℃ / min, holding for 6h to obtain the Ga2-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0137] To further investigate the effects of changing the support material and introducing Ga as a promoter on catalyst performance, two comparative examples were established, keeping the content of the metal active component constant. The specific steps are as follows:

[0138] Comparative Example 2

[0139] The preparation of a Ga-free hydrotreating catalyst is as follows: Based on the catalyst, the raw materials are weighed with a NiO content of 4 wt% and a MoO3 content of 12 wt% (based on oxides). 1.56 g of Ni(NO3)2·6H2O and 1.47 g of (NH4)6Mo7O are... 24 Dissolve the catalyst in 4H2O and mix the dissolved catalyst to obtain an impregnation solution. Weigh 8.40g of the titanium-aluminum composite oxide support described in Example 15 and add the impregnation solution dropwise to the surface of the support. Dry the catalyst in the dark for 12h, then dry it at 60℃ for 12h, and then dry it at 120℃ for 12h. Finally, place the catalyst in a muffle furnace and heat it to 550℃ at a rate of 1℃ / min and hold it for 4h to obtain the NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0140] Comparative Example 3

[0141] A Ga-containing hydrogenation catalyst was prepared using γ-Al₂O₃ as the support. The specific steps are as follows: Step 1: Based on the catalyst, the raw materials were weighed with a NiO content of 4 wt% and a MoO₃ content of 12 wt% (based on oxides). 1.56 g of Ni(NO₃)₂·6H₂O and 1.47 g of (NH₄)₆Mo₇O₇ were added. 24 Dissolve the γ-Al2O3 support in 4H2O and mix the solutions to obtain an impregnation solution. Weigh 8.40g of γ-Al2O3 support and add the impregnation solution dropwise to the surface of the support. Dry the support in the dark for 12h, then dry it at 60℃ for 12h, and then dry it at 120℃ for 12h.

[0142] Step 2: Weigh the raw materials to achieve a total Ga2O3 loading of 1 wt% in the final catalyst, based on oxides and catalyst. Dissolve 0.27 g of gallium nitrate (Ga(NO3)3) to obtain an impregnation solution; weigh 9.73 g of the NiMo-impregnated titanium-aluminum composite oxide support from Step 1, and add the impregnation solution dropwise onto the support surface; dry in the dark for 12 h, then at 60 °C for 6 h, followed by drying at 120 °C for 6 h; finally, place it in a muffle furnace and heat it to 550 °C at a rate of 1 °C / min, holding for 4 h to obtain the Ga1-NiMo / TiO2-Al2O3 hydrogenation catalyst.

[0143] Application Example 2

[0144] Using low-quality diesel oil (sulfur content 1620 μg / g) as feedstock, the catalytic performance of the above eight catalysts was evaluated in a fixed-bed hydrotreating microreactor. The catalyst loading was 2 ml, and the reaction conditions were: temperature 340℃, pressure 4 MPa, hydrogen-to-oil volume ratio 150, and volume hourly space velocity 20 h⁻¹. -1 Before catalytic evaluation, the catalyst needs to be pre-sulfurized. The sulfidation conditions are: temperature 320℃, pressure 4MPa, sulfidation time 5h, hydrogen-to-oil ratio 100, and volumetric hourly space velocity 10h⁻¹. -1 The results of the desulfurization performance of the obtained catalysts on low-quality diesel oil are summarized in Table 2.

[0145] Table 2. Evaluation results of hydrodesulfurization performance

[0146]

[0147]

[0148] According to the evaluation results of hydrodesulfurization performance (Table 2), the desulfurization rate (Examples 18-22) exhibits a volcano-like trend of first increasing and then decreasing with the increase of Ti:Al ratio and Ga dopant content. The optimal desulfurization rate (99.85%) was obtained when the Ti:Al ratio was 2:8 and the Ge content was 4 wt%, approximately 1.1 times that of γ-Al₂O₃. When the Ti:Al ratio was 4:6 and the Ge content was 4 wt%, the desulfurization rate decreased to 99.12%, but was still better than γ-Al₂O₃ (94.32%). This indicates that the desulfurization rate is affected not only by the Ga dopant content but also by the Ti:Al ratio. Furthermore, unilateral adjustment of the Ti:Al ratio can also effectively improve the desulfurization rate (94.32% (Comparative Example 3) → 96.57% (Comparative Example 2)), indicating that the supported hydrodesulfurization catalyst formed by loading the NiMo active phase on the TiO2-Al2O3 composite oxide support synthesized in this invention has a better desulfurization efficiency than Comparative Example 3, but its ability to improve the desulfurization rate is limited and not as good as the catalyst containing Ga promoter (Examples 18-22).

[0149] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent changes made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing a hydrogenation catalyst, characterized in that, The hydrogenation catalyst comprises a support and an active component and an additive supported on the support, wherein the support is a TiO2-Al2O3 composite oxide with an ordered mesoporous structure; the active component includes oxides of molybdenum and nickel, and the additive is an oxide of metallic Ge or Ga; based on the catalyst, the content of molybdenum, calculated as oxides, is 10wt%~15wt%, the content of nickel, calculated as oxides, is 1wt%~5wt%, and the content of the additive, calculated as oxides, is 1wt%; the catalyst includes the following steps: Step 1, preparing the catalyst using aluminum source, titanium source, template agent, acid, and ethanol as raw materials. The TiO2-Al2O3 composite oxide support has an ordered mesoporous structure; the molar ratio of titanium source to aluminum source is 2:8; Step 2: Dissolve the precursor of the active component to obtain an impregnation solution; add the impregnation solution dropwise to the surface of the TiO2-Al2O3 composite oxide support, and then dry it to obtain the TiO2-Al2O3 composite oxide support impregnated with the active component; Step 3: Dissolve the precursor of the auxiliary agent to obtain an impregnation solution; add the impregnation solution dropwise to the surface of the TiO2-Al2O3 composite oxide support impregnated with the active component, and then dry and calcine it.

2. The method for preparing the hydrogenation catalyst according to claim 1, characterized in that, In step one, the aluminum source is one or more of aluminum isopropoxide, sodium aluminate, aluminum isobutoxide, aluminum tert-butoxide, aluminum nitrate, aluminum chloride, and aluminum sulfate; the titanium source is one or more of titanium isopropoxide, tetrabutyl titanate, methyl titanate, ethyl titanate, titanium oxysulfate, titanium tetrachloride, and barium metatitanate; the acid is one or more of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid; and the template agent is one or more of P123, F127, CTAB, and CTAC.

3. The method for preparing the hydrogenation catalyst according to claim 1, characterized in that, Step one specifically includes: (a) dissolving the aluminum source in ethanol and stirring to obtain solution A; dissolving the template agent in ethanol and stirring to obtain solution B; adding acid dropwise to solution A to obtain solution C; adding solution C dropwise to solution B and stirring to obtain solution D; adding the titanium source dropwise to solution D and stirring to obtain the initial sol; (b) aging the initial sol described in (a) and then calcining it to obtain an ordered mesoporous TiO2-Al2O3 composite oxide.

4. The method for preparing the hydrogenation catalyst according to claim 1, characterized in that, In step two, the precursor of the active component includes a nickel-containing compound and a molybdenum-containing compound. The nickel-containing compound is at least one of nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, and nickel chloride. The molybdenum-containing compound is at least one of molybdenum oxide, molybdate, and secondary molybdate. The molybdate is at least one of ammonium heptamolybdate tetrahydrate, molybdenum nitrate, and molybdenum sulfate.

5. The method for preparing the hydrogenation catalyst according to claim 1, characterized in that, In step three, the roasting temperature is 300℃~900℃ and the roasting time is 4~8h.

6. The hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 5.

7. The hydrotreating catalyst according to claim 6, characterized in that, The TiO2 content in the TiO2-Al2O3 composite oxide is 5%~40% by mass.

8. The hydrotreating catalyst according to claim 6, characterized in that, Based on the catalyst, the content of molybdenum, calculated as oxide, is 10wt% to 15wt%, the content of nickel, calculated as oxide, is 1wt% to 5wt%, and the content of additives, calculated as oxide, is 1wt%.

9. The application of the hydrotreating catalyst according to claim 6 in diesel hydrodesulfurization.

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