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

Abstract

The invention discloses preparation and application of a sulfur-resistant non-noble metal catalyst for removing carbon monoxide, and belongs to the technical field of air pollution treatment. The preparation method comprises the following steps: preparing a cerium modified alumina mixed oxide carrier, loading the active components of the catalyst, and roasting and activating the catalyst. The catalyst has the beneficial effects that a small amount of cerium modified alumina is added, and the activity of the main active species is protected by utilizing the characteristic that cerium oxide preferentially reacts with SO2; the particle size of the active component is regulated and controlled by specifically controlling the nucleation rate, so that the catalyst with better carbon monoxide sulfur-resistant stability in a sulfur-containing atmosphere is prepared.

Description

Technical field:

[0001] The invention belongs to the technical field of air pollution treatment, and more specifically relates to the preparation and application of a non-precious metal catalyst for removing carbon monoxide with sulfur resistance. Background technology:

[0002] At present, my country's air pollution has not been completely controlled. After particulate matter, sulfur oxides and nitrogen oxides are removed from the flue gas emitted by the steel, coking and petrochemical industries, a large amount of CO is still present, with a concentration of 8000-10000 mg / Nm 3 , which will pollute the atmosphere and endanger human health.

[0003] Currently, the most commonly used method to control CO emissions is catalytic oxidation. Supported precious metal catalysts such as Pt, Pd and Au have good activity towards carbon monoxide, but their high price and scarce resources limit the large-scale application of precious metal catalysts.

[0004] Among metal oxide catalysts, copper manganese oxide catalysts have been proven to be good carbon monoxide catalysts. The invention patent CN107537515B discloses the preparation of a supported copper manganese catalyst, which exhibits good low-temperature catalytic oxidation of carbon monoxide performance. However, flue gas has the characteristic of containing sulfur at low temperatures, and copper manganese oxide catalysts have a low carbon monoxide oxidation rate. 2 Very sensitive and easy to 2 The reaction generates sulfate, which rapidly reduces the activity of the catalyst. Moreover, these sulfur oxides are difficult to decompose, resulting in irreversible deactivation of the catalyst. 2 Combining the characteristics of the above materials, a sulfur-resistant non-precious metal catalyst for removing carbon monoxide was proposed by using cerium as an auxiliary agent to modify the alumina carrier and adopting different atmosphere calcination treatments, and by controlling a certain nucleation rate. Summary of the invention:

[0005] In order to solve the above problems and overcome the shortcomings of the prior art, the present invention provides a non-precious metal catalyst for sulfur-resistant removal of carbon monoxide, which can effectively solve the problems of high precious metal cost and poor stability of copper-manganese catalysts against sulfur poisoning, and achieve high sulfur resistance that traditional copper-manganese catalysts do not have.

[0006] The specific technical solution of the present invention to solve the above technical problems is: a non-precious metal catalyst for sulfur-resistant removal of carbon monoxide and a preparation method thereof, characterized in that the preparation method is as follows:

[0007] (1) Preparation of cerium-modified alumina mixed oxide support:

[0008] Alumina is added to a cerium metal salt solution, and after stirring, rotary evaporation, drying, grinding and calcining, a cerium-modified alumina mixed oxide carrier is obtained;

[0009] (2) Loading of active components of catalyst:

[0010] ① Fully disperse the cerium-modified alumina mixed oxide carrier in deionized water to form a suspension A, and maintain a certain temperature;

[0011] ② Dissolve copper and manganese metal salts in deionized water and add them to suspension A to form suspension B;

[0012] ③ Slowly add the precipitant dropwise into the suspension B, adjust the pH of the suspension to 8-9, and form precipitate C;

[0013] ④ Transfer the precipitate C to the reactor and control the reaction temperature and pressure for aging;

[0014] ⑤ Filter, wash, dry and grind the aged precipitate to obtain solid powder D;

[0015] (3) Calcination activation of catalyst:

[0016] The solid powder D is calcined in a calcination atmosphere to obtain a catalyst.

[0017] The aging reaction conditions in step ④ meet the following requirements:

[0018]

[0019] Where n is the number of solute molecules; p is the system pressure (KPa); m is the mass of a single atom (g); k is the Boltzmann constant (J / K); T is the system temperature (K); V 0 is the volume of a single molecule (mL); q is the specific surface energy of the solid-fluid interface (N / m); C is the solution concentration (mol / L); C 0 is the concentration of saturated solution (mol / L).

[0020] Furthermore, the nucleation rate I of the sulfur-resistant non-precious metal catalyst for removing carbon monoxide prepared by the preparation method is controlled at 2.3-8.5 m / s. -3 *s -1 .

[0021] Furthermore, the metal salt in step (1) is cerium nitrate, the cerium content is 1-5wt% of the carrier, stirring is performed at a certain speed for 6-12h, water is removed by rotary evaporation at 80°C, and air drying is performed at 100°C for 10-12h. The calcination temperature is 550°C, the heating rate is 5°C / min, and the insulation time is 6h.

[0022] Furthermore, the cerium-modified alumina in step ① is continuously stirred at room temperature at a certain rotation speed for 3-4 hours to allow the carrier to be fully dispersed in deionized water to form a suspension.

[0023] Furthermore, the copper and manganese metal salt solution in step ② is one or a combination of two or more of nitrate, acetate or sulfate, and the molar ratio of copper to manganese is 1 / 4-2 / 1.

[0024] Furthermore, the precipitant in step ③ is one or a combination of two or more of sodium carbonate, sodium hydroxide, ammonia water, and sodium bicarbonate, with a concentration of 0.1-0.5 mol / L.

[0025] Furthermore, in step ④, the aging temperature is 25-60°C, the pressure is 0.1-3.0 MPa, the aging is carried out for 3-10 hours, and the drying condition is forced air drying at 100°C for 10-12 hours.

[0026] Furthermore, in step (3), the calcination atmosphere is one or more gases selected from air, nitrogen or carbon monoxide mixed gas, the gas flow rate is 60 mL / min, the calcination temperature is 400°C, the heating rate is 5°C / min, and the holding time is 4h.

[0027] The non-precious metal catalyst for sulfur-resistant carbon monoxide removal prepared by the preparation method can remove 0-500 ppm of sulfur dioxide and 10000-20000 ppm of carbon monoxide at 250-300° C. and 5000-20000 h. -1 Under the condition of space velocity, the efficiency of removing carbon monoxide is stable at more than 90%

[0028] The beneficial effects of the present invention are:

[0029] The present invention modifies alumina by adding a small amount of cerium, and utilizes cerium oxide to preferentially react with SO 2 The characteristics of the reaction protect the activity of the main active species, and by specifically controlling the nucleation rate and then regulating the particle size of the active component, a catalyst with better carbon monoxide anti-sulfur stability in a sulfur-containing atmosphere is prepared.

[0030] Compared with the prior art, the present invention can achieve 0-500ppm sulfur dioxide and 10000-20000ppm carbon monoxide at 250-300℃ and 5000-20000h -1 Under the conditions of air velocity, the efficiency of removing carbon monoxide is stable at more than 92%, which is suitable for the purification of flue gas in the steel, coking and petrochemical industries. Description of the drawings:

[0031] Figure 1 1 and 2 are X-ray diffraction patterns of Examples 1 and 3 of the present invention and Comparative Example 1.

[0032] Figure 2 These are transmission electron microscope images and scanning electron microscope images of Example 1 of the present invention.

[0033] Figure 3 It is the X-ray photoelectron spectrum diagram of Examples 1 and 3 of the present invention and Comparative Example 1.

[0034] Figure 4 1 is a graph showing the carbon monoxide oxidation performance of Example 1 of the present invention and Comparative Example 1.

[0035] Figure 5 It is a graph of the anti-sulfur performance of Example 1 of the present invention.

[0036] Figure 6 It is the anti-sulfur performance diagram of Example 3 of the present invention. Specific implementation method:

[0037] In the description of the present invention, specific details are only for a full understanding of the embodiments of the present invention, but those skilled in the art should know that the implementation of the present invention is not limited to these details. In addition, well-known structures and functions are not described or shown in detail to avoid blurring the key points of the embodiments of the present invention. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0038] Specific implementation of the present invention:

[0039] In order to better understand the present invention, a specific embodiment is used for illustration. It is worth emphasizing that the effect of this embodiment is not substantially different from the various embodiments within the protection scope of the present invention, including the respective reagents and the content ratio of the reagents, and all of them can achieve the effects described in the present invention and solve the above-mentioned problems. Other combinations are not described here.

[0040] Embodiment 1:

[0041] (1) 154.5 mg of cerium nitrate hexahydrate and 3 g of aluminum oxide were added to 100 mL of deionized water, stirred at a certain speed for 12 h at room temperature, and the water was removed by rotary evaporation at 80 ° C. The powder sample was placed in a muffle furnace, and the temperature was increased from room temperature to 550 ° C at a heating rate of 5 ° C / min, and kept at this temperature for 6 h to obtain a cerium-alumina mixed oxide support;

[0042] (2) Add 1g of cerium-modified alumina mixed oxide support to a flask containing 100mL of deionized water, place the flask in an oil bath, adjust the temperature to 40°C, and stir continuously at a certain speed for 3-4h to fully disperse it to form suspension A, add 313mg of manganese acetate tetrahydrate and 154.3mg of copper nitrate trihydrate to suspension A to obtain suspension B; add 424mg of sodium carbonate to 20mL of deionized water to prepare a 0.2mol / L sodium carbonate solution, slowly drop it into suspension B at a certain speed at a drop rate of 2mL / min, and adjust the pH to 8-9 to obtain precipitate C, transfer the precipitate to a high-pressure reactor, and age it for 4h at a temperature of 25°C and a pressure of 1.5MPa. Filter the aged precipitate and wash it three times with deionized water, dry the obtained filter cake at 100°C for 12h, and then calcine it at 400°C for 4h in a 60mL / min carbon monoxide mixed gas flow to obtain a catalyst powder. Tableting and granulation, sieving (40-60 meshes), to obtain a sulfur-resistant non-precious metal catalyst for removing carbon monoxide;

[0043] Embodiment 2:

[0044] (1) 154.5 mg of cerium nitrate hexahydrate and 3 g of aluminum oxide were added to 100 mL of deionized water, stirred at a certain speed for 12 h at room temperature, and the water was removed by rotary evaporation at 80 ° C. The powder sample was placed in a muffle furnace, and the temperature was increased from room temperature to 550 ° C at a heating rate of 5 ° C / min, and kept at this temperature for 6 h to obtain a cerium-alumina mixed oxide support;

[0045] (2) Add 1g of cerium-modified alumina mixed oxide support to a flask containing 100mL of deionized water, place the flask in an oil bath, adjust the temperature to 40°C, and continue stirring at a certain speed for 3-4h to fully disperse it to form suspension A, add 313mg of manganese acetate tetrahydrate and 154.3mg of copper nitrate trihydrate to suspension A to obtain suspension B; add 424mg of sodium carbonate to 20mL of deionized water to prepare a 0.2mol / L sodium carbonate solution, slowly drop it into suspension B at a certain speed at a drop rate of 2mL / min, and adjust the pH to 8-9 to obtain precipitate C, transfer the precipitate to a high-pressure reactor, and age it for 4h at a temperature of 40°C and a pressure of 1.5MPa. Filter the aged precipitate and wash it three times with distilled water, dry the obtained filter cake at 100°C for 12h, and then calcine it at 400°C for 4h in a 60mL / min carbon monoxide mixed gas flow to obtain catalyst powder. Tableting and granulation, sieving (40-60 meshes), to obtain a sulfur-resistant non-precious metal catalyst for removing carbon monoxide;

[0046] Embodiment 3:

[0047] (1) 154.5 mg of cerium nitrate hexahydrate and 3 g of aluminum oxide were added to 100 mL of deionized water, stirred at a certain speed for 12 h at room temperature, and the water was removed by rotary evaporation at 80 ° C. The powder sample was placed in a muffle furnace, and the temperature was increased from room temperature to 550 ° C at a heating rate of 5 ° C / min, and kept at this temperature for 6 h to obtain a cerium-alumina mixed oxide support;

[0048] (2) Add 1g of cerium-modified alumina mixed oxide support to a flask containing 100mL of deionized water, place the flask in an oil bath, adjust the temperature to 40°C, and stir continuously at a certain speed for 3-4h to fully disperse it to form suspension A, add 313mg of manganese acetate tetrahydrate and 154.3mg of copper nitrate trihydrate to suspension A to obtain suspension B; add 424mg of sodium carbonate to 20mL of deionized water to prepare a 0.2mol / L sodium carbonate solution, slowly drop it into suspension B at a certain speed at a drop rate of 2mL / min, and adjust the pH to 8-9 to obtain precipitate C, transfer the precipitate to a high-pressure reactor, and age it for 4h at a temperature of 60°C and a pressure of 1.5MPa. Filter the aged precipitate and wash it three times with distilled water, dry the obtained filter cake at 100°C for 12h, and then calcine it at 400°C for 4h in a 60mL / min carbon monoxide counter-mixed gas flow to obtain catalyst powder. The product is tableted and granulated, and sieved (40-60 meshes) to obtain a sulfur-resistant non-precious metal catalyst for removing carbon monoxide.

[0049] Embodiment 4:

[0050] (1) 154.5 mg of cerium nitrate hexahydrate and 3 g of aluminum oxide were added to 100 mL of deionized water, stirred at a certain speed for 12 h at room temperature, and the water was removed by rotary evaporation at 80 ° C. The powder sample was placed in a muffle furnace, and the temperature was increased from room temperature to 550 ° C at a heating rate of 5 ° C / min, and kept at this temperature for 6 h to obtain a cerium-alumina mixed oxide support;

[0051] (2) Add 1 g of cerium-modified alumina mixed oxide support to a flask containing 100 mL of deionized water, place the flask in an oil bath, adjust the temperature to 40°C, and continue stirring at a certain speed for 3-4 hours to fully disperse it to form a suspension A, add 313 mg of manganese acetate tetrahydrate and 154.3 mg of copper nitrate trihydrate to the suspension A to obtain a suspension B; add 424 mg of sodium carbonate to 20 mL of deionized water to prepare a 0.2 mol / L sodium carbonate solution, slowly add it dropwise to the suspension B at a certain speed at a drop rate of 2 mL / min, and adjust the pH to 8-9 to obtain a precipitate C, transfer the precipitate to a high-pressure reactor, and age it for 4 hours at a temperature of 40°C and a pressure of 0.1 MPa (normal pressure). The aged precipitate was filtered and washed three times with deionized water, and the obtained filter cake was dried at 100°C for 12 hours, and then calcined at 400°C for 4 hours in a 60mL / min carbon monoxide mixed gas flow to obtain catalyst powder. The powder was pressed into tablets and granulated, and sieved (40-60 mesh) to obtain a sulfur-resistant non-precious metal catalyst for removing carbon monoxide.

[0052] Embodiment 5:

[0053] (1) 154.5 mg of cerium nitrate hexahydrate and 3 g of aluminum oxide were added to 100 mL of deionized water, stirred at a certain speed for 12 h at room temperature, and the water was removed by rotary evaporation at 80 ° C. The powder sample was placed in a muffle furnace, and the temperature was increased from room temperature to 550 ° C at a heating rate of 5 ° C / min, and kept at this temperature for 6 h to obtain a cerium-alumina mixed oxide support;

[0054] (2) Add 1g of cerium-modified alumina mixed oxide support to a flask containing 100mL of deionized water, place the flask in an oil bath, adjust the temperature to 40°C, and continue stirring at a certain speed for 3-4h to fully disperse it to form suspension A, add 313mg of manganese acetate tetrahydrate and 154.3mg of copper nitrate trihydrate to suspension A to obtain suspension B; add 424mg of sodium carbonate to 20mL of deionized water to prepare a 0.2mol / L sodium carbonate solution, slowly drop it into suspension B at a certain speed at a drop rate of 2mL / min, and adjust the pH to 8-9 to obtain precipitate C, transfer the precipitate to a high-pressure reactor, and age it for 4h at a temperature of 40°C and a pressure of 3MPa. Filter the aged precipitate and wash it three times with deionized water, dry the obtained filter cake at 100°C for 12h, and then calcine it at 400°C for 4h in a 60mL / min carbon monoxide mixed gas flow to obtain a catalyst powder. The product is tableted and granulated, and sieved (40-60 meshes) to obtain a sulfur-resistant non-precious metal catalyst for removing carbon monoxide.

[0055] In the aging conditions of the above embodiment, n is the number of solute molecules; p is the system pressure (KPa); m is the mass of a single atom (g); k is the Boltzmann constant (J / K); T is the system temperature (K); V0 is the volume of a single molecule (mL); q is the specific surface energy of the solid-fluid interface (N / m); C is the solution concentration (mol / L); C0 is the saturated solution concentration (mol / L), and meets

[0056]

[0057] 2. Catalyst activity test:

[0058] The sieved catalyst particles were placed in a fixed bed reactor and fed with a carbon monoxide mixture (2% CO / 18% O 2 / 80%N 2 ), airspeed 10000h -1 The reaction tail gas is monitored by a flue gas analyzer. Under the temperature condition of 125°C, the CO conversion rate is above 99.99%.

[0059] 3. Test of the catalyst's sulfur resistance:

[0060] 150 mL / min of SO was introduced into the reactor. 2 (500ppm / N2), the temperature was maintained at 270°C, and other test conditions remained unchanged. The CO removal efficiency of the catalyst was stabilized at more than 95%.

[0061] In order to more intuitively demonstrate the process advantages of the present invention, the preparation method of the present invention using a non-precious metal catalyst is compared with the method of using an equivalent replacement method in the same process.

[0062] Comparative Example 1:

[0063] Add 1g of alumina carrier to a flask containing 100mL of deionized water, place the flask in an oil bath, adjust the temperature to 40°C, and stir continuously at 400rpm for 3-4h to fully disperse it to form suspension A. Add 313mg of manganese acetate tetrahydrate and 154.3mg of copper nitrate trihydrate to suspension A to obtain suspension B. Add 424mg of sodium carbonate to 20mL of deionized water to prepare a 0.2mol / L sodium carbonate solution. At a speed of 400r / min, slowly drop it into suspension B at a drop rate of 2mL / min, and adjust the pH to 8-9 to obtain precipitate C. Transfer the precipitate to a high-pressure reactor and age it for 4h at a temperature of 40°C and a pressure of 1MPa. Filter the aged precipitate and wash it three times with distilled water. The filter cake is dried at 100°C for 12h, and then calcined at 400°C for 4h in an air flow of 60mL / min to obtain a catalyst powder. The product is tableted and granulated, and sieved (40-60 meshes) to obtain a sulfur-resistant non-precious metal catalyst for removing carbon monoxide.

[0064] Comparative Example 2:

[0065] The preparation method is the same as that in Example 3, except that the preparation process of this comparative example is carried out at room temperature and pressure, that is, aging is carried out at room temperature and pressure (25°C, 0.1MPa) for 4h.

[0066] Comparative Example 3:

[0067] The preparation method is the same as that of Example 3, except that during the preparation of this comparative example, an alumina carrier is added.

[0068] Table 1: Preparation of catalysts with different cerium contents and different calcination atmospheres and comparison of their carbon monoxide oxidizability and anti-sulfur stability

[0069]

[0070] From the data analysis in Table 1, we can see that:

[0071] (1) It can be seen from Examples 1-5 that:

[0072] Comparing the carbon monoxide oxidation activity and anti-sulfur stability of the catalysts prepared in Examples 1-5 of the present invention and Comparative Example 1, the catalysts calcined in the reaction atmosphere have better carbon monoxide oxidation activity and significantly improved anti-sulfur stability.

[0073] Through the above comparison, it is found that after adding cerium in the embodiment, the carbon monoxide oxidation performance and anti-sulfur stability of the catalyst are better, and the amount of cerium added has a significant effect on the carbon monoxide oxidation performance of the catalyst, but the anti-sulfur stability within 50 hours is not much different, but the anti-sulfur stability of the catalyst in Example 1 without adding cerium is significantly increased; the carbon monoxide oxidation performance and anti-sulfur stability of the catalyst obtained by calcining in the reaction atmosphere are improved, which is related to the increase in the surface oxygen vacancy content.

[0074] The present invention modifies alumina by adding a small amount of cerium, and utilizes cerium oxide to preferentially react with SO 2 The characteristics of the reaction protect the activity of the main active species, thereby preparing a catalyst with better carbon monoxide anti-sulfur stability in a sulfur-containing atmosphere.

[0075] The catalysts prepared in the examples of the present invention and comparative example 1 were characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy.

[0076] In the X-ray diffraction pattern, the characteristic peaks of aluminum oxide and cerium oxide were present in Examples 1 and 3, but no characteristic peaks of copper and manganese oxide were found. 2 / N 2 The catalyst obtained by calcination has lower characteristic peak intensity and more uniform dispersion of copper and manganese oxide particles.

[0077] In the scanning electron microscope image, Example 1 exhibits a nano-leaf-like morphology, which is a typical alumina morphology, indicating that the loading of the active component metal has little effect on the catalyst morphology, and obvious large copper-manganese oxide particles are found.

[0078] In the X-ray photoelectron spectrum, trivalent cerium and tetravalent cerium are present in both Example 1 and Example 3. The catalyst obtained by calcining in the reaction atmosphere contains more trivalent cerium, which means the formation of more oxygen vacancies. The high concentration of surface oxygen vacancies can improve the catalytic oxidation activity and anti-sulfur stability of the catalyst.

[0079] Comparing the carbon monoxide oxidation activity and anti-sulfur stability of the catalysts prepared in Example 1 of the present invention and Comparative Example 1, the catalyst calcined in the reaction atmosphere has better carbon monoxide oxidation activity and significantly improved anti-sulfur stability.

[0080] (2) Comparative Examples 2-3 show that:

[0081] Among them, the difference between Comparative Example 2 and the present invention is that the process is carried out at room temperature and pressure, that is, aging is carried out for 4 hours at room temperature and pressure (25°C, 0.1MPa); the difference between Comparative Example 3 and the present invention is that an alumina carrier is added.

[0082] The anti-sulfur stability of Comparative Examples 2 and 3 within 50 hours is not much different from that of Comparative Example 1. It can be seen that the carbon monoxide oxidation performance and anti-sulfur stability of the catalyst obtained by calcining in the reaction atmosphere of the present invention are improved, which is related to the increase in the surface oxygen vacancy content. This relationship is closely related to the temperature and pressure in the preparation process and the type of carrier in the preparation process.

[0083] This may be due to:

[0084] Although Comparative Example 2 adds a small amount of cerium to modify alumina as in the present invention, cerium oxide is preferentially reacted with SO 2 However, due to the different temperatures and pressures in the preparation process and the different types of carriers in the preparation process, the carbon monoxide oxidation performance and anti-sulfur stability cannot be improved as in the present invention.

[0085] However, in Comparative Example 2, no modified alumina as in the present invention is added, resulting in that the carbon monoxide oxidation performance and anti-sulfur stability cannot be improved as in the present invention.

[0086] In summary:

[0087] The present invention modifies alumina by adding a small amount of cerium, and utilizes cerium oxide to preferentially react with SO 2 The characteristics of the reaction protect the activity of the main active species, and by specifically controlling the nucleation rate and then regulating the particle size of the active component, a catalyst with better carbon monoxide anti-sulfur stability in a sulfur-containing atmosphere is prepared.

[0088] Compared with the prior art, the present invention can achieve 0-500ppm sulfur dioxide and 10000-20000ppm carbon monoxide at 250-300℃ and 5000-20000h -1 Under the conditions of air velocity, the efficiency of removing carbon monoxide is stable at more than 92%, which is suitable for the purification of flue gas in the steel, coking and petrochemical industries.

Claims

1. A non-precious metal catalyst for sulfur-resistant removal of carbon monoxide and a preparation method thereof, characterized in that: The preparation method is as follows: (1) Preparation of cerium-modified alumina mixed oxide support: Alumina is added to a cerium metal salt solution, and after stirring, rotary evaporation, drying, grinding and calcining, a cerium-modified alumina mixed oxide carrier is obtained; (2) Loading of active components of catalyst: ① Fully disperse the cerium-modified alumina mixed oxide carrier in deionized water to form a suspension A, and maintain a certain temperature; ② Dissolve copper and manganese metal salts in deionized water and add them to suspension A to form suspension B; ③ Slowly add the precipitant dropwise into the suspension B, adjust the pH of the suspension to 8-9, and form precipitate C; ④ Transfer the precipitate C to the reactor and control the reaction temperature and pressure for aging; ⑤ Filter, wash, dry and grind the aged precipitate to obtain solid powder D; (3) Calcination activation of catalyst: The solid powder D is calcined in a calcination atmosphere to obtain a catalyst.

2. The non-precious metal catalyst for removing carbon monoxide with sulfur resistance and its preparation method according to claim 1, characterized in that The aging reaction conditions in step ④ meet the following requirements: Where n is the number of solute molecules; p is the system pressure (KPa); m is the mass of a single atom (g); k is the Boltzmann constant (J / K); T is the system temperature (K); V0 is the volume of a single molecule (mL); q is the specific surface energy of the solid-fluid interface (N / m); C is the solution concentration (mol / L); and C0 is the saturated solution concentration (mol / L).

3. The non-precious metal catalyst for removing carbon monoxide with sulfur resistance and its preparation method according to claim 2, characterized in that The nucleation rate I of the non-precious metal catalyst for sulfur-resistant carbon monoxide removal prepared by the preparation method is controlled at 2.3-8.5 m / s. -3 *s -1 .

4. The non-precious metal catalyst for removing carbon monoxide with sulfur resistance and the preparation method thereof according to claim 1, characterized in that The metal salt in step (1) is cerium nitrate, and the cerium content is 1-5wt% of the carrier. The mixture is stirred at a certain speed for 6-12 hours, and the water is removed by rotary evaporation at 80°C. The mixture is dried by forced air at 100°C for 10-12 hours. The calcination temperature is 550°C, the heating rate is 5°C / min, and the insulation time is 6 hours.

5. The non-precious metal catalyst for removing carbon monoxide with sulfur resistance and the preparation method thereof according to claim 1, characterized in that The cerium-modified alumina in step ① is continuously stirred at room temperature at a certain speed for 3-4 hours to allow the carrier to be fully dispersed in deionized water to form a suspension.

6. The non-precious metal catalyst for removing carbon monoxide with sulfur resistance and the preparation method thereof according to claim 1, characterized in that The copper and manganese metal salt solution in step ② is one or a combination of two or more of nitrate, acetate or sulfate, and the molar ratio of copper to manganese is 1 / 4-2 / 1.

7. The non-precious metal catalyst for removing carbon monoxide with sulfur resistance and the preparation method thereof according to claim 1, characterized in that The precipitant in step ③ is one or a combination of two or more of sodium carbonate, sodium hydroxide, ammonia water, and sodium bicarbonate, with a concentration of 0.1-0.5 mol / L.

8. The non-precious metal catalyst for removing carbon monoxide with sulfur resistance and the preparation method thereof according to claim 1, characterized in that In step ④, the aging temperature is 25-60°C, the pressure is 0.1-3.0MPa, the aging is carried out for 3-10h, and the drying condition is forced air drying at 100°C for 10-12h.

9. The non-precious metal catalyst for removing carbon monoxide with sulfur resistance and the preparation method thereof according to claim 1, characterized in that In step (3), the calcination atmosphere is one or more gases selected from air, nitrogen or carbon monoxide mixed gas, the gas flow rate is 60 mL / min, the calcination temperature is 400° C., the heating rate is 5° C. / min, and the holding time is 4 h.

10. The sulfur-resistant non-precious metal catalyst for removing carbon monoxide and the preparation method thereof according to any one of claims 1 to 9, characterized in that The non-precious metal catalyst for sulfur-resistant carbon monoxide removal prepared by the preparation method can remove 0-500 ppm of sulfur dioxide and 10000-20000 ppm of carbon monoxide at 250-300° C. and 5000-20000 h. -1 Under the space velocity conditions, the efficiency of removing carbon monoxide is stable at more than 90%.

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