Sulfur-resistant non-noble metal catalyst for removing carbon monoxide and preparation method thereof

Abstract

The invention discloses a sulfur-resistant non-noble metal catalyst for removing carbon monoxide and a preparation method thereof. The preparation method comprises the following steps: step 1, dissolving aluminum oxide, cerium-containing metal salt and a precipitator in a solvent, fully mixing, and dispersing to obtain a colloidal dispersion system; a hydrothermal product is obtained after the hydrothermal reaction, and solid powder A is obtained after the hydrothermal product is roasted; step 2, dropwise adding a copper-containing metal salt solution into the solid powder A under a ball-milling condition to obtain a turbid liquid; carrying out heat preservation roasting to obtain solid powder B; 3, roasting the molybdenum-containing metal salt, and performing thermal decomposition to obtain solid powder C; and 4, adding the solid powder C obtained in the step 3 into the turbid liquid of the solid powder B, dispersing, and roasting to obtain the required catalyst. The obtained catalyst is stable in overall structure and can still keep good catalytic performance in a sulfur-containing environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, in particular to a sulfur-resistant non-noble metal catalyst for removing carbon monoxide and a preparation method thereof. BACKGROUND

[0002] Tunnels and underground spaces (such as highway tunnels, subway tunnels, underground pipe galleries, etc.) are closed or semi-closed confined spaces, and their fire accidents have the characteristics of fast smoke diffusion, high concentration of toxic gases, long residence time, and great difficulty in personnel escape and rescue. Once a fire occurs, the toxic gases enriched in the smoke are the core inducement for the casualties of trapped personnel, and the harm is much higher than that of ordinary open space fires.

[0003] Carbon monoxide is the main toxic component in the smoke of tunnel and underground space fires, and its toxic effect is greatly amplified in a closed environment. At the same time, the daily driving of vehicles in tunnels will leave behind sulfur-containing gases such as SO2 and H2S. The high-temperature environment of a fire will further cause building materials, vehicle rubber, etc. to burn and release more SO2, forming a complex smoke environment dominated by "CO + SO2" synergistic pollution. Current common CO emission control technologies mainly include adsorption separation method, solution absorption method, direct combustion method, cryogenic method, and catalytic oxidation method, etc. Among them, the catalytic oxidation method can convert CO into harmless CO2 at a relatively low temperature, and is the most direct and efficient technology for removing CO. However, existing researches are mostly based on ideal simulated smoke conditions, ignoring the fatal impact of SO2 in actual tunnel smoke on the catalyst - SO2 is prone to irreversible chemical reaction with the active components of the catalyst, forming stable sulfides deposited on the surface of the catalyst, causing the active sites to be completely covered, and ultimately causing the catalyst to rapidly deactivate and unable to continuously remove CO.

[0004] Existing CO oxidation catalysts have obvious technical shortcomings: noble metal catalysts represented by Pt, Rh, Pd, etc. have high catalytic activity, but are expensive and prone to sintering at high temperatures in tunnel fires, making it difficult to meet the needs of large-scale and long-term use in tunnel projects. Traditional non-noble metal oxide catalysts (such as single CuO, CeO2-based catalysts) have low cost, but have poor resistance to SO2 poisoning, and the CO removal efficiency in tunnel sulfur-containing smoke drops sharply to inactivation, making it unable to adapt to the scene requirements of continuous smoke exhaust and purification after a tunnel fire. SUMMARY

[0005] The present application provides a sulfur-resistant non-noble metal catalyst for removing carbon monoxide and a preparation method thereof to solve the problems existing in the prior art.

[0006] The technical scheme adopted by the present application is: a preparation method of a sulfur-resistant non-noble metal catalyst for removing carbon monoxide, comprising the following steps: Step 1: Alumina, cerium-containing metal salt, and precipitant are dissolved in a solvent and thoroughly mixed to obtain a colloidal dispersion system. A hydrothermal reaction is then performed to obtain a hydrothermal product, which is calcined to obtain solid powder A. The cerium-containing metal salt accounts for 9 wt.% of the mass of the alumina. Step 2: The copper-containing metal salt solution is slowly added dropwise to the powder A solution to obtain a suspension; after calcination at a certain temperature, solid powder B is obtained; the copper-containing metal salt accounts for 7 wt.% of the mass of the cerium-containing metal salt powder A. Step 3: After calcination of the molybdenum-containing metal salt, thermal decomposition yields solid powder C; wherein the solid powder C accounts for 7–11 wt.% of the mass of the cerium-containing metal salt B. Step 4: Add the solid powder C obtained in step 3 to the suspension of solid powder B, disperse it, and then calcine it to obtain the desired catalyst.

[0007] Furthermore, in step 1, the cerium-containing metal salt is cerium nitrate, the precipitant is 1,3,5-pyromellitic acid, and the molar ratio of the cerium-containing metal salt to the precipitant is 1:1.

[0008] Furthermore, in step 1, the hydrothermal reaction temperature is 120 °C and the reaction time is 12 h.

[0009] Furthermore, in step 1, the hydrothermal product is heated to 500 °C at a rate of 2 °C / min for calcination for 4 h.

[0010] Furthermore, the alumina and cerium-containing metal salts in step 1 are first pretreated, and the pretreatment process is as follows: Dry at 120 °C for 4–6 hours, then calcine at 300 °C for 4 hours by increasing the temperature at a rate of 1–2 °C / min.

[0011] Furthermore, in step 2, the copper-containing metal salt is copper nitrate, the calcination temperature is 400 ℃, the heating rate is 2 ℃ / min, and the holding time is 3 h.

[0012] Furthermore, in step 3, the molybdenum metal salt is ammonium molybdate, with a thermal decomposition temperature of 500 ℃, a heating rate of 2 ℃ / min, and a holding time of 2 h.

[0013] Furthermore, in step 4, the calcination temperature is 400 ℃, the heating rate is 5 ℃ / min, and the holding time is 3h.

[0014] Furthermore, the dispersion process in step 4 is as follows: First, dispersion is performed using a shear dispersion emulsifier, and then dispersion is performed using an ultrasonic disperser.

[0015] A non-precious metal catalyst for sulfur-resistant carbon monoxide removal, wherein the catalyst has a carbon monoxide removal efficiency greater than 50%.

[0016] The beneficial effects of this invention are: The catalyst obtained in this invention belongs to a high-performance transition metal composite oxide catalyst system. With copper oxide as the core active component, a MoO3-CuO-CeO2 / γ-Al2O3 composite catalytic system with a specific crystal structure is formed through precise doping and interface control of cerium and molybdenum. High-purity precursors containing molybdenum, copper, and cerium are used. Through uniform dispersion and post-treatment of the precursors, the active components exhibit high dispersibility and chemical homogeneity on the surface of the γ-Al2O3 support. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the preparation method of the present invention.

[0018] Figure 2 This is a SEM image of the catalyst obtained in Example 2 of the present invention.

[0019] Figure 3 The XRD patterns of the catalysts obtained in Examples 1-3 and Comparative Example 1 of this invention are shown.

[0020] Figure 4 This is a comparison of the sulfur resistance performance of the catalysts obtained in Comparative Example 1 and Comparative Example 2 of the present invention.

[0021] Figure 5 The catalytic performance of the catalysts obtained in Examples 1-3 of this invention is shown.

[0022] Figure 6 The sulfur resistance performance of the catalyst obtained in Example 2 of this invention and the control group are shown. Detailed Implementation

[0023] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0024] A method for preparing a non-precious metal catalyst for sulfur-resistant carbon monoxide removal includes the following steps: Step 1: Alumina, cerium-containing metal salt, and precipitant were dissolved in a solvent and thoroughly mixed to obtain a colloidal dispersion system. A hydrothermal reaction was then carried out to obtain a hydrothermal product, which was subsequently calcined to obtain solid powder A. The cerium-containing metal salt comprised 9 wt% of the alumina. The cerium-containing metal salt was cerium nitrate, and the precipitant was 1,3,5-pyromellitic acid, with a molar ratio of cerium-containing metal salt to precipitant of 1:1. The hydrothermal reaction temperature was 120 °C, and the reaction time was 12 h. The hydrothermal product was then calcined at a rate of 2 °C / min to 500 °C for 4 h.

[0025] Alumina and cerium-containing metal salts first undergo pretreatment, the process of which is as follows: Dry at 120 °C for 4–6 hours, then calcine at 300 °C for 4 hours by increasing the temperature at a rate of 1–2 °C / min.

[0026] Step 2: The copper-containing metal salt solution is slowly added dropwise to the powder A solution to obtain a suspension; after calcination at a constant temperature, solid powder B is obtained; the copper-containing metal salt accounts for 7 wt% of the mass of the cerium-containing metal salt powder A; the copper-containing metal salt is copper nitrate; the calcination temperature is 400 ℃, the heating rate is 2 ℃ / min, and the holding time is 3 h.

[0027] Step 3: After calcination of the molybdenum-containing metal salt, thermal decomposition yields solid powder C; wherein the solid powder C accounts for 7-11 wt% of the mass of the cerium-containing metal salt B. The molybdenum-containing metal salt is ammonium molybdate, with a thermal decomposition temperature of 500 ℃, a heating rate of 2 ℃ / min, and a holding time of 2 h.

[0028] Step 4: Add the solid powder C obtained in step 3 to the suspension of solid powder B, disperse it, and then calcine it to obtain the desired catalyst.

[0029] The calcination temperature was 400 ℃, the heating rate was 5 ℃ / min, and the holding time was 3 h. The dispersion process is as follows: First, dispersion is performed using a shear dispersion emulsifier, and then dispersion is performed using an ultrasonic disperser.

[0030] Example 1 A method for preparing a non-precious metal catalyst for sulfur-resistant carbon monoxide removal includes the following steps: Step 1: Mix 68.1 mg of cerium nitrate hexahydrate, 300 mg of nano-gamma alumina, 33 mg of 1,3,5-pyromellitic acid, 30 mL of deionized water and 30 mL of ethanol; stir continuously at 500 r / min for 1 h at room temperature.

[0031] Cerium nitrate hexahydrate and nano-γ-alumina were pretreated by drying at 120 °C for 4 hours, calcining at 300 °C at a heating rate of 1 °C / min, and holding at that temperature for 2 hours.

[0032] The mixture was hydrothermally reacted at 120 °C for 12 h in a programmed temperature-controlled high-pressure hydrothermal synthesis reactor. The filtered precipitate was washed three times each with deionized water and ethanol, with each washing lasting 10 min under stirring at 10000 r / min, until the pH reached 7.

[0033] The precipitate was dried in a programmed temperature vacuum drying oven at 80 °C for 10 h. The dried product was then transferred to a programmed temperature tube furnace and heated to 500 °C at a rate of 2 °C / min in air atmosphere. The temperature was then held for calcination for 4 h to obtain CeO2 / γ-Al2O3.

[0034] Step 2: Add 330 mg of CeO2 / γ-Al2O3 to a 15 mL beaker of deionized water to obtain a suspension; add 70.2 mg of copper nitrate trihydrate to the suspension and stir continuously at 500 r / min for 1 h at room temperature; dry the precipitate in a vacuum drying oven at 80℃ for 7 h; transfer the dried product to a tube furnace and heat it to 400℃ at a rate of 2℃ / min in air atmosphere, and calcine it for 3 h to obtain CuO-CeO2 / γ-Al2O3.

[0035] Step 3: 50 mg of ammonium molybdate tetrahydrate was calcined at 500 °C with a heating rate of 2 °C / min and a holding time of 2 h to obtain 25.2 mg of molybdenum trioxide powder.

[0036] Step 4: Dissolve molybdenum trioxide powder in 15 mL of deionized water to obtain a molybdenum trioxide solution. Add 360 mg of CuO-CeO2 / γ-Al2O3 to a beaker containing 15 mL of deionized water, and slowly add the molybdenum trioxide solution. Stir slowly at 500 r / min for 1 h at room temperature. After standing at room temperature for 12 h, dry in a forced-air environment at 80 ℃ for 7 h. Then calcine at 250 ℃ with a heating rate of 5 ℃ / min for 1.5 h, and finally calcine at 400 ℃ with a heating rate of 2 ℃ / min for 3 h to obtain a non-precious metal catalyst for sulfur-resistant carbon monoxide removal, namely the 7wt%MoO3-7wt%CuO-9wt%CeO2 / γ-Al2O3 catalyst powder shown in the attached figure.

[0037] Example 2 A method for preparing a non-precious metal catalyst for sulfur-resistant carbon monoxide removal includes the following steps: Step 1: Mix 68.1 mg of cerium nitrate hexahydrate, 300 mg of nano-gamma alumina, 33 mg of 1,3,5-pyromellitic acid, 30 mL of deionized water and 30 mL of ethanol; stir continuously at 500 r / min for 1 h at room temperature.

[0038] Cerium nitrate hexahydrate and nano-γ-alumina were pretreated by drying at 120 °C for 6 hours, calcining at 300 °C with a heating rate of 1 °C / min, and holding at that temperature for 2 hours.

[0039] The mixture was hydrothermally reacted at 120 °C for 12 h in a programmed temperature-controlled high-pressure hydrothermal synthesis reactor. The filtered precipitate was washed three times each with deionized water and ethanol, with each washing lasting 10 min under stirring at 8000 r / min, until the pH reached 7.

[0040] The precipitate was dried in a programmed temperature vacuum drying oven at 80 °C for 10 h. The dried product was then transferred to a programmed temperature tube furnace and heated to 500 °C at a rate of 2 °C / min in air atmosphere. The temperature was then held for calcination for 4 h to obtain CeO2 / γ-Al2O3.

[0041] Step 2: Add 330 mg of CeO2 / γ-Al2O3 to a 15 mL beaker of deionized water to obtain a suspension; add 70.2 mg of copper nitrate trihydrate to the suspension and stir continuously at 500 r / min for 1 h at room temperature; dry the precipitate in a vacuum drying oven at 80℃ for 8 h; transfer the dried product to a tube furnace and heat it to 400℃ at a rate of 2℃ / min in air atmosphere, and calcine it for 3 h to obtain CuO-CeO2 / γ-Al2O3.

[0042] Step 3: 59.4 mg of ammonium molybdate tetrahydrate was calcined at 500 °C with a heating rate of 2 °C / min and a holding time of 2 h to obtain 32.4 mg of molybdenum trioxide powder.

[0043] Step 4: Dissolve molybdenum trioxide powder in 15 mL of deionized water to obtain a molybdenum trioxide solution. Add 360 mg of CuO-CeO2 / γ-Al2O3 to a beaker containing 15 mL of deionized water, and slowly add the molybdenum trioxide solution. Stir slowly at 500 r / min for 1 h at room temperature. After standing at room temperature for 12 h, dry in a forced-air environment at 80 ℃ for 6 h. Then calcine at 250 ℃ with a heating rate of 5 ℃ / min for 1.5 h, and finally calcine at 400 ℃ with a heating rate of 2 ℃ / min for 3 h to obtain a non-precious metal catalyst for sulfur-resistant carbon monoxide removal, namely the 9wt%MoO3-7wt%CuO-9wt%CeO2 / γ-Al2O3 catalyst powder shown in the attached figure.

[0044] Example 3 A method for preparing a non-precious metal catalyst for sulfur-resistant carbon monoxide removal includes the following steps: Step 1: Mix 68.1 mg of cerium nitrate hexahydrate, 300 mg of nano-gamma alumina, 33 mg of 1,3,5-pyromellitic acid, 30 mL of deionized water and 30 mL of ethanol; stir continuously at 500 r / min for 1 h at room temperature.

[0045] Cerium nitrate hexahydrate and nano-γ-alumina were pretreated by drying at 120 °C for 5 hours, calcining at 300 °C with a heating rate of 1 °C / min, and holding at that temperature for 2 hours.

[0046] The mixture was hydrothermally reacted at 120 °C for 12 h in a programmed temperature-controlled high-pressure hydrothermal synthesis reactor. The filtered precipitate was washed three times each with deionized water and ethanol, with each washing lasting 10 min under stirring at 9000 r / min, until the pH reached 7.

[0047] The precipitate was dried in a programmed temperature vacuum drying oven at 80 °C for 10 h. The dried product was then transferred to a programmed temperature tube furnace and heated to 500 °C at a rate of 2 °C / min in air atmosphere. The temperature was then held for calcination for 4 h to obtain CeO2 / γ-Al2O3.

[0048] Step 2: Add 330 mg of CeO2 / γ-Al2O3 to a 15 mL beaker of deionized water to obtain a suspension; add 70.2 mg of copper nitrate trihydrate to the suspension and stir continuously at 500 r / min for 1 h at room temperature; dry the precipitate in a vacuum drying oven at 80℃ for 8 h; transfer the dried product to a tube furnace and heat it to 400℃ at a rate of 2℃ / min in air atmosphere, and calcine it for 3 h to obtain CuO-CeO2 / γ-Al2O3.

[0049] Step 3: 72.6 mg of ammonium molybdate tetrahydrate was calcined at 500 °C with a heating rate of 2 °C / min and a holding time of 2 h to obtain 39.5 mg of molybdenum trioxide powder.

[0050] Step 4: Dissolve molybdenum trioxide powder in 15 mL of deionized water to obtain a molybdenum trioxide solution. Add 360 mg of CuO-CeO2 / γ-Al2O3 to a beaker containing 15 mL of deionized water, and slowly add the molybdenum trioxide solution. Stir slowly at 500 r / min for 1 h at room temperature. After standing at room temperature for 12 h, dry in a forced-air environment at 80 ℃ for 8 h. Then calcine at 250 ℃ with a heating rate of 5 ℃ / min for 1.5 h, and finally calcine at 400 ℃ with a heating rate of 2 ℃ / min for 3 h to obtain a non-precious metal catalyst for sulfur-resistant carbon monoxide removal, namely the 11wt%MoO3-7wt%CuO-9wt%CeO2 / γ-Al2O3 catalyst powder shown in the attached figure.

[0051] Comparative Example 1 A method for preparing a catalyst for sulfur removal of carbon monoxide includes the following steps: Step 1: Mix 68.1 mg of cerium nitrate hexahydrate, 300 mg of nano-gamma alumina, 33 mg of 1,3,5-pyromellitic acid, 30 mL of deionized water and 30 mL of ethanol; stir continuously at 500 r / min for 1 h at room temperature.

[0052] Cerium nitrate hexahydrate and nano-γ-alumina were pretreated by drying at 120 °C for 5 hours, calcining at 300 °C with a heating rate of 1 °C / min, and holding at that temperature for 2 hours.

[0053] The mixture was hydrothermally reacted at 120 °C for 12 h in a programmed temperature-controlled high-pressure hydrothermal synthesis reactor. The filtered precipitate was washed three times each with deionized water and ethanol, with each washing lasting 10 min under stirring at 10000 r / min, until the pH reached 7.

[0054] The precipitate was dried in a programmed temperature vacuum drying oven at 80 °C for 10 h. The dried product was then transferred to a programmed temperature tube furnace and heated to 500 °C at a rate of 2 °C / min in air atmosphere. The temperature was then held for calcination for 4 h to obtain CeO2 / γ-Al2O3.

[0055] Step 2: Add 330 mg of CeO2 / γ-Al2O3 to a 15 mL beaker of deionized water to obtain a suspension; add 70.2 mg of copper nitrate trihydrate to the suspension and stir continuously at 500 r / min for 1 h at room temperature; dry the precipitate in a programmed temperature vacuum drying oven at 80℃ for 7 h; transfer the dried product to a programmed temperature tube furnace and calcine at 400℃ at a rate of 2℃ / min in air atmosphere for 3 h to obtain CuO-CeO2 / γ-Al2O3, i.e., 7wt% CuO-9wt% CeO2 / γ-Al2O3 catalyst powder.

[0056] Comparative Example 2 A method for preparing a catalyst for sulfur removal of carbon monoxide includes the following steps: Mix 300 mg of nano-γ-alumina with 15 mL of deionized water; add 63.8 mg of copper nitrate trihydrate and stir continuously at 500 r / min for 1 h at room temperature.

[0057] Nano-γ-alumina was pretreated by drying at 120 ℃ for 5 hours, calcining at 300 ℃ with a heating rate of 1 ℃ / min, and holding at that temperature for 2 hours.

[0058] The mixture was hydrothermally reacted at 120 °C for 12 h in a programmed temperature-controlled high-pressure hydrothermal synthesis reactor. The filtered precipitate was washed three times each with deionized water and ethanol, with each washing lasting 10 min under stirring at 10000 r / min, until the pH reached 7.

[0059] The precipitate was dried in a programmed temperature vacuum drying oven at 80 °C for 7 h. The dried product was then transferred to a programmed temperature tube furnace and heated to 400 °C at a rate of 2 °C / min under air atmosphere, and calcined for 3 h to obtain CuO / γ-Al2O3, i.e., 7 wt.% CuO / γ-Al2O3.

[0060] The obtained catalyst powder was sieved (40-60 mesh). The results of activity and sulfur resistance tests on samples from the examples and comparative examples are shown in Table 1. The methods are as follows: Catalyst activity test: Take 0.1 g of sieved catalyst particles and put them into a fixed-bed quartz tube reactor with an inner diameter of 6 mm. The simulated flue gas consists of CO, O2, and N2, with a CO concentration of 4000 ppm and a reaction temperature of 400℃. The reaction tail gas is monitored online using a flue gas analyzer (testo 350) to obtain the CO conversion rate.

[0061] Catalyst sulfur resistance test: under simulated sulfur-containing atmosphere (4000 ppm CO, 50 ppm SO2, equilibrium gas is N2), reaction temperature 400 ℃, space velocity 10000 h⁻¹ -1 The efficiency of the catalyst in removing CO under certain conditions.

[0062] Table 1. Test results of catalyst activity and sulfur resistance performance in Examples 1-3 and Comparative Examples 1 and 2

[0063] Figure 4 To compare the sulfur resistance performance of the catalysts obtained in Comparative Example 1 and Comparative Example 2, it can be seen from the figure that the catalyst with added Ce has a significantly better sulfur resistance effect than the one without. The sulfur resistance efficiency of the catalyst obtained in Comparative Example 1 is about 20% at 400 °C. The catalyst obtained in Comparative Example 2 is rapidly poisoned and deactivated after contact with SO2 at 400 °C.

[0064] Figure 5 The figures show the performance of the catalysts obtained in Examples 1-3. As can be seen from the figures, the catalysts obtained in the examples have a stable conversion rate of about 90% at 380°C.

[0065] Figure 6 The graph shows the sulfur resistance performance of the catalysts obtained in Example 2 and the control group. As can be seen from the graph, the sulfur resistance stability of the catalysts obtained in the Example 2 is significantly higher than that of the control group.

[0066] The catalyst obtained in this invention incorporates cerium dioxide, copper oxide, and molybdenum trioxide, which have a synergistic effect. CeO2 nanoparticles are highly dispersed on Al2O3, creating active sites, providing oxygen vacancies, and enhancing the thermal stability of the support. After calcination, Cu... 2+ The copper will be converted into CuO. Due to the presence of CeO2, CuO can be highly dispersed on the CeO2 surface, avoiding the agglomeration of copper particles, exposing more active sites, and greatly promoting the reaction rate. It can be seen that the sulfur resistance performance is improved by 24.9% after adding CeO2 compared with the control. Mo forms highly dispersed MoO3 on the catalyst surface. MoO3 preferentially reacts with the active component CuO and the sulfur species SO2. As a sacrificial site for the reaction with SO2, Mo can promote the dissociation of sulfides and help reduce the accumulation of sulfides on the catalyst surface. The strong basic sites on the CeO2 surface are one of the reasons why it easily forms stable cerium sulfate. MoO3 is an acidic oxide. Its introduction will cover or neutralize some of the strong basic sites on the CeO2 surface, change its surface acidity and basicity, inhibit the formation rate and amount of cerium sulfate, and thus prevent catalyst poisoning. The sulfur resistance of the catalyst with added Mo is 22.9% higher than that without added Mo. Therefore, the addition of Mo can improve the overall structural stability of the catalyst, enabling it to maintain good catalytic performance in sulfur-containing environments.

Claims

1. A method for preparing a non-precious metal catalyst for sulfur-resistant carbon monoxide removal, characterized in that, Includes the following steps: Step 1: Alumina, cerium-containing metal salt, and precipitant are dissolved in a solvent and thoroughly mixed to obtain a colloidal dispersion system. A hydrothermal reaction is then performed to obtain a hydrothermal product, which is calcined to obtain solid powder A. The cerium-containing metal salt accounts for 9 wt.% of the mass of the alumina. Step 2: The copper-containing metal salt solution is slowly added dropwise to the powder A solution to obtain a suspension; after calcination at a certain temperature, solid powder B is obtained; the copper-containing metal salt accounts for 7 wt.% of the mass of the cerium-containing metal salt powder A. Step 3: After calcination of the molybdenum-containing metal salt, thermal decomposition yields solid powder C; wherein the mass percentage of solid powder C and cerium-containing metal salt powder B is 7-11 wt.%. Step 4: Add the solid powder C obtained in step 3 to the suspension of solid powder B, disperse it, and then calcine it to obtain the desired catalyst.

2. The preparation method of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal according to claim 1, characterized in that, In step 1, the cerium-containing metal salt is cerium nitrate, the precipitant is 1,3,5-pyromellitic acid, and the molar ratio of the cerium-containing metal salt to the precipitant is 1:

1.

3. The preparation method of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal according to claim 1, characterized in that, In step 1, the hydrothermal reaction temperature is 120 °C and the reaction time is 12 h.

4. The preparation method of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal according to claim 1, characterized in that, In step 1, the hydrothermal product is heated to 500 °C at a rate of 2 °C / min and calcined for 4 h.

5. The preparation method of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal according to claim 1, characterized in that, In step 1, the alumina and cerium-containing metal salts first undergo pretreatment, which is as follows: Dry at 120 °C for 4–6 hours, then calcine at 300 °C for 4 hours by increasing the temperature at a rate of 1–2 °C / min.

6. The preparation method of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal according to claim 1, characterized in that, In step 2, the copper-containing metal salt is copper nitrate, the calcination temperature is 400 ℃, the heating rate is 2 ℃ / min, and the holding time is 3 h.

7. The preparation method of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal according to claim 1, characterized in that, In step 3, the molybdenum metal salt is ammonium molybdate, with a thermal decomposition temperature of 500 ℃, a heating rate of 2 ℃ / min, and a holding time of 2 h.

8. The preparation method of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal according to claim 1, characterized in that, In step 4, the calcination temperature is 400 ℃, the heating rate is 5 ℃ / min, and the holding time is 3 h.

9. The preparation method of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal according to claim 1, characterized in that, The dispersion process in step 4 is as follows: First, dispersion is performed using a shear dispersion emulsifier, and then dispersion is performed using an ultrasonic disperser.

10. The non-precious metal catalyst for sulfur removal and carbon monoxide removal obtained by any one of the preparation methods of claims 1 to 9, characterized in that, The catalyst has a carbon monoxide removal efficiency greater than 50%.

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