Hydrogenation-hydrolysis coupling desulfurization catalyst as well as preparation method and application thereof

Abstract

The invention discloses a hydrogenation-hydrolysis coupling desulfurization catalyst, and relates to the technical field of desulfurization catalysts, a preparation method comprises the following steps: (1) adding a molybdenum source, an inorganic metal salt and a sulfur source into deionized water, and uniformly mixing to obtain a mixture A; (2) sequentially adding sepiolite and organic acid into the mixture A, and reacting to obtain a mixture B; and (3) performing hydrothermal reaction on the mixture B to obtain a product, washing and drying the product, and reducing to obtain the product. Two-dimensional active metal nanosheets grow in situ on sepiolite one-dimensional nanofibers by adopting an organic acid-assisted hydrothermal method, and finally the hydrogenation-hydrolysis coupling desulfurization catalyst with a 1D / 2D vertical heterostructure and efficient desulfurization performance is synthesized. The catalyst provided by the invention has the advantages of simple preparation method, high catalyst activity and product selectivity, low organic sulfur conversion reaction temperature and strong antitoxic ability, and effectively prolongs the service life and stability of the catalyst.

Description

Technical Field

[0001] The present invention relates to the technical field of desulfurization catalysts, and particularly relates to a hydrogenation-hydrolysis coupled desulfurization catalyst, a preparation method thereof and an application thereof. Background Art

[0002] The metallurgical industry, mainly including the ferrous metallurgy industry, non-ferrous metallurgy industry, rare metal metallurgy industry and powder metallurgy industry, is an important production industry in the national economy. The by-product is metallurgical gas containing CO. CO is not only an excellent high-calorific fuel, but also an important chemical raw material, which can be used to prepare a variety of high-value-added chemical products such as HCOOH, Hac, DMC, and DMF. However, the metallurgical gas contains impurities such as sulfides, which limits its high-value resource utilization. Taking the blast furnace gas (BFG) by-produced in iron and steel metallurgy as an example, it has the characteristics of large gas production and low calorific value. Smelting 1t of pig iron can produce 1700-2500m 3 of BFG.

[0003] BFG contains 22-27 vol% CO, 13-19 vol% CO2 and 1-4 vol% H2, and can be used as a direct fuel or a raw material after further purification, with high utilization value. However, BFG also contains sulfides such as COS, CS2, H2S, thioether, and mercaptan, and the total sulfur content is 100-200 mg·Nm -3 . The sulfur in BFG usually converts to SO2 during combustion, causing environmental pollution and harming human health. The process technology for removing H2S in BFG has been quite mature in the industry. However, due to the stability of organic sulfur, it is difficult to directly remove it, and conventional desulfurization methods are difficult to meet the requirements of deep desulfurization and often difficult to meet the emission standards.

[0004] At present, one of the strategies to solve the problem of difficult-to-remove organic sulfur is to first convert it into H2S, and then remove H2S to achieve the purpose of efficient and deep desulfurization. Hydrolysis and hydrogenation are common methods to convert organic sulfur into H2S. Hydrolytic desulfurization refers to the hydrolysis reaction of organic sulfur in the presence of water and a catalyst to generate H2S. It can directly utilize the water vapor carried in the coal gas and has the characteristics of low desulfurization temperature but low desulfurization precision. Hydrodesulfurization (HDS) refers to the hydroconversion reaction of organic sulfur with hydrogen under the action of a catalyst to generate H2S that is easily removed. The hydroconversion process has a wide applicable temperature range and high conversion rate. At the same time, it can also directly utilize the H2 in the gas for the desulfurization reaction, but it has high temperature requirements and usually reaches complete conversion only above 280°C. For example, CN 114917935 A discloses a preparation and synthesis process of a petroleum hydrodesulfurization catalyst with a high-activity phase Ni-Mo-S and its application method in petroleum hydrodesulfurization. By in-situ introducing H2 regulation in the suspension formed by ammonium heptamolybdate as the molybdenum source, thiourea as the sulfur source, and nickel nitrate, and high-temperature activation, a Ni-MoS2 hydrodesulfurization catalyst is obtained. The hydrodesulfurization conversion efficiency of the catalyst for thiophene in petroleum reaches up to 96%. CN 112619648 A discloses a copper-cobalt-based catalyst for hydrolytic removal of organic sulfur and its preparation method. Through a hydrothermal-assisted co-precipitation synthesis method combined with high-temperature calcination, a copper-doped cobalt tetroxide catalyst is prepared, which exhibits high crystallinity, nanosheet-like, mainly mesoporous, and high ion diffusion rate, and has high catalytic hydrolysis performance for carbonyl sulfide. It can be seen from the above that hydrodesulfurization and hydrolytic desulfurization technologies have been widely used, but the hydro-hydrolysis coupling catalytic desulfurization technology has rarely been reported at present.

[0005] Therefore, it is an urgent technical problem in the field to provide a hydro-hydrolysis coupling desulfurization catalyst for deep removal of various forms of sulfur in coal gas at low temperature and its preparation method. Summary of the Invention

[0006] In order to solve the problems existing in the prior art pointed out in the background art, the purpose of the present invention is to propose a hydro-hydrolysis coupling desulfurization catalyst, its preparation method and application. The present invention uses 1D sepiolite as the growth substrate and adopts an organic acid-assisted hydrothermal method to construct a vertical 1D / 2D M x MoS2 / DO-SEP composite catalyst, and regulates the hydro-hydrolysis coupling catalytic desulfurization performance of the catalyst by controlling the type and proportion of transition metal doping. The plate length and number of layers of MoS2 in the catalyst can also be regulated by changing the type and content of organic acids; in the constructed composite catalyst, M x MoS2 is uniformly loaded on DO-SEP, and its structure shows an ideal 1D / 2D structure, having the advantages of a large specific surface area, pore volume and rich hydroxyl sites of sepiolite, and at the same time maximizing the exposure of M x MoS2x Defects and active sites on MoS2, and there is no strong interaction force between the active component and the carrier in the traditional hydrotreating catalyst, enabling the organic sulfur in the reaction system to fully utilize the hydroxyl sites and exposed edge sites in the catalyst in China to achieve hydrodesulfurization-hydrolysis coupling catalytic conversion in a lower temperature range.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] A preparation method of a hydrodesulfurization-hydrolysis coupling desulfurization catalyst, comprising the following specific steps:

[0009] (1) Add a molybdenum source, an inorganic metal salt, and a sulfur source to deionized water, and mix evenly to obtain a mixture A;

[0010] (2) Sequentially add sepiolite and an organic acid to the mixture A and react to obtain a mixture B;

[0011] (3) Wash and dry the product obtained by hydrothermal reaction of the mixture B, and then obtain a hydrodesulfurization-hydrolysis coupling desulfurization catalyst, namely M x MoS2 / DO-SEP composite material, where x represents the molar ratio of M (metal ion) to Mo.

[0012] The present invention in-situ grows two-dimensional active metal nanosheets on sepiolite one-dimensional nanofibers by adopting an organic acid-assisted hydrothermal method, and finally synthesizes a hydrodesulfurization-hydrolysis coupling desulfurization catalyst with a 1D / 2D vertical heterostructure and high desulfurization performance, completely converting the organic sulfur in blast furnace gas into H2S that is easily removed; the catalyst preparation method of the present invention is simple, the catalyst activity and product selectivity are high, the organic sulfur conversion reaction temperature is low, the anti-poisoning ability is strong, and the service life and stability of the catalyst are effectively extended.

[0013] Preferably, the molar ratio of the metal ion in the inorganic metal salt to the molybdenum source in step (1) is 0-0.8;

[0014] The molar volume ratio of the molybdenum source, the sulfur source, and the deionized water is 1-2 mmol: 30-60 mmol: 70-140 mL;

[0015] The mixing parameters are: time is 30-60 min, temperature is room temperature, and rotation speed is 800-1000 r / min.

[0016] Preferably, the molybdenum source in step (1) is ammonium molybdate ((NH4)6Mo7O 24 ·4H2O) or sodium molybdate (Na2MoO4·2H2O); the sulfur source is thiourea (CH4N2S) or L-cysteine (C6H 12(N2O4S2), and the inorganic metal salt is nickel nitrate (Ni(NO3)2·6H2O), cobalt nitrate (Co(NO3)2·6H2O), or ammonium metatungstate (H 28 N6O 41 W 12 ) of any one kind.

[0017] Preferably, the ratio of the molybdenum source, the sepiolite, and the organic acid in step (2) is 1-2 mmol: 1-1.5 g: 20-30 mL;

[0018] The parameters for the reaction after adding the sepiolite are: stirring at room temperature for 20-30 min, with a rotation speed of 800-1000 r / min;

[0019] The parameters for the reaction after adding the organic acid are: stirring at room temperature for 20-24 h, with a rotation speed of 800-1000 r / min, and the organic acid is any one of formic acid, acetic acid, or propionic acid.

[0020] In the preparation of the hydrodesulfurization-hydrolysis coupling desulfurization catalyst of the present invention, based on the unique structure and induction effect of the sepiolite support, under the action of the organic acid, through the Mo-O heterointerface, two-dimensional (2D) M x The edges of the MoS2 nanosheets grow on the one-dimensional nanofibers of sepiolite to form a 1D / D vertical structure; the organic acid is beneficial to the formation of few-layer MoS2 nanosheets with shorter plate lengths, synergistically promoting the exposure of defects and catalytic active sites. The sepiolite is rich in hydroxyl groups and can be used as a hydrolysis active site. The prepared MoS2 / DO-SEP composite material has both hydrodesulfurization and hydrolysis catalytic capabilities. x MoS2 nanosheets, synergistically promoting the exposure of defects and catalytic active sites. The sepiolite is rich in hydroxyl groups and can be used as a hydrolysis active site. The prepared M x MoS2 / DO-SEP composite material simultaneously has hydrodesulfurization and hydrolysis catalytic abilities.

[0021] Preferably, the following pretreatment is carried out before adding the sepiolite to remove the mineral impurities contained in the sepiolite. The specific steps are: placing the sepiolite in deionized water, stirring at room temperature for 20-24 h and then filtering, transferring the filter cake to vacuum dry at 80-90 °C for 10-12 h, and grinding through a 100-mesh sieve;

[0022] Among them, the mass-volume ratio of the sepiolite to the deionized water is 5 g: 100-125 mL, and the rotation speed of stirring is 900-1000 r / min.

[0023] Preferably, the parameters of the hydrothermal reaction in step (3) are: reacting at 200-220 °C for 12-24 h;

[0024] The washing is carried out by repeatedly washing with ethanol and deionized water;

[0025] The drying is vacuum drying at 70-90 °C for 10-15 h;

[0026] The reduction steps are as follows: Introduce a mixed gas of H2 / N2, and raise the temperature to 180 - 200 °C for reaction for 6 - 8 h.

[0027] Preferably, the volume fraction of H2 in the mixed gas is 8 - 10%, the gas flow rate is 180 - 200 mL / min, and the heating rate is 2 °C / min.

[0028] A hydrodesulfurization - hydrolysis coupling desulfurization catalyst obtained by the above - mentioned preparation method.

[0029] In the hydrodesulfurization - hydrolysis coupling catalyst prepared by the present invention, 2D M x MoS2 nanosheets grow vertically on 1D sepiolite nanofibers to construct a vertical 1D / 2D M x MoS2 / DO - SEP composite catalyst. Sepiolite and M x MoS2 cooperate to expose defects and catalytic active sites, enabling it to have excellent performance in catalytic conversion of various forms of sulfur in metallurgical gas by low - temperature hydrodesulfurization - hydrolysis coupling.

[0030] Preferably, the hydrodesulfurization - hydrolysis coupling desulfurization catalyst is renewable. It is regenerated by using superheated steam containing a certain concentration of hydrogen, and then dried with dry hot air. The number of cycles is ≥3.

[0031] Preferably, the specific regeneration steps are as follows: Introduce superheated steam with a hydrogen concentration of 5 - 10% to regenerate the hydrodesulfurization - hydrolysis coupling desulfurization catalyst. The temperature of the superheated steam is 250 - 300 °C, the purging time is 10 - 20 h, and then it is dried with dry hot air at 6 - 80 °C. The activity of the hydrodesulfurization - hydrolysis coupling desulfurization catalyst after regeneration can be increased to more than 95%.

[0032] Application of a hydrodesulfurization - hydrolysis coupling desulfurization catalyst obtained by the above - mentioned preparation method in metallurgical gas desulfurization.

[0033] Preferably, the catalytic temperature of the catalyst is 150 - 200 °C.

[0034] Preferably, the raw gas led out from the metallurgical gas conduit is subjected to dust removal, dechlorination, and deoxidation pretreatment and then sent to a hydrodesulfurization - hydrolysis coupling catalytic conversion tower. The tower is filled with a hydrodesulfurization - hydrolysis coupling desulfurization catalyst. Through the coupling action of hydrodesulfurization and hydrolysis, the organic sulfur in the blast furnace gas is converted into H2S. The gas after hydrodesulfurization - hydrolysis coupling is sent to a hydrogen sulfide removal tower to remove the originally contained H2S and the H2S converted from organic sulfur in the gas.

[0035] Preferably, the sulfur-containing pollutants in the metallurgical gas are mainly 60-80% organic sulfur (including carbonyl sulfide, carbon disulfide, thioether, and mercaptan) and 20-40% inorganic sulfur (hydrogen sulfide); after dust removal, dechlorination, and deoxidation, the oxygen concentration in the gas is 0.001-0.01%, and the dust concentration in the gas is 5 mg·Nm -3 Next, the hydrogen chloride content in the gas is less than 0.2 mg·Nm -3 Next; the temperature of the hydro - hydrolysis desulfurization catalytic conversion tower is controlled at 150-200 °C, the water vapor content is 5-10%, and the H2 content is 3-5%; the conversion rate of organic sulfur is above 99%, and the product selectivity reaches 100%.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The preparation process of the composite catalyst of the present invention is simple, and the raw materials are easy to obtain;

[0038] (2) During the desulfurization reaction of the catalyst of the present invention, pre-sulfidation is not required, which avoids the incomplete pre-sulfidation from affecting the reaction activity of the catalyst and also reduces the energy consumption during the catalyst preparation process;

[0039] (3) Due to the doping of Ni, Co or W in the catalyst of the present invention, more S vacancies are generated at the edges of M x MoS2, and at the same time, in cooperation with hydroxyl groups, efficient hydro - hydrolysis coupling catalytic desulfurization is realized; M x MoS2 / DO-SEP composite material has a larger specific surface area and adsorption capacity, which can provide more reaction active sites, thereby improving the hydro - hydrolysis coupling catalytic desulfurization rate;

[0040] (4) The hydro - hydrolysis coupling catalyst of the present invention has strong regenerability. After the activity of the catalyst decreases, the activity is significantly improved through regeneration, effectively extending the service efficiency of the equipment and the service life of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. The drawings in this description are only the embodiments of the present invention.

[0042] Figure 1 For the MoS prepared in Example 2 2 / Test result diagram of the conversion rate and product selectivity of the DO-SEP hydro - hydrolysis coupling desulfurization catalyst for organic sulfur in blast furnace gas;

[0043] Figure 2 For the pure-phase Ni prepared in Comparative Example 1 0.2Test result diagram of the conversion rate and product selectivity of organic sulfur in blast furnace gas by MoS2 catalytic desulfurizer;

[0044] Figure 3 W prepared for Comparative Example 2 0.8 Test result diagram of the conversion rate and product selectivity of organic sulfur in blast furnace gas by MoS2 / DO-SEP(N-OA) desulfurization catalyst;

[0045] Figure 4 Co prepared for Comparative Example 3 0.5 Catalytic desulfurization effect diagram of MoS2 / DO-SEP desulfurization catalyst for hydrogenation and hydrolysis condition exploration at 170°C;

[0046] Figure 5 Process flow diagram for the catalyst to remove various forms of sulfur in blast furnace gas;

[0047] Figure 6 XRD pattern of the MoS2 / DO-SEP hydrogenation-hydrolysis coupled desulfurization catalyst prepared in Example 2;

[0048] Figure 7 SEM image of the MoS2 / DO-SEP hydrogenation-hydrolysis coupled desulfurization catalyst prepared in Example 2;

[0049] Figure 8 TEM spectrum and HRTEM image of the MoS2 / DO-SEP hydrogenation-hydrolysis coupled desulfurization catalyst prepared in Example 2;

[0050] Figure 9 Regeneration efficiency diagram of the hydrogenation-hydrolysis coupled desulfurization catalyst prepared in Examples 1-5. Detailed implementation manners

[0051] The following describes the embodiments of the present invention. The examples are shown in the accompanying drawings. The embodiments described with reference to the accompanying drawings are exemplary and are intended to explain the present invention, rather than being construed as a limitation of the present invention.

[0052] Example 1

[0053] A hydrogenation-hydrolysis coupled desulfurization catalyst, and the preparation method specifically includes the following steps:

[0054] (1) Dissolve 1236 mg (1 mmol) (NH4)6Mo7O 24 ·4H2O, 2283 mg (30 mmol) CH4N2S, and 407 mg (1.4 mmol) Ni(NO3)2·6H2O in 70 mL of deionized water, and stir at room temperature at a rotation speed of 850 r / min for 55 min to obtain a mixture A; wherein the molar ratio of Ni:Mo is 0.2;

[0055] (2) Add 1 g of DO-SEP to mixture A, stir at 1000 r / min for 20 min, then add 20 mL of formic acid, and stir at room temperature for 20 h to obtain mixture B. The preparation method of DO-SEP is as follows: Under magnetic stirring at a speed of 900 r / min, weigh 5 g of sepiolite (SEP) and place it in 125 mL of deionized water. Continuously stir at room temperature for 24 h, then filter. Transfer the filter cake to a vacuum dryer at 80 °C for 12 h, grind it through a 100-mesh sieve to obtain DO-SEP;

[0056] (3) Place mixture B in a hydrothermal reaction kettle, heat it continuously at 210 °C for 12 h to obtain product C. Let product C cool naturally to room temperature, after centrifugal separation, wash it repeatedly with ethanol and deionized water, and dry it in a vacuum at 70 °C for 15 h to obtain sample D. Place sample D in a tubular furnace, introduce a H2 / N2 mixed gas with a flow rate of 200 mL / min and a H2 volume fraction of 10%, heat it to 180 °C at a rate of 2 °C / min and keep it for 8 h to obtain Ni 0.2 MoS2 / DO-SEP composite material, namely the hydrodesulfurization-hydrolysis coupling desulfurization catalyst;

[0057] As Figure 5 , the specific implementation steps for a hydrodesulfurization-hydrolysis coupling desulfurization catalyst to remove organic sulfur in blast furnace gas are provided:

[0058] 1) The blast furnace gas containing 65% organic sulfur (including carbonyl sulfide, carbon disulfide, thioether, and mercaptan) and 35% inorganic sulfur (hydrogen sulfide) led out from the outlet pipe of the gas duct is passed through a bag dust removal device and a dechlorination and deoxygenation pretreatment tower in sequence for dust removal, dechlorination, and deoxygenation pretreatment, and then the gas is sent into the hydrodesulfurization-hydrolysis coupling catalytic conversion tower. After dust removal, dechlorination, and deoxygenation, the oxygen concentration in the gas is 0.005%, the dust concentration in the gas is below 5 mg·Nm -3 Below, the hydrogen chloride content in the gas is below 0.2 mg·Nm -3 Below;

[0059] 2) Fill 50 mg of Ni 0.2 MoS2 / DO-SEP composite material into the hydrodesulfurization-hydrolysis coupling catalytic conversion tower. Control the temperature of the hydrodesulfurization-hydrolysis desulfurization catalytic conversion tower at 180 °C, the water vapor content at 5%, and the H2 content at 5% for catalytic conversion to obtain desulfurized gas. The conversion rate of organic sulfur is above 99%, and the product selectivity reaches 100%. Send the desulfurized gas into the hydrogen sulfide removal tower, and use alkali-modified activated carbon to remove the original H2S and the H2S converted from organic sulfur in the gas;

[0060] 3) After the activity of the hydrodesulfurization-hydrolysis coupling desulfurization catalyst decreases, superheated steam with a hydrogen concentration of 6% is introduced to regenerate the hydrodesulfurization-hydrolysis coupling desulfurization catalyst. The temperature of the superheated steam is 280 °C, the purging time is 15 h, and then it is dried with dry hot air at 70 °C; Figure 7 It is a regeneration efficiency diagram. As can be seen from the figure, the activity of the regenerated hydrodesulfurization-hydrolysis coupling desulfurization catalyst can be increased to more than 95%, and it can be recycled and regenerated 3 times.

[0061] Example 2

[0062] A hydrodesulfurization-hydrolysis coupling desulfurization catalyst, and the preparation method specifically includes the following steps:

[0063] (1) Dissolve 1854 mg (1.5 mmol) of (NH4)6Mo7O 24 ·4H2O and 3424 mg (40 mmol) of CH4N2S in 95 mL of deionized water, and stir at room temperature at a rotation speed of 900 r / min for 45 min to obtain mixture A;

[0064] (2) Add 1.5 g of DO-SEP to mixture A, stir at 900 r / min for 25 min, then add 25 mL of propionic acid, and stir at room temperature for 22 h to obtain mixture B; among them, the preparation method of DO-SEP is: under magnetic stirring at a rotation speed of 950 r / min, weigh 5 g of sepiolite (SEP) and place it in 100 mL of deionized water, continuously stir at room temperature for 22 h, then filter, transfer the filter cake to vacuum drying at 90 °C for 10 h, grind it through a 100-mesh sieve to obtain DO-SEP;

[0065] (3) Place mixture B in a hydrothermal reaction kettle, continuously heat it at 200 °C for 15 h to obtain product C. Naturally cool product C to room temperature, after centrifugal separation, wash it repeatedly with ethanol and deionized water, and vacuum dry it at 80 °C for 12 h to obtain sample D; place sample D in a tubular furnace, introduce a H2 / N2 mixed gas with a flow rate of 190 mL / min and a H2 volume fraction of 9%, heat it to 200 °C at a rate of 2 °C / min and keep it for 6 h to obtain the MoS2 / DO-SEP composite material, that is, the hydrodesulfurization-hydrolysis coupling desulfurization catalyst;

[0066] Figure 6To obtain the XRD pattern of the MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst, as can be seen from the figure, diffraction peaks of the (110), (131), (400), (331), and (191) lattice planes of sepiolite were observed at 2θ = 7.4°, 20.6°, 26.6°, 28.0°, and 35.0° in the XRD spectrum of the MoS2 / DO-SEP catalyst (PDF#75-1597); in addition, diffraction peaks at 2θ = 14.0°, 32.9°, 39.6°, and 58.8° attributed to the (002), (100), (103), and (110) crystal planes of the MoS2 nanosheet crystals (PDF#73-1508) indicate that MoS2 was successfully synthesized on sepiolite in the composite material; based on the (002) peak of MoS2, XRD was used as a simple and convenient method to judge the number of layers of MoS2 nanosheets. Compared with pure-phase MoS2, only weak diffraction peaks of the (002) crystal plane appeared in the XRD spectrum of the MoS2 / DO-SEP catalyst, indicating that there was almost no self-accumulation of the MoS2 (002) plane in MoS2 / DO-Sep, and MoS2 was highly dispersed in the composite material.

[0067] Figure 7 To obtain the SEM images of the MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst, among which, (a) is the SEM image of DO-SEP; (b) is the SEM image of MoS2 / DO-SEP; (c) is the EDS spectrum of MoS2 / DO-SEP. In Figure 7 (a), it can be observed that the morphology of DO-Sep is one-dimensional nanofibers, and the clean surface is suitable as a catalyst support. In the SEM image (b) of MoS2 / DO-SEP, it can be observed that MoS2 is uniformly dispersed on sepiolite nanofibers. According to the EDS (c) analysis, the weight percentage of the S element (7.54%) is lower than that of the Mo element (9.01%). Therefore, it can be reasonably concluded that there are a large number of S vacancies on MoS2 in MoS2 / DO-Sep.

[0068] Figure 8 To obtain the TEM and HRTEM spectra of the MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst, among which, (a) is the TEM spectrum of MoS2 / DO-SEP, (b) is the HRTEM spectrum of MoS2 / DO-SEP, and (c-c5) is the Mapping element spectrum of MoS2 / DO-SEP; from Figure 8 (a), it can be seen that the uniform structure indicates that MoS2 has successfully grown on sepiolite nanofibers, and MoS2 is vertically and uniformly dispersed on sepiolite nanofibers. In Figure 8In (b), it can be clearly observed that MoS2 has a good layered structure and is well supported on the surface of sepiolite nanofibers. The few-layer MoS2 flakes are highly dispersed in the composite material, which is consistent with the conclusion obtained from XRD. In the Mapping elemental spectrum of MoS2 / DO-SEP (c-c1), the overlapping distribution regions of Si, O, and Mg belong to sepiolite, while the overlapping distribution regions of the corresponding S and Mo elements of MoS2 are located outside the Si, O, and Mg elements. These results further confirm that the few-layer molybdenum disulfide nanosheets and sepiolite nanofibers in the MoS2 / DO-Sep composite material form a 1D / 2D vertical heterostructure.

[0069] Such as Figure 5 , the specific implementation steps of a hydrodesulfurization-hydrolysis coupling desulfurization catalyst for removing organic sulfur in blast furnace gas are as follows:

[0070] 1) The blast furnace gas containing 60% organic sulfur (including carbonyl sulfide, carbon disulfide, thioether, and mercaptan) and 40% inorganic sulfur (hydrogen sulfide) led out from the outlet pipe of the gas duct is successively passed through a bag filter and a dechlorination and deoxygenation pretreatment tower for dust removal, dechlorination, and deoxygenation pretreatment, and then the gas is sent into a hydrodesulfurization-hydrolysis coupling catalytic conversion tower. After dust removal, dechlorination, and deoxygenation, the oxygen concentration in the gas is 0.008%, and the dust concentration in the gas is 5 mg·Nm -3 Hereinafter, the hydrogen chloride content in the gas is less than 0.2 mg·Nm -3 Hereinafter;

[0071] 2) 50 mg of the MoS2 / DO-SEP composite material is filled into the hydrodesulfurization-hydrolysis coupling catalytic conversion tower. The temperature of the hydrodesulfurization-hydrolysis desulfurization catalytic conversion tower is controlled at 200 °C, the water vapor content is 6%, and the H2 content is 4% for catalytic conversion to obtain desulfurized gas. The conversion rate of organic sulfur is above 99%, and the product selectivity reaches 100%. The desulfurized gas is sent into a hydrogen sulfide removal tower, and alkali-modified activated carbon is used to remove the originally contained H2S and the H2S converted from organic sulfur in the gas. At the same time, the conversion rate of organic sulfur and the product selectivity of the MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst for blast furnace gas are tested under different temperature conditions of 100 - 200 °C. The results are as Figure 1 shown, where (a) is the conversion rate effect diagram of the MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst for COS, CS2, CH3SH, and CH3SCH3; (b) is the H2S selectivity effect diagram corresponding to the MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst. It can be seen from the figure that under the action of the MoS2 / DO-SEP catalyst, COS, CS2, CH3SH, and CH3SCH3 are completely converted at 200 °C, and the H2S selectivity is close to 100%;

[0072] 3) After the activity of the hydrodesulfurization-hydrolysis coupling desulfurization catalyst decreases, superheated steam with a hydrogen concentration of 8% is introduced to regenerate the hydrodesulfurization-hydrolysis coupling desulfurization catalyst. The temperature of the superheated steam is 250 °C, the purging time is 20 h, and then it is dried with dry hot air at 80 °C; Figure 7 It is a regeneration efficiency diagram. As can be seen from the figure, the activity of the regenerated hydrodesulfurization-hydrolysis coupling desulfurization catalyst can be increased to more than 95%, and it can be recycled and regenerated 4 times.

[0073] Example 3

[0074] A hydrodesulfurization-hydrolysis coupling desulfurization catalyst, and the preparation method specifically includes the following steps:

[0075] (1) Dissolve 1236 mg (1.3 mmol) of (NH4)6Mo7O 24 ·4H2O, 4806 mg (20 mmol) of C6H 12 N2O4S2 and 21713 mg (7.3 mmol) of H 28 N6O 41 W 12 in 90 mL of deionized water, and stir for 40 min under the condition of a rotation speed of 950 r / min to obtain a mixture A, where the molar ratio of W:Mo is 0.8;

[0076] (2) Add 1.3 g of DO-SEP to the mixture A, stir at 800 r / min for 30 min, then add 30 mL of propionic acid, and stir at room temperature for 23 h to obtain a mixture B; among them, the preparation method of DO-SEP is: under magnetic stirring at a rotation speed of 1000 r / min, weigh 5 g of sepiolite (SEP) and place it in 110 mL of deionized water, continuously stir at room temperature for 20 h, then filter, transfer the filter cake to vacuum dry at 85 °C for 10 h, grind it through a 100-mesh sieve to obtain DO-SEP;

[0077] (3) Place the mixture B in a hydrothermal reaction kettle, continuously heat at 220 °C for 18 h to obtain a product C. Naturally cool the product C to room temperature, after centrifugal separation, wash it repeatedly with ethanol and deionized water, and vacuum dry at 85 °C for 10 h to obtain a sample D; place the sample D in a tubular furnace, introduce a H2 / N2 mixed gas with a flow rate of 180 mL / min and a H2 volume fraction of 8%, and heat it to 190 °C at a rate of 2 °C / min and keep it for 7 h to obtain a W 0.8 MoS2 / DO-SEP composite material, that is, the hydrodesulfurization-hydrolysis coupling desulfurization catalyst;

[0078] As Figure 5 , provide the specific implementation steps for a hydrodesulfurization-hydrolysis coupling desulfurization catalyst to remove organic sulfur in blast furnace gas:

[0079] 1) The blast furnace gas containing 70% organic sulfur (including carbonyl sulfide, carbon disulfide, thioether, and mercaptan) and 30% inorganic sulfur (hydrogen sulfide) led out from the outlet of the gas duct is successively passed through a bag dust removal device and a dechlorination and deoxygenation pretreatment tower for dust removal, dechlorination, and deoxygenation pretreatment, and then the gas is sent into a hydrogenation-hydrolysis coupling catalytic conversion tower. After dust removal, dechlorination, and deoxygenation, the oxygen concentration in the gas is 0.003%, and the dust concentration in the gas is 5 mg·Nm -3 Next, the hydrogen chloride content in the gas is less than 0.2 mg·Nm -3 Next;

[0080] 2) 50 mg of W 0.8 MoS2 / DO-SEP composite material is filled into the hydrogenation-hydrolysis coupling catalytic conversion tower. The temperature of the hydrogenation-hydrolysis desulfurization catalytic conversion tower is controlled at 190 °C, the water vapor content is 8%, and the H2 content is 3%. Catalytic conversion is carried out to obtain desulfurized gas. The conversion rate of organic sulfur is above 99%, and the product selectivity reaches 100%. The desulfurized gas is sent into a hydrogen sulfide removal tower, and alkali-modified activated carbon is used to remove the originally contained H2S and the H2S converted from organic sulfur in the gas;

[0081] 3) After the activity of the hydrogenation-hydrolysis coupling desulfurization catalyst decreases, superheated steam with a hydrogen concentration of 10% is introduced to regenerate the hydrogenation-hydrolysis coupling desulfurization catalyst. The temperature of the superheated steam is 300 °C, the purging time is 10 h, and then it is dried with dry hot air at 65 °C; Figure 7 For the regeneration efficiency diagram, it can be seen from the figure that the activity of the hydrogenation-hydrolysis coupling desulfurization catalyst after regeneration can be increased to above 95%, and it can be recycled and regenerated 4 times.

[0082] Example 4

[0083] A hydrogenation-hydrolysis coupling desulfurization catalyst, and the preparation method specifically includes the following steps:

[0084] (1) Dissolve 2225 mg (1.8 mmol) of (NH4)6Mo7O 24 ·4H2O, 2283 mg (55 mmol) of CH4N2S, and 1834 mg (6.3 mmol) of Co(NO3)2·6H2O in 130 mL of deionized water, and stir for 30 min under the condition of a rotation speed of 1000 r / min to obtain a mixture A, where the molar ratio of Co:Mo is 0.5;

[0085] (2) Add 1.8 g of DO-SEP to the mixture A, stir at 950 r / min for 25 min, then add 27 mL of acetic acid, and stir at room temperature for 21 h to obtain mixture B; among them, the preparation method of DO-SEP is as follows: under magnetic stirring at a rotation speed of 900 r / min, weigh 5 g of sepiolite (SEP) and place it in 120 mL of deionized water, continuously stir at room temperature for 24 h, then filter, transfer the filter cake to vacuum dry at 80 °C for 11 h, grind it through a 100-mesh sieve to obtain DO-SEP;

[0086] (3) Place mixture B in a hydrothermal reaction kettle, continuously heat at 220 °C for 24 h to obtain product C. After product C is naturally cooled to room temperature, centrifuge and separate it, and wash it repeatedly with ethanol and deionized water, then vacuum dry at 90 °C for 10 h to obtain sample D; place sample D in a tubular furnace, introduce a H2 / N2 mixed gas with a flow rate of 195 mL / min and a H2 volume fraction of 8%, heat it at a rate of 2 °C / min to 195 °C and keep it for 8 h to obtain Co 0.5 MoS2 / DO-SEP composite material, that is, a hydrodesulfurization-hydrolysis coupling desulfurization catalyst;

[0087] As Figure 5 , provide the specific implementation steps of a hydrodesulfurization-hydrolysis coupling desulfurization catalyst for removing organic sulfur in blast furnace gas:

[0088] 1) The blast furnace gas containing 80% organic sulfur (including carbonyl sulfide, carbon disulfide, thioether, mercaptan) and 20% inorganic sulfur (hydrogen sulfide) led out from the outlet pipe of the gas conduit is successively passed through a bag dust removal device and a dechlorination and deoxygenation pretreatment tower for dust removal, dechlorination, and deoxygenation pretreatment, and then the gas is sent into a hydrodesulfurization-hydrolysis coupling catalytic conversion tower. After dust removal, dechlorination, and deoxygenation, the oxygen concentration in the gas is 0.001%, the dust concentration in the gas is below 5 mg·Nm -3 Hereinafter, the hydrogen chloride content in the gas is below 0.2 mg·Nm -3 Hereinafter;

[0089] 2) Fill 50 mg of Co 0.5 MoS2 / DO-SEP composite material into the hydrodesulfurization-hydrolysis coupling catalytic conversion tower. The temperature of the hydrodesulfurization-hydrolysis desulfurization catalytic conversion tower is controlled at 170 °C, the water vapor content is 10%, and the H2 content is 5%. Carry out catalytic conversion to obtain desulfurized gas. The conversion rate of organic sulfur is above 99%, and the product selectivity reaches 100%; send the desulfurized gas into a hydrogen sulfide removal tower, and use alkali-modified activated carbon to remove the original H2S and the H2S converted from organic sulfur in the gas;

[0090] 3) After the activity of the hydrodesulfurization-hydrolysis coupling desulfurization catalyst decreases, superheated steam with a hydrogen concentration of 10% is introduced to regenerate the hydrodesulfurization-hydrolysis coupling desulfurization catalyst. The temperature of the superheated steam is 260 °C, the purging time is 18 h, and then it is dried with dry hot air at 75 °C; Figure 7 It is a regeneration efficiency diagram. As can be seen from the figure, the activity of the regenerated hydrodesulfurization-hydrolysis coupling desulfurization catalyst can be increased to more than 95%, and it can be recycled and regenerated 3 times.

[0091] Example 5

[0092] A hydrodesulfurization-hydrolysis coupling desulfurization catalyst, the preparation method specifically includes the following steps:

[0093] (1) Dissolve 1694 mg (7 mmol) of Na2MoO4·2H2O and 3605 mg (15 mmol) of C6H 12 N2O4S2 in 70 mL of deionized water, and stir for 60 min under the condition of a rotation speed of 800 r / min to obtain mixture A;

[0094] (2) Add 1 g of DO-SEP to mixture A, stir at 850 r / min for 30 min, then add 23 mL of acetic acid, and stir at room temperature for 24 h to obtain mixture B; among them, the preparation method of DO-SEP is: under magnetic stirring at a rotation speed of 1000 r / min, weigh 5 g of sepiolite (SEP) and place it in 125 mL of deionized water, continuously stir at room temperature for 20 h and then filter, transfer the filter cake to vacuum dry at 80 °C for 12 h, grind it through a 100-mesh sieve to obtain DO-SEP;

[0095] (3) Place mixture B in a hydrothermal reaction kettle, continuously heat at 200 °C for 18 h to obtain product C. Naturally cool product C to room temperature, after centrifugal separation, wash it repeatedly with ethanol and deionized water, and vacuum dry at 75 °C for 15 h to obtain sample D; place sample D in a tubular furnace, introduce a H2 / N2 mixed gas with a flow rate of 185 mL / min and a H2 volume fraction of 9%, and heat it to 190 °C at a rate of 2 °C / min and hold for 7 h to obtain the MoS2 / DO-SEP composite material, that is, the hydrodesulfurization-hydrolysis coupling desulfurization catalyst;

[0096] As Figure 5 , provide the specific implementation steps for a hydrodesulfurization-hydrolysis coupling desulfurization catalyst to remove organic sulfur in blast furnace gas:

[0097] 1) The blast furnace gas containing 75% organic sulfur (including carbonyl sulfide, carbon disulfide, thioether, and thiol) and 25% inorganic sulfur (hydrogen sulfide) led out from the outlet of the gas conduit is subjected to dust removal, dechlorination, and deoxidation pretreatment, and then the gas is sent into the hydrogenation-hydrolysis coupling catalytic conversion tower. The oxygen concentration in the gas after dust removal, dechlorination, and deoxidation is 0.01%, and the dust concentration in the gas is 5 mg·Nm -3 Hereinafter, the hydrogen chloride content in the gas is less than 0.2 mg·Nm -3 Hereinafter;

[0098] 2) 50 mg of MoS2 / DO-SEP composite material is filled into the hydrogenation-hydrolysis coupling catalytic conversion tower. The temperature of the hydrogenation-hydrolysis desulfurization catalytic conversion tower is controlled at 150 °C, the water vapor content is 8%, and the H2 content is 5%. Catalytic conversion is carried out to obtain desulfurized gas. The conversion rate of organic sulfur is above 99%, and the product selectivity reaches 100%. The desulfurized gas is sent into the hydrogen sulfide removal tower, and the modified activated carbon with alkali is used to remove the originally contained H2S and the H2S converted from organic sulfur in the gas;

[0099] 3) After the activity of the hydrogenation-hydrolysis coupling desulfurization catalyst decreases, superheated steam with a hydrogen concentration of 8% is introduced to regenerate the hydrogenation-hydrolysis coupling desulfurization catalyst. The temperature of the superheated steam is 270 °C, the purging time is 16 h, and then it is dried with dry hot air at 80 °C; Figure 7 It is a regeneration efficiency diagram. As can be seen from the figure, the activity of the hydrogenation-hydrolysis coupling desulfurization catalyst after regeneration can be increased to above 95%, and it can be recycled and regenerated 4 times.

[0100] Comparative Example 1

[0101] Compared with the Ni 0.2 MoS2 / DO-SEP catalyst in Example 1, Ni 0.2 MoS2 was prepared. The preparation method was not to add DO-SEP, and the remaining steps were exactly the same as those of the raw materials and Example 1;

[0102] Adopt the same specific implementation steps as in the example to remove organic sulfur in the blast furnace gas. The conversion rate of organic sulfur is below 75%, and the product selectivity is below 90%;

[0103] At the same time, the conversion rate and product selectivity of Ni 0.2 MoS2 desulfurization catalyst for organic sulfur in blast furnace gas were tested under different temperature conditions of 100 - 200 °C. The results are as Figure 2 shown. Among them, (a) is the conversion rate effect diagram of Ni 0.2 MoS2 desulfurization catalyst for COS, CS2, CH3SH, and CH3SCH3; (b) is the H2S selectivity effect diagram corresponding to Ni 0.2 MoS2 desulfurization catalyst. As can be seen from the figure, the pure phase Ni0.2 The conversion of organic sulfur by the MoS2 desulfurization catalyst is not ideal, and the average removal rate at 200 °C is less than 50%.

[0104] Comparative Example 2

[0105] Compared with Example 3W 0.8 The MoS2 / DO-SEP catalyst was compared, and W without adding organic acid was prepared 0.8 MoS2 / DO-SEP(N-OA) (N-OA means no organic acid added), and the preparation method was not to add organic acid, and the remaining steps were exactly the same as those of the raw materials and Example 3;

[0106] Using the same specific implementation steps for removing organic sulfur in blast furnace gas as in the example, the conversion rate of organic sulfur was below 96%, and the product selectivity was less than 90%;

[0107] At the same time, under different temperature conditions of 100-200 °C, W 0.8 The conversion rate and product selectivity of the MoS2 / DO-SEP desulfurization catalyst for organic sulfur in blast furnace gas were tested. The results were as follows Figure 3 shown, where (a) is the conversion rate effect diagram of the MoS2 / DO-SEP desulfurization catalyst for COS, CS2, CH3SH and CH3SCH3; (b) is the selectivity effect diagram of the MoS2 / DO-SEP desulfurization catalyst corresponding to H2S. As can be seen from the figure, W 0.8 The conversion efficiency of the MoS2 / DO-SEP desulfurization catalyst for organic sulfur was significantly improved, but its catalytic conversion performance for organic sulfur was not as good as that of the MoS2 / DO-SEP desulfurization catalyst prepared with the assistance of organic acid (such as 0.8 );The experiment shows that the 1D / 2D vertical MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst constructed by sepiolite supported MoS2 has obvious catalytic conversion performance for organic sulfur, and its catalytic activity for organic sulfur can be further improved by organic acid-assisted synthesis. 0.8 MoS2 / DO-SEP desulfurization catalyst has significantly improved the conversion efficiency of organic sulfur, but its performance in catalytically converting organic sulfur is not as good as that of the MoS2 / DO-SEP desulfurization catalyst prepared with the assistance of organic acid (such as Figure 1 );The experiment shows that the 1D / 2D vertical MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst constructed by sepiolite supported MoS2 has obvious catalytic conversion performance for organic sulfur, and its catalytic activity for organic sulfur can be further improved by organic acid-assisted synthesis. x MoS2 constructed 1D / 2D vertical MoS2 x MoS2 / DO-SEP hydrodesulfurization-hydrolysis coupling desulfurization catalyst has obvious catalytic conversion performance for organic sulfur, and its catalytic activity for organic sulfur can be further improved by organic acid-assisted synthesis.

[0108] Comparative Example 3

[0109] The Co prepared in Example 4 0.5 The MoS2 / DO-SEP catalyst was tested for exploring the hydrodesulfurization and hydrolysis catalytic conversion desulfurization conditions. The specific steps were as follows:

[0110] 1) The blast furnace gas containing 80% organic sulfur (including carbonyl sulfide, carbon disulfide, thioether, and mercaptan) and 20% inorganic sulfur (hydrogen sulfide) led out from the outlet of the gas duct is subjected to dust removal, dechlorination, and deoxidation pretreatment, and then the gas is sent into the hydrogenation-hydrolysis coupling catalytic conversion tower. After dust removal, dechlorination, and deoxidation, the oxygen concentration in the gas is 0.001%, and the dust concentration in the gas is 5 mg·Nm -3 Hereinafter, the hydrogen chloride content in the gas is less than 0.2 mg·Nm -3 Hereinafter;

[0111] 2) 50 mg of Co 0.5 MoS2 / DO-SEP composite material is filled into the hydrogenation-hydrolysis coupling catalytic conversion tower, and the conditions are as follows:

[0112] The temperature of the hydrogenation-hydrolysis desulfurization catalytic conversion tower is controlled at 170 °C, the water vapor content is 10%, the H2 content is 5%, and it lasts for 4 h. The concentrations of COS, CS2, CH3SH, and CH3SCH3 in the tail gas are detected;

[0113] The temperature of the hydrogenation-hydrolysis desulfurization catalytic conversion tower is controlled at 170 °C, the water vapor content is 10%, the H2 content is 0%, and it lasts for 4 h. The concentrations of COS, CS2, CH3SH, and CH3SCH3 in the tail gas are detected;

[0114] The temperature of the hydrogenation-hydrolysis desulfurization catalytic conversion tower is controlled at 170 °C, the water vapor content is 0%, the H2 content is 5%, and it lasts for 4 h. The concentrations of COS, CS2, CH3SH, and CH3SCH3 in the tail gas are detected;

[0115] The relevant results are as Figure 4 , as can be seen from the figure, when both H2 and H2O exist in the hydrogenation-hydrolysis coupling catalytic conversion tower, the conversion rates of CS2, COS, CH3SH, and CH3SCH3 by the Co 0.5 MoS2 / DO-SEP catalyst reach 100%; if H2O is cut off, the conversion rates of CS2, COS, CH3SH, and CH3SCH3 drop to 70%, 60%, 20%, and 25% respectively; if H2 is cut off and H2O is introduced, the conversion rates of CS2, COS, CH3SH, and CH3SCH3 reach 85%, 97%, 95%, and 90% respectively; the experiment shows that Co 0.5 MoS2 / DO-SEP catalyst has excellent hydrogenation-hydrolysis coupling catalytic conversion performance for organic sulfur.

[0116] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for preparing a hydrogenation-hydrolysis coupled desulfurization catalyst, characterized in that: The specific steps include: (1) adding a molybdenum source, an inorganic metal salt and a sulfur source into deionized water and mixing them uniformly to obtain a mixture A; (2) adding sepiolite and an organic acid to the mixture A in sequence for reaction to obtain a mixture B; (3) The product obtained by subjecting the mixture B to a hydrothermal reaction is washed and dried, and then reduced to obtain a hydrogenation-hydrolysis coupled desulfurization catalyst.

2. The method for preparing a hydrogenation-hydrolysis coupled desulfurization catalyst according to claim 1, characterized in that: The molar ratio of the metal ion in the inorganic metal salt to the molybdenum source in step (1) is 0-0.8; The molar volume ratio of the molybdenum source, the sulfur source and the deionized water is 1-2 mmol: 30-60 mmol: 70-140 mL; The mixing parameters are: time of 30-60 min, temperature of room temperature, and rotation speed of 800-1000 r / min.

3. The method for preparing a hydrogenation-hydrolysis coupled desulfurization catalyst according to claim 1, characterized in that: In step (1), the molybdenum source is ammonium molybdate or sodium molybdate; the sulfur source is thiourea or L-cystine; and the inorganic metal salt is any one of nickel nitrate, cobalt nitrate and ammonium metatungstate.

4. The method for preparing a hydrogenation-hydrolysis coupled desulfurization catalyst according to claim 1, characterized in that: In step (2), the ratio of the molybdenum source, the sepiolite and the organic acid is 1-2 mmol: 1-1.5 g: 20-30 mL; The reaction parameters after the sepiolite is added are: stirring at room temperature for 20-30 minutes, and the rotation speed is 800-1000r / min; The reaction parameters after the organic acid is added are: stirring at room temperature for 20-24 hours, and a rotation speed of 800-1000 r / min. The organic acid is any one of formic acid, acetic acid or propionic acid.

5. The method for preparing a hydrogenation-hydrolysis coupled desulfurization catalyst according to claim 4, characterized in that: The sepiolite is subjected to the following pretreatment before being added, and the specific steps are: placing the sepiolite in deionized water, stirring at room temperature for 20-24 hours, filtering, transferring the filter cake to 80-90° C. and vacuum drying for 10-12 hours, and grinding through a 100-mesh sieve; Wherein, the mass volume ratio of the sepiolite to the deionized water is 5g:100-125mL, and the stirring speed is 900-1000r / min.

6. The method for preparing a hydrogenation-hydrolysis coupled desulfurization catalyst according to claim 1, characterized in that: The parameters of the hydrothermal reaction in step (3) are: reaction at 200-220° C. for 12-24 h; The washing is repeated with ethanol and deionized water; The drying is performed by vacuum drying at 70-90° C. for 10-15 hours; The reduction step is: introducing a mixed gas of H2 / N2, heating to 180-200°C and reacting for 6-8h.

7. The method for preparing a hydrogenation-hydrolysis coupled desulfurization catalyst according to claim 6, characterized in that: The volume fraction of H2 in the mixed gas is 8-10%, the gas flow rate is 180-200 mL / min, and the heating rate is 2°C / min.

8. A hydrogenation-hydrolysis coupled desulfurization catalyst obtained by the preparation method according to any one of claims 1 to 7.

9. Use of a hydrogenation-hydrolysis coupled desulfurization catalyst obtained by the preparation method according to any one of claims 1 to 7 in the desulfurization of metallurgical coal gas.

10. The use according to claim 9, characterized in that: The catalytic temperature of the catalyst is 150-200°C.

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