Hydrodesulfurization catalyst, method for preparing the same, and use thereof

Abstract

The present application relates to a kind of hydrodesulfurization catalyst and its preparation method and application, it is related to the field of hydrodesulfurization catalyst, the catalyst includes carrier and active metal component supported on the carrier, the carrier is nanoflower spherical catalyst carrier f-TiO2@BNO.Compared with prior art the present application provides a kind of high activity hydrodesulfurization catalyst, with f-TiO2@BNO as catalyst carrier, with highly exposed surface, there is strong interaction between active metal, it is favorable to the load of active metal, can give full play to the catalytic activity of active metal and ensure its catalytic stability;And can prevent H2S adsorption, promote hydrogenation reaction to proceed;Using the hydrodesulfurization catalyst of the present application, can under the condition of low temperature (<300 ℃), normal pressure, low hydrogen concentration (1%~3%), to the sulfur component such as methyl mercaptan, carbonyl sulfur in natural gas, carry out rapid hydrodesulfurization, conversion rate reaches more than 90%, and catalyst need not be presulfurized treatment.

Description

Technical Field

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

[0002] Natural gas is the world's most important gaseous fossil fuel, playing an increasingly vital role in the energy consumption structures of various countries. However, natural gas often contains gaseous sulfides such as hydrogen sulfide (H2S) and organic sulfur compounds, including carbon disulfide (CS2), carbonyl sulfide (COS), mercaptans (RSH), sulfides (RSR′), and disulfides (RSSR′). These sulfides are toxic, have a strong odor, and are corrosive, not only affecting the service life of natural gas extraction equipment but also contributing to the formation of sulfur oxides (SO4) during subsequent combustion. x This will cause significant air pollution. In the natural gas chemical and purification process, natural gas must undergo desulfurization treatment; therefore, accurate analysis of the sulfide content in natural gas is of great importance for natural gas purification.

[0003] Hydrogen sulfide gas detection technology is mature, and a series of hydrogen sulfide gas detectors with convenient operation, low investment cost, fast response speed, and high test accuracy are available on the market, which can be directly used for accurate analysis of hydrogen sulfide content in natural gas. Simultaneously, by catalytically hydrogenating organic sulfur in natural gas to convert it into hydrogen sulfide and alkanes (e.g., RSR'+H2→RH+R'H+H2S), the content of organic sulfur in natural gas can be indirectly determined. However, due to the complex composition of natural gas and the diverse types of organic sulfur, despite significant progress in the catalytic hydrogenation conversion of organic sulfur in natural gas, and the development of various hydrogenation catalysts, the conversion rate of organic sulfur is still generally low, making real-time online detection difficult. Furthermore, the activity of catalysts decays significantly over long-term use, significantly affecting detection accuracy and result reproducibility. How to improve catalytic hydrogenation efficiency and achieve high-efficiency conversion of sulfides (conversion rate >90%) remains a pressing problem and a technological bottleneck in this field.

[0004] Current hydrodesulfurization catalysts are mainly used in petroleum desulfurization processes, primarily involving liquid-phase reactions, while research on natural gas gas molecules is scarce. Commonly used hydrodesulfurization catalysts typically require pre-sulfurization and high temperature and pressure to achieve the desulfurization conversion of sulfur-containing components. Currently reported catalysts mainly consist of Pd, Pt metals or Co-Mo, Ni-Mo, Ni-W, Ni-Co-Mo composite metals or metal sulfides supported on various porous supports (such as silica and alumina), with organic sulfur catalyzing at the metal center. Summarizing the various supported hydrogenation catalysts reported in recent years, it is not difficult to find that they generally have the following shortcomings: (1) The supports used are generally porous and have a large specific surface area, but their pore size is often small (<10nm). A large number of active components exist inside the pores, which is not conducive to the contact of the guest and will affect the timely transfer and diffusion of the product, resulting in a low conversion rate of the reaction; (2) The active components are often loaded by impregnation-calcination process, and their particle size is large and unevenly distributed, making it difficult to exert ideal catalytic activity. Moreover, the binding force between the active components and the support is often weak, and they are easy to fall off under typical hydrogenation reaction conditions (300℃, high pressure), making it difficult to ensure the long-term stability of the catalyst; (3) The low electronegativity of Al in the alumina support is conducive to the shift of electrons to the active components, resulting in high catalytic hydrogenation activity. However, the alkaline nature of alumina makes it easy to accumulate acidic H2S products, which is not conducive to the forward reaction; Silica is an acidic oxide and will not retain H2S, but the high electronegativity of Si is not conducive to the activation of the active components.

[0005] Existing technologies have disclosed methods and applications for preparing nano-flower-shaped titanium dioxide as a catalyst support, or oxygen-doped boron nitride as a catalyst support. For example, patent CN1272398A discloses the application of a TiO2-supported catalyst in the hydrogenation conversion of organic sulfur in natural gas; the literature "Polar bonds induced strong Pd-support electronic interaction drives remarkably enhanced oxygen reduction activity and stability" discloses the application of Pd / p-BNO catalysts in oxygen reduction reactions; patent CN115084555A discloses a ruthenium catalyst supported by a carbon-coated flower-shaped titanium dioxide / titanium dioxide heterostructure; and patent CN107774292A discloses a method for preparing a metal-supported catalyst on an oxygen-doped boron nitride catalyst support. In the prior art, TiO2 is a commonly used support for the hydrogenation conversion of organic sulfur in natural gas, while oxygen-doped boron nitride materials are mostly used in photocatalytic reactions. Therefore, there is an urgent need to develop a novel hydrodesulfurization catalyst for gas-phase reactions of natural gas. Summary of the Invention

[0006] The technical problem to be solved by this invention is to provide a hydrodesulfurization catalyst, its preparation method, and its application. The aim is to provide a highly efficient catalyst for the conversion and degradation of sulfur-containing components in natural gas under mild reaction conditions, specifically for gas-phase reactions of natural gas.

[0007] The technical solution of the present invention to solve the above-mentioned technical problems is as follows:

[0008] In a first aspect, there is a hydrodesulfurization catalyst, the catalyst comprising a support and an active metal component supported on the support, wherein the support is a nano-flower-shaped catalyst support f-TiO2@BNO.

[0009] The beneficial effects of this invention are:

[0010] (1) The present invention uses oxygen-doped boron nitride (BNO) and nano-flower-shaped titanium dioxide (f-TiO2) materials with highly exposed surfaces to prepare catalyst support f-TiO2@BNO, which is not only beneficial to the loading of active metals, but also ensures rapid guest mass transfer.

[0011] (2) The catalyst support f-TiO2@BNO of the present invention has a strong interaction with the active metal, which can make the active metal uniformly loaded on the surface of the support in the form of nano clusters, so as to give full play to the catalytic activity of the active metal and ensure its catalytic stability.

[0012] (3) The catalyst support f-TiO2@BNO of the present invention has acidic properties and low overall electronegativity. It can not only enhance the catalytic activity of active metals, but also prevent H2S adsorption and promote the forward hydrogenation reaction.

[0013] Furthermore, the mass percentage of BNO in the nanoflower-shaped catalyst support f-TiO2@BNO is 0.1% to 3.5%.

[0014] The beneficial effects of adopting the above-mentioned further scheme are as follows: Adding a small amount of oxygen-doped boron nitride (BNO) to nano-flower-shaped titanium dioxide (f-TiO2) has the following effects: ① BNO mainly adheres to the TiO2 surface and has excellent chemical stability, thus improving the lifetime of the support itself; ② BNO has a strong binding ability with metals and can be used to load active metals, preventing metal particles from detaching or agglomerating; ③ BNO has a certain adsorption and enrichment effect on sulfur-containing components, which can enrich the target sulfur-containing gas components near the active metal for rapid conversion.

[0015] Furthermore, the active metal component includes any one or a combination of at least two of Pd, Pt, Ni, Cu, and Ru.

[0016] The beneficial effects of adopting the above-mentioned further scheme are: the above-mentioned metals are all commonly used metal catalysts in the catalytic hydrogenation process, and have high hydrogenation activity; and the present invention is precisely to use the hydrogenation reaction to convert sulfur-containing organic molecules into hydrogen sulfide, so the above-mentioned metals are selected.

[0017] Furthermore, the loading amount of the active metal component on the support is 0.8 wt% to 1.5 wt%.

[0018] The beneficial effects of adopting the above-mentioned further solution are: optimizing the load and setting a relatively low load can save costs on the one hand, and improve the dispersion of metal on the other hand, preventing metal particles from agglomerating into large particles.

[0019] Secondly, a method for preparing a hydrodesulfurization catalyst includes the following steps:

[0020] (1) Nano-flower-shaped catalyst support f-TiO2@BNO was prepared by alkaline etching method;

[0021] (2) A metal active component was introduced onto the nano-flower-shaped catalyst support f-TiO2@BNO by adsorption-reduction method to obtain catalyst M / f-TiO2@BNO; M in catalyst M / f-TiO2@BNO is a metal active component.

[0022] The beneficial effects of adopting the above-mentioned further scheme are: the adsorption-reduction method can ensure that the active metals on the catalyst are combined with the support through strong interactions, thereby effectively improving the stability and lifespan of the catalyst.

[0023] Furthermore, step (1) includes the following specific steps:

[0024] (1-1) A salt solution (e.g., NaCl solution) is added to an organic dispersion (anhydrous ethanol or methanol) to obtain solution A; BNO is dispersed in solution A to obtain solution B; an organic titanium source is added to solution B and mixed evenly to obtain a milky white solution C; solution C is washed (e.g., with anhydrous ethanol), centrifuged, and dried to obtain TiO2@BNO nanospheres;

[0025] (1-2) Disperse the TiO2@BNO nanospheres in pure water, add ammonia, mix well, and then carry out a high-temperature modification reaction, for example in an oven, to obtain the modified nanoflower-shaped catalyst support f-TiO2@BNO.

[0026] The beneficial effect of adopting the above-mentioned further scheme is that TiO2@BNO nanospheres are simultaneously etched with flower-shaped morphology on their surface in an ammonia environment using the temperature of a reaction oven, thereby increasing the specific surface area and providing more sites for subsequent metal loading.

[0027] Further, in step (1-1), the concentration of the salt solution is 0.05–0.5 mol / L, and the volume ratio of the salt solution to the organic dispersion is 0.5–10:200–1000; the volume ratio of BNO to the salt solution is 1–10:0.5–10 mg / mL; the organic titanium source is any one or a combination of at least two of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, and the volume ratio of the organic titanium source to BNO is 0.01–0.08:1–10 mol / mg; the number of centrifugation and washing cycles is 3–6, the drying temperature is 60–80℃, and the drying time is 12–24 h;

[0028] In steps (1-2), the concentration of the TiO2@BNO nanospheres dispersed in pure water is 5-20 mg / mL; the mass concentration of the ammonia water is 22%-25%, and the ratio of TiO2@BNO nanospheres to ammonia water is 0.3 g:(4-15) mL; the temperature of the high-temperature modification reaction is 110-160℃, and the reaction time is 8-24 h. After the high-temperature modification reaction is completed, the solid powder is separated by centrifugation and washed by centrifugation. The obtained solid powder is then placed in an oven for thorough drying. During washing, it needs to be washed 3-6 times with deionized water and then 2-3 times with ethanol. The drying temperature is 60-80℃, and the drying time is 12-24 h.

[0029] The beneficial effects of adopting the above-mentioned further scheme are: water washing, alcohol washing, and centrifugal washing remove residual ammonia from the catalyst surface.

[0030] Furthermore, step (2) includes the following specific steps:

[0031] (2-1) Disperse the nano-flower-shaped catalyst support f-TiO2@BNO in deionized water, then add an active metal salt solution dropwise, mix well to obtain solution D; add a reducing agent to solution D to obtain solution E;

[0032] (2-2) The solution E was sequentially separated, washed and dried to obtain catalyst M / f-TiO2@BNO.

[0033] The beneficial effect of adopting the above-mentioned further scheme is that sodium borohydride is used to reduce active metal ions, so that they are converted into active metal elements and supported on the catalyst support.

[0034] Further, in step (2-1), the concentration of the nano-flower-shaped catalyst support f-TiO2@BNO dispersed in deionized water is 20-60 mg / mL; the active metal salt solution is any one or a combination of at least two of palladium chloride, platinum chloride, copper chloride, and nickel chloride; the metal ion concentration is 0.32 mol / L, and the volume of the metal salt solution is 0.1-3 mL; the mass ratio of the nano-flower-shaped catalyst support f-TiO2@BNO to the active metal salt in solution D is 100:0.5-100:5; the reducing agent includes at least one of sodium borohydride and potassium borohydride; the amount of sodium borohydride used is sufficient to fully reduce the active metal salt.

[0035] In step (2-2), the washing process involves washing with deionized water 3 to 6 times, centrifugation at a speed of 7000 to 10000 r / min for 3 to 5 minutes, and drying at a temperature of 60 to 80℃ for 10 to 20 hours.

[0036] The beneficial effect of adopting the above-mentioned further scheme is that centrifugal washing, water washing and alcohol washing can remove various impurity salts from the surface of the catalyst.

[0037] Thirdly, the application of a hydrodesulfurization catalyst, wherein the aforementioned hydrodesulfurization catalyst is used in the catalytic treatment of hydrodesulfurization of gaseous sulfides in natural gas.

[0038] The beneficial effects of adopting the above scheme are: the catalyst M / f-TiO2@BNO has a high conversion rate of sulfur-containing components in natural gas at normal pressure and temperature of 260℃, and has strong resistance to interference from CO, O2 and other substances. Attached Figure Description

[0039] Figure 1 The images show scanning electron microscope (SEM) images of the TiO2@BNO carrier prepared in this invention. Images a and b represent TiO2@BNO nanospheres, while images c and d show clearly morphologically distinct nanoflower-like f-TiO2@BNO carriers. Detailed Implementation

[0040] The principles and features of this invention are described below. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they should be performed according to the techniques or conditions described in the literature in this field, or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0041] Example 1

[0042] This embodiment relates to a method for preparing a hydrodesulfurization catalyst, comprising the following steps: adding 0.2M NaCl solution to 500mL of anhydrous ethanol solution, then dispersing 5mg of oxygen-doped boron nitride (BNO) additive powder into the solution, then rapidly adding 0.05mol of tetraisopropyl titanate, and stirring vigorously at room temperature for 5h until the solution turns milky white; then washing three times with anhydrous ethanol by centrifugation, and then drying in a drying oven at 80℃ for 2h to obtain TiO2@BNO nanospheres; taking 0.3g of TiO2@BNO nanospheres and dispersing them in 40mL of pure water, and adding 5mL of ammonia water (concentration of 13.38mol / L, commercially available concentrated ammonia water), stirring at room temperature for 10min, and then transferring to a reaction vessel; placing the reaction vessel in a 120℃ oven for high-temperature hydrothermal reaction for 12h; washing the white solid after hydrothermal reaction three times with anhydrous ethanol by centrifugation, and placing the resulting solution in a 60℃ drying oven for 2h to obtain the modified support material f-TiO2@BNO; taking 1g The f-TiO2@BNO carrier material was dispersed in deionized water, and then 0.3 mL of PdCl2 solution (concentration of 0.017 mol / mL) was added dropwise. The mixture was stirred vigorously at room temperature for 7 h. Subsequently, 20 mg of sodium borohydride powder was added to the solution, and the solid in the solution was washed three times by centrifugation with anhydrous ethanol. The solid powder was then dried in a 60 °C oven to obtain Pd / f-TiO2@BNO with an active component loading of 1 wt%.

[0043] Example 2

[0044] This embodiment relates to a method for preparing a hydrodesulfurization catalyst, comprising the following steps: 0.5M NaCl solution is added to 500mL of anhydrous ethanol solution, then 10mg of oxygen-doped boron nitride (BNO) additive powder is dispersed into the solution, followed by rapid addition of 0.03mol tetraethyl titanate, and vigorous stirring at room temperature for 5h until the solution turns milky white. The solution is then washed three times with anhydrous ethanol by centrifugation, and dried in a drying oven at 80℃ for 2h to obtain TiO2@BNO nanospheres; 0.3g of TiO2@BNO nanospheres are dispersed in 40mL of pure water, and 7mL of ammonia (concentration 13.38mol / L, commercially available concentrated ammonia) is added. After stirring at room temperature for 10min, the mixture is transferred to a reaction vessel; the reaction vessel is placed in a 120℃ oven for a high-temperature hydrothermal reaction for 12h; the mixture is then placed in a 60℃ drying oven for 2h to obtain a modified anhydrous ethanol-washed white solid after hydrothermal reaction three times, and the resulting solution is used as the support material f-TiO2@BNO; 1g of... The f-TiO2@BNO support material was dispersed in deionized water, and then 0.5 mL of PtCl4 solution (concentration 0.052 mol / mL) was added dropwise. The mixture was stirred vigorously at room temperature for 7 h. Subsequently, 40 mg of sodium borohydride powder was added to the solution, and the solid in the solution was washed three times by centrifugation with anhydrous ethanol. The solid powder was then dried in a 60 °C oven to obtain Pt / f-TiO2@BNO with an active component loading of 1.5 wt%.

[0045] Example 3

[0046] This embodiment relates to a method for preparing a hydrodesulfurization catalyst, comprising the following steps: adding 0.3M NaCl solution to 500mL of anhydrous ethanol solution, then dispersing 8mg of oxygen-doped boron nitride additive (BNO) powder into the solution, then rapidly adding 0.04mol of tetrabutyl titanate, and stirring vigorously at room temperature for 8h until the solution turns milky white. The TiO2@BNO nanospheres were then washed three times with anhydrous ethanol by centrifugation and dried at 80°C for 2 hours in a drying oven to obtain TiO2@BNO nanospheres. 1 g of TiO2@BNO nanospheres were dispersed in 40 mL of pure water, and 15 mL of ammonia (13.38 mol / L, commercially available concentrated ammonia) was added. After stirring at room temperature for 10 minutes, the mixture was transferred to a reaction vessel. The reaction vessel was placed in a 120°C oven for a high-temperature hydrothermal reaction for 12 hours. The white solid after hydrothermal reaction was washed three times with anhydrous ethanol by centrifugation, and the resulting solution was placed in a 60°C drying oven for 2 hours to obtain the modified support material f-TiO2@BNO. 1 g of f-TiO2@BNO support material was dispersed in deionized water, and then 0.25 mL of... NiCl2 solution (concentration 0.071 mol / mL) was stirred vigorously at room temperature for 7 h. Then, 40 mg of sodium borohydride powder was added to the solution. The solid in the solution was washed three times by centrifugation with anhydrous ethanol. The solid powder was then dried in an oven at 60 °C to obtain Ni / f-TiO2@BNO with an active component loading of 0.8 wt%.

[0047] Test case

[0048] Catalytic hydrodesulfurization reaction was carried out using the catalyst materials obtained in Examples 1, 2, and 3, pure BNO, f-TiO2, and f-TiO2@BNO.

[0049] 0.6 g of the corresponding catalyst was mixed evenly with an appropriate amount of coarse quartz sand and packed into a fixed-bed reactor. The reaction temperature was set at 280℃, the gas flow rate at 500 mL / min, the carrier gas was methane, the concentration of sulfur-containing components was set at 50 ppm, and the hydrogen content was set at 3%. The catalyst activity was determined by detecting hydrogen sulfide gas in the reaction tail gas. The test results are shown in Tables 1 and 2 below:

[0050] Table 1. Comparison of the activities of several catalysts

[0051]

[0052]

[0053] Table 2 Comparison of catalytic activities of supports

[0054]

[0055] As shown in Tables 1 and 2, all three catalysts can effectively convert the two representative sulfur-containing organic molecules; the activity order of the three catalysts is Pd>Pt>Ni; ③ No metal is supported, and the support itself has no catalytic activity.

[0056] Figure 1 These are scanning electron microscope (SEM) images of the TiO2@BNO carrier prepared in this invention. Images a and b represent TiO2@BNO nanospheres, while images c and d show clearly morphologically distinct nanofloral-like f-TiO2@BNO carriers. Figure 1 It can be seen that smooth TiO2@BNO nanospheres were obtained, and clear nanoflower-shaped f-TiO2@BNO nanospheres were obtained by etching with ammonia.

[0057] In summary, this invention provides a highly active hydrodesulfurization catalyst compared to existing technologies. Using f-TiO2@BNO as the catalyst support, it possesses a highly exposed surface with strong interactions with the active metal, which is beneficial for the loading of the active metal, fully utilizing its catalytic activity while ensuring its catalytic stability. Furthermore, it prevents H2S adsorption and promotes the forward hydrogenation reaction. Using this hydrodesulfurization catalyst, rapid hydrodesulfurization of sulfur-containing components such as methanethiol and carbonyl sulfide in natural gas can be achieved under low temperature (<300℃), normal pressure, and low hydrogen concentration (1%–3%) conditions, with a conversion rate exceeding 90%, and the catalyst does not require pre-sulfurization treatment.

[0058] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0059] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A hydrodesulfurization catalyst characterized by, The catalyst comprises a support and an active metal component loaded on the support. The support is a nano-flower-shaped catalyst support f-TiO2@BNO. In the nano-flower-shaped catalyst support f-TiO2@BNO, BNO is attached to the surface of f-TiO2. In the nano-flower-shaped catalyst support f-TiO2@BNO, BNO is oxygen-doped boron nitride. In the nano-flower-shaped catalyst support f-TiO2@BNO, f-TiO2 is nano-flower-shaped titanium dioxide material. The active metal component includes any one or a combination of at least two of Pd, Pt, Ni, Cu, and Ru.

2. The hydrodesulfurization catalyst according to claim 1, wherein The mass percentage of BNO in the nanoflower-shaped catalyst support f-TiO2@BNO is 0.1%~3.5%.

3. The hydrodesulfurization catalyst according to any one of claims 1 to 2, characterized by, The loading amount of the active metal component on the carrier is 0.8wt%~1.5wt%.

4. A process for the preparation of a hydrodesulfurization catalyst according to any one of claims 1 to 3, characterized in that Includes the following steps: (1) Nanoflower-shaped catalyst support f-TiO2@BNO was prepared by alkaline etching method; (2) A metal active component was introduced onto the nano-flower-shaped catalyst support f-TiO2@BNO by adsorption-reduction method to obtain catalyst M / f-TiO2@BNO; M in catalyst M / f-TiO2@BNO is a metal active component; Step (1) includes the following specific steps: (1-1) Add the salt solution to the anhydrous organic dispersion to obtain solution A; disperse BNO into solution A to obtain solution B; An organic titanium source was added to solution B and mixed thoroughly to obtain a milky white solution C. The solution C was washed, centrifuged, and dried to obtain TiO2@BNO nanospheres. (1-2) The TiO2@BNO nanospheres were dispersed in pure water, ammonia was added, and after mixing, a high-temperature modification reaction was carried out to obtain the modified nanoflower-shaped catalyst support f-TiO2@BNO; the temperature of the high-temperature modification reaction was 110~160℃, and the reaction time was 8~24 h; Step (2) includes the following specific steps: (2-1) Disperse the nano-flower-shaped catalyst support f-TiO2@BNO into deionized water, then add an active metal salt solution dropwise, mix well, and obtain solution D; Adding a reducing agent to solution D yields solution E; (2-2) The solution E is sequentially separated, washed and dried to obtain catalyst M / f-TiO2@BNO.

5. The method for preparing a hydrodesulfurization catalyst according to claim 4, characterized in that, In step (1-1), the concentration of the salt solution is 0.05~0.5 mol / L, and the volume ratio of the salt solution to the organic dispersion is 0.5~10:200~1000; the volume ratio of BNO to the salt solution is 1~10:0.5~10 mg / mL; the organic titanium source is any one or a combination of at least two of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, and the volume ratio of the organic titanium source to BNO is 0.01~0.08:1~10 mol / mg; the number of centrifugation and washing cycles is 3~6, ​​the drying temperature is 60~80℃, and the drying time is 12~24 h; In steps (1-2), the concentration of the TiO2@BNO nanospheres dispersed in pure water is 5~20 mg / mL, the mass concentration of the ammonia water is 22%~25%, and the ratio of the amount of TiO2@BNO nanospheres to ammonia water is 0.3g:(4~10)mL.

6. The method for preparing a hydrodesulfurization catalyst according to claim 4, characterized in that, In step (2-1), the concentration of the nano-flower-shaped catalyst support f-TiO2@BNO dispersed in deionized water is 20~60 mg / mL; the active metal salt solution is any one or a combination of at least two of palladium chloride, platinum chloride, copper chloride, and nickel chloride; the mass ratio of the nano-flower-shaped catalyst support f-TiO2@BNO to the active metal salt in solution D is 100:0.5~100:5; the reducing agent includes at least one of sodium borohydride and potassium borohydride. In step (2-2), deionized water is used for washing 3 to 6 times, centrifugation is performed at a speed of 7000 to 10000 r / min for 3 to 5 minutes, and drying is carried out at a temperature of 60 to 80℃ for 10 to 20 hours.

7. The application of a hydrodesulfurization catalyst, characterized in that, The hydrodesulfurization catalyst according to any one of claims 1 to 3 is used in the catalytic treatment of hydrodesulfurization of gaseous sulfides in natural gas.

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