Manganese-based catalyst as well as preparation method and application thereof

Abstract

The invention belongs to the field of catalyst material preparation, and particularly relates to a manganese-based catalyst and a preparation method and application thereof. The preparation method comprises the following steps: dispersing a manganese-based carrier and an acidic solution in water, then transferring the solution into a reaction kettle for hydrothermal reaction, cooling and separating after the reaction is finished, and drying to obtain an acid-modified manganese-based carrier; under the stirring condition, transition metal salt is dissolved in water, the acid-modified manganese-based carrier is added, and a solid is obtained after filtering and drying; and finally, calcining the obtained solid to obtain the manganese-based catalyst. In a humid environment, the manganese-based catalyst shows higher chlorobenzene conversion rate, ozone conversion rate and COx selectivity than traditional catalysts, and has good long-term stability.

Description

Technical Field

[0001] The invention belongs to the field of catalyst material preparation, and specifically relates to a manganese-based catalyst and a preparation method and application thereof. Background Art

[0002] As one of the typical chlorinated volatile organic compounds (Cl-VOCs), chlorobenzene emitted during steel sintering, smelting, solid waste treatment, glass manufacturing and organic synthesis is an important precursor of aerosols, particulate matter (PM) and photochemical smog. Catalytic combustion technology can catalytically burn chlorobenzene into harmless CO2 / H2O and soluble acidic gases (HCl / Cl2). It has the characteristics of low cost and low harm of by-products, and is therefore of great significance in terms of environmental protection. However, higher degradation temperatures will lead to the formation of toxic by-products. In addition, the accumulation of chlorine-containing intermediates during the catalytic combustion of chlorobenzene will also lead to catalyst poisoning and deactivation. The ozone-enhanced catalytic combustion method can alleviate the above problems. It can eliminate chlorobenzene at low temperatures (<150°C) and has a high resistance to chlorine poisoning and chlorine-containing by-product inhibition. This catalytic combustion method is also called catalytic ozonation. Under optimal conditions, the amount of ozone emission is extremely low, so the synergistic elimination of chlorobenzene and O3 can be achieved. Therefore, it is necessary to develop catalysts that can achieve synergistic degradation with ozone. Summary of the invention

[0003] The purpose of the present invention is to provide a manganese-based catalyst and its preparation method and application, so as to solve the problem of using ozone to synergistically degrade chlorobenzene in a low-temperature and humid environment. The synergistic activation strategy of ozone and water molecules greatly improves the catalytic combustion activity and stability of chlorobenzene, and provides a new idea for the development of high-performance catalysts for Cl-VOC degradation.

[0004] The implementation process of the present invention is as follows:

[0005] A method for preparing a manganese-based catalyst comprises the following steps:

[0006] (1) dispersing a manganese-based carrier and an acidic solution in water, subjecting the dispersion to a hydrothermal reaction, cooling after the reaction, separating, and drying to obtain an acid-modified manganese-based carrier;

[0007] (2) dissolving a transition metal salt in water under stirring, adding the acid-modified manganese-based support of step (1), and filtering and drying to obtain a solid;

[0008] (3) calcining the solid obtained in step (2) to obtain a manganese-based catalyst.

[0009] Furthermore, the manganese-based carrier is selected from any one or more of SmMn2O5, YMn2O5, CoMn2O4, CoMnO3, MnO2, Mn2O3 or Mn3O4, or is prepared by co-precipitation method.

[0010] Furthermore, the acidic solution is selected from any one or more of boric acid, acetic acid, formic acid, benzoic acid or phosphoric acid; and the transition metal salt is selected from soluble nickel salt, soluble iron salt, soluble cobalt salt, soluble copper salt and soluble chromium salt.

[0011] Furthermore, the mass ratio of the manganese-based support to the acid solution is 1:(0.2-0.4); the mass ratio of the manganese-based support to the transition metal salt solution is 1:(0.0005-0.05).

[0012] Furthermore, the temperature of the hydrothermal reaction in step (1) is 80-150° C., and the time of the hydrothermal reaction is 1-3 hours; the temperature of the calcination in step (3) is 300-500° C., and the time of the calcination is 2-3 hours.

[0013] Furthermore, the preparation process of the manganese-based carrier comprises the following steps:

[0014] The samarium salt and the manganese salt are dissolved in water, and then a precipitant is added to adjust the pH to 9-11 to generate a precipitate, and a precursor is obtained after separation and drying, and finally the precursor is calcined to obtain a manganese-based carrier.

[0015] Furthermore, the samarium salt is selected from Sm(NO3)3·6H2O; the manganese salt is selected from Mn(CH3COO)2·4H2O or Mn(NO3)2·4H2O; and the precipitant is selected from any one of ammonia water, NaOH or KOH.

[0016] Furthermore, the molar ratio of the samarium salt to the manganese salt is (0.5-1):2; the calcination temperature is 500-800° C., and the calcination time is 2-3 hours.

[0017] A manganese-based catalyst is obtained by the above-mentioned preparation method, and the transition metal loading amount in the manganese-based catalyst is 0.05wt.% to 5wt.%.

[0018] The application of the above manganese-based catalyst in the synergistic degradation of chlorobenzene with ozone in a low-temperature and humid environment. The conversion rate of chlorobenzene under room temperature and high humidity (25°C, RH=100%) can reach 97.8%, and the efficiency of decomposing and activating ozone at room temperature can reach 100%; and after 50 hours of continuous operation, the chlorobenzene conversion rate of the manganese-based catalyst is always maintained at more than 90%, CO x The selectivity was maintained above 87%, showing extremely high stability, indicating that the manganese-based catalyst has excellent resistance to chlorine and water poisoning.

[0019] Positive effects of the present invention:

[0020] (1) The present invention prepares a manganese-based catalyst by introducing an acidic group and a transition metal single atom. The obtained catalyst exhibits good chlorobenzene degradation efficiency in an ozone-coordinated low-temperature and humid environment, and at 25°C and a relative humidity of 100%, the manganese-based catalyst can achieve a chlorobenzene conversion rate of 97.8% and maintain stable catalytic activity during 50 hours of continuous operation.

[0021] (2) The manganese-based catalyst of the present invention uses ozone synergistic technology and uses ozone as an oxidant. Compared with traditional air, it has stronger oxidizing properties and can achieve efficient catalytic combustion of chlorobenzene at low temperatures (<150°C), reducing the problem of by-product generation caused by high-temperature reactions and saving energy.

[0022] (3) Most existing catalysts are susceptible to poisoning by water and chlorine. However, the present invention introduces acidic groups, and the acidic sites can decompose ozone to form active oxygen species, which can promote the decomposition of water during the reaction process. Assisted by the synergistic effect between single atoms, the manganese-based catalyst has excellent resistance to chlorine poisoning and water poisoning, and can operate stably for a long time under high humidity conditions, thereby improving the service life and stability of the catalyst.

[0023] (4) The manganese-based catalyst of the present invention selectively generates singlet oxygen with a long life and migration distance by efficiently activating ozone. 1 O2), thereby improving the oxidation efficiency of organic pollutants such as chlorobenzene.

[0024] (5) In the catalyst regulation strategy used in the present invention, the synergistic effect of the acidic groups and transition metal single atoms significantly improves the activation efficiency of ozone and water molecules, and enhances the activity and CO2 selectivity of the manganese-based catalyst in a humid environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The activity diagram of the synergistic catalytic oxidation performance of chlorobenzene and ozone in a wet environment for the products obtained in Examples 1-4;

[0026] Figure 2 This is a graph showing the combustion activity of chlorobenzene of the catalyst of Example 4 at different humidity levels;

[0027] Figure 3 This is a graph of the ozone activation performance of the products obtained in Examples 1-4 in a humid environment;

[0028] Figure 4 The combustion activity diagram of chlorobenzene at different humidity in Example 1;

[0029] Figure 5 The chlorobenzene mineralization rate of the products obtained in Examples 1-4 at different temperatures;

[0030] Figure 6 This is a stability diagram of the manganese-based catalyst obtained in Example 4 when operated in a wet environment for 50 hours. DETAILED DESCRIPTION

[0031] The present invention will be further described below in conjunction with the embodiments.

[0032] The present invention designs a manganese-based catalyst suitable for use in a humid atmosphere. By introducing an acidic group and a single-atom synergistic regulation mechanism, the electron transfer efficiency is further improved, thereby effectively activating water molecules and ozone, generating highly active oxygen species, and promoting hydrolysis and dechlorination reactions. In a humid environment, the manganese-based catalyst can achieve a chlorobenzene conversion rate of 97.8% and maintain stable catalytic activity during 50 hours of continuous operation. The synergistic effect of the acidic group and the transition metal single atom effectively activates ozone to generate singlet oxygen ( 1 O2), achieving efficient low-temperature catalytic combustion, inhibiting the formation of by-products, and significantly enhancing the ability to resist chlorine and water poisoning.

[0033] Example 1 Preparation of manganese-based carrier SMO

[0034] 0.005 mol Sm(NO3)3·6H2O and 0.02 mol Mn(CH3COO)2·4H2O were dissolved in 100 mL of water, and then ammonia water was added as a precipitant to adjust the pH to 10 to produce a precipitate. The precipitate was separated and then placed in an oven at 105°C for drying to obtain a precursor. Finally, the precursor was placed in a muffle furnace and calcined at 600°C for 3 hours to obtain a manganese-based carrier, referred to as SMO.

[0035] Example 2 Preparation of acid-modified manganese-based carrier SMO-A

[0036] 1 g of the manganese-based carrier SMO obtained in Example 1 and 0.3 g of boric acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 120° C. for 2 hours. After the reaction was completed, it was naturally cooled and separated to obtain a precipitate, which was then placed in a 105° C. oven for drying to obtain an acid-modified manganese-based carrier, referred to as SMO-A.

[0037] Example 3 Preparation of manganese-based carrier M / SMO loaded with transition metals

[0038] Under stirring conditions, 0.002 g of nickel acetate tetrahydrate was dissolved in 60 mL of water, and then 1 g of the manganese-based carrier SMO obtained in Example 1 was dispersed in the solution, and the precipitate was separated by filtration, and then placed in a 105° C. oven for drying to obtain a manganese-based carrier loaded with nickel, referred to as M / SMO.

[0039] Example 4 Preparation of manganese-based catalyst M / SMO-A

[0040] (1) Under stirring conditions, 0.002 g of nickel acetate tetrahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support SMO-A prepared in Example 2 was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0041] (2) The solid obtained in step (1) was calcined at 400° C. for 3 hours to obtain a manganese-based catalyst, referred to as M / SMO-A, wherein the transition metal Ni loading in the manganese-based catalyst was 0.2%.

[0042] Application performance testing:

[0043] For comparison, SMO was prepared by using unmodified SMO. The catalytic activity test of the manganese-based catalyst M / SMO-A prepared in Example 4 was carried out in a fixed bed reactor with a catalyst loading volume of 10*10cm -3 The initial gas concentration is 100 ppm chlorobenzene, 1500 ppm ozone, 10 vol% oxygen and balance nitrogen, and the space velocity (WHSV) is 20,000 mL g -1 ·h -1 .

[0044] The product of Example 1-4 is used as a catalyst. Figure 1 It can be seen that by comparing the catalytic activities of the catalysts of Examples 1-4 in a high humidity atmosphere, the conversion rates of all catalysts show a trend of first increasing and then decreasing as the temperature increases. Among them, the conversion rate of SMO has the most significant trend with temperature change, reaching the maximum conversion rate (90.8%) from 25°C (81.3%) to 35°C, and then decreasing to 71.7% when it continues to rise to 100°C; while the conversion rate of M / SMO-A does not change significantly with temperature, rising from 97.8% at 25°C to 99.7% at 50°C, and then only slightly decreasing to 96.5% when it rises to 100°C; the highest conversion rates of SMO-A and M / SMO are 94.1% (40°C) and 95.3% (35°C), respectively.

[0045] from Figure 2 It can be seen that for the manganese-based catalyst M / SMO-A prepared in Example 4, the effect of humidity on the conversion rate is relatively small, showing its excellent performance in a high humidity (RH=100%) environment.

[0046] from Figure 3 It can be seen that the manganese-based catalyst M / SMO-A prepared in Example 4 exhibits an ozone conversion rate of 100% in the entire temperature range of 25 to 100°C, and the ozone conversion rates of the other three catalysts at low temperatures are difficult to meet emission requirements.

[0047] from Figure 4It can be seen that, when the manganese-based carrier SMO prepared in Example 1 is used as a catalyst, humidity has a great influence on the catalytic combustion performance of chlorobenzene. As the relative humidity increases, the conversion rate continues to decrease.

[0048] The product of Example 1-4 is used as a catalyst. Figure 5 It can be seen that the CO x The selectivity of the catalysts increased with increasing temperature, but only the catalyst prepared in Example 4 showed a CO selectivity of more than 90% in the whole temperature range of 25-100°C. x Selectivity: The COx selectivity of the other three catalysts is low, indicating that a large amount of chlorobenzene has not been completely mineralized.

[0049] from Figure 6 It can be seen that the catalyst prepared in Example 4 can maintain a chlorobenzene degradation efficiency of more than 90% and a mineralization rate of more than 80% when operated for 50 hours under the condition of RH=100%.

[0050] Example 5 Preparation of manganese-based carrier

[0051] 0.01 mol Sm(NO3)3·6H2O and 0.02 mol Mn(NO3)2·4H2O were dissolved in 100 mL of water, and then a precipitant 0.1 mol / L KOH solution was added to adjust the pH to 9 to produce a precipitate. The precipitate was separated and then placed in a 105°C oven for drying to obtain a precursor. Finally, the precursor was placed in a muffle furnace and calcined at 800°C for 2 hours to obtain a manganese-based carrier.

[0052] Example 6 Preparation of manganese-based carrier

[0053] 0.01 mol Sm(NO3)3·6H2O and 0.02 mol Mn(CH3COO)2·4H2O were dissolved in 100 mL of water, and then a precipitant 0.1 mol / L NaOH solution was added to adjust the pH to 11 to produce a precipitate. The precipitate was separated and then placed in a 105°C oven for drying to obtain a precursor. Finally, the precursor was placed in a muffle furnace and calcined at 500°C for 3 hours to obtain a manganese-based carrier.

[0054] Example 7 Manganese-based catalyst

[0055] (1) 1 g of the manganese-based carrier SMO obtained in Example 5 and 0.2 g of acetic acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 120° C. for 2 hours. After the reaction was completed, the solution was naturally cooled and separated to obtain a precipitate, which was then placed in an oven at 105° C. for drying to obtain an acid-modified manganese-based carrier.

[0056] (2) Under stirring conditions, 0.05 g of nickel acetate tetrahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support obtained in step (1) was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0057] (3) The solid obtained in step (2) is calcined at 400° C. for 3 hours to obtain a manganese-based catalyst, wherein the transition metal Ni loading amount in the manganese-based catalyst is 5%.

[0058] Example 8 Manganese-based catalyst

[0059] (1) 1 g of a manganese-based carrier CoMnO3 and 0.2 g of acetic acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 120 °C for 2 hours. After the reaction was completed, the precipitate was naturally cooled and separated, and then placed in a 105 °C oven for drying to obtain an acid-modified manganese-based carrier.

[0060] (2) Under stirring conditions, 0.002 g of chromium nitrate nonahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support obtained in step (1) was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0061] (3) The solid obtained in step (2) is calcined at 400° C. for 3 hours to obtain a manganese-based catalyst, wherein the transition metal Cr loading amount in the manganese-based catalyst is 0.2%.

[0062] Example 9 Manganese-based catalyst

[0063] (1) 1 g of a manganese-based carrier CoMn2O4 and 0.2 g of formic acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 80°C for 3 hours. After the reaction was completed, the precipitate was naturally cooled and separated, and then placed in a 105°C oven for drying to obtain an acid-modified manganese-based carrier.

[0064] (2) Under stirring conditions, 0.003 g of cobalt nitrate hexahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support obtained in step (1) was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0065] (3) The solid obtained in step (2) is calcined at 300° C. for 3 hours to obtain a manganese-based catalyst, wherein the transition metal Co loading amount in the manganese-based catalyst is 0.3%.

[0066] Example 10 Manganese-based catalyst

[0067] (1) 1 g of manganese-based carrier YMn2O5 and 0.3 g of benzoic acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 100°C for 2 hours. After the reaction was completed, it was naturally cooled and separated to obtain a precipitate, which was then placed in a 105°C oven for drying to obtain an acid-modified manganese-based carrier.

[0068] (2) Under stirring conditions, 0.002 g of ferric chloride hexahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support obtained in step (1) was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0069] (3) The solid obtained in step (2) is calcined at 400° C. for 3 hours to obtain a manganese-based catalyst, wherein the transition metal Fe loading in the manganese-based catalyst is 0.2%.

[0070] Example 11 Manganese-based catalyst

[0071] (1) 1 g of a manganese-based carrier SmMn2O5 and 0.4 g of phosphoric acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 150°C for 1 hour. After the reaction was completed, the solution was naturally cooled and separated to obtain a precipitate, which was then placed in an oven at 105°C for drying to obtain an acid-modified manganese-based carrier.

[0072] (2) Under stirring conditions, 0.001 g of copper sulfate pentahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support obtained in step (1) was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0073] (3) The solid obtained in step (2) is calcined at 500° C. for 2 hours to obtain a manganese-based catalyst, wherein the transition metal Cu loading amount in the manganese-based catalyst is 0.1%.

[0074] Example 12 Manganese-based catalyst

[0075] (1) 1 g of a manganese-based carrier MnO2 and 0.2 g of formic acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 90 °C for 1 hour. After the reaction was completed, the solution was naturally cooled and separated to obtain a precipitate, which was then placed in an oven at 105 °C for drying to obtain an acid-modified manganese-based carrier.

[0076] (2) Under stirring conditions, 0.003 g of cobalt nitrate hexahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support obtained in step (1) was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0077] (3) The solid obtained in step (2) is calcined at 300° C. for 3 hours to obtain a manganese-based catalyst, wherein the transition metal Cr loading amount in the manganese-based catalyst is 0.3%.

[0078] Example 13 Manganese-based catalyst

[0079] (1) 1 g of a manganese-based carrier Mn2O3 and 0.3 g of acetic acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 110°C for 3 hours. After the reaction was completed, the solution was naturally cooled and separated to obtain a precipitate, which was then placed in an oven at 105°C for drying to obtain an acid-modified manganese-based carrier.

[0080] (2) Under stirring conditions, 0.0005 g of ferric chloride hexahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support obtained in step (1) was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0081] (3) The solid obtained in step (2) is calcined at 400° C. for 3 hours to obtain a manganese-based catalyst, wherein the transition metal Fe loading in the manganese-based catalyst is 0.05%.

[0082] Example 14 Manganese-based catalyst

[0083] (1) 1 g of a manganese-based carrier Mn3O4 and 0.3 g of acetic acid were dispersed in 60 mL of water, and then the solution was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 120°C for 1 hour. After the reaction was completed, the solution was naturally cooled and separated to obtain a precipitate, which was then placed in an oven at 105°C for drying to obtain an acid-modified manganese-based carrier.

[0084] (2) Under stirring conditions, 0.002 g of copper sulfate pentahydrate was dissolved in 60 mL of water, and then 1 g of the acid-modified manganese-based support obtained in step (1) was dispersed in the solution, and a precipitate was obtained by filtration and then placed in an oven at 105° C. for drying to obtain a solid;

[0085] (3) The solid obtained in step (2) is calcined at 400° C. for 2 hours to obtain a manganese-based catalyst, wherein the transition metal Cu loading in the manganese-based catalyst is 0.2%.

[0086] The present invention can effectively activate ozone and water molecules by precisely modifying acidic groups and highly dispersed transition metal single atoms on the surface of the manganese-based carrier, significantly improving the catalytic combustion efficiency and anti-toxicity of chlorobenzene. In a humid environment, the manganese-based catalyst of the present invention exhibits higher chlorobenzene conversion rate, ozone conversion rate and CO conversion rate than traditional catalysts. x Selectivity and good long-term stability.

[0087] The above contents are further detailed descriptions of the present invention in combination with specific preferred embodiments, and the specific implementation of the present invention cannot be limited to these descriptions. For ordinary technicians in the field to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, which should be regarded as falling within the protection scope of the present invention.

Claims

1. A method for preparing a manganese-based catalyst, characterized in that: The steps include: (1) dispersing a manganese-based carrier and an acidic solution in water, subjecting the dispersion to a hydrothermal reaction, cooling after the reaction, separating, and drying to obtain an acid-modified manganese-based carrier; (2) dissolving a transition metal salt in water under stirring, adding the acid-modified manganese-based support of step (1), and filtering and drying to obtain a solid; (3) calcining the solid obtained in step (2) to obtain a manganese-based catalyst.

2. The method for preparing a manganese-based catalyst according to claim 1, characterized in that: The manganese-based carrier is selected from any one or more of SmMn2O5, YMn2O5, CoMn2O4, CoMnO3, MnO2, Mn2O3 or Mn3O4, or is prepared by co-precipitation method.

3. The method for preparing a manganese-based catalyst according to claim 1, characterized in that: The acidic solution is selected from any one or more of boric acid, acetic acid, formic acid, benzoic acid or phosphoric acid; the transition metal salt is selected from soluble nickel salt, soluble iron salt, soluble cobalt salt, soluble copper salt and soluble chromium salt.

4. The method for preparing a manganese-based catalyst according to claim 1, characterized in that: The mass ratio of the manganese-based carrier to the acidic solution is 1:(0.2-0.4); the mass ratio of the manganese-based carrier to the transition metal salt solution is 1:(0.0005-0.05).

5. The method for preparing a manganese-based catalyst according to claim 1, characterized in that: The temperature of the hydrothermal reaction in step (1) is 80-150° C., and the time of the hydrothermal reaction is 1-3 hours; the temperature of the calcination in step (3) is 300-500° C., and the time of the calcination is 2-3 hours.

6. The method for preparing a manganese-based catalyst according to claim 2, characterized in that: The preparation process of the manganese-based carrier comprises the following steps: The samarium salt and the manganese salt are dissolved in water, and then a precipitant is added to adjust the pH to 9-11 to generate a precipitate, and a precursor is obtained after separation and drying, and finally the precursor is calcined to obtain a manganese-based carrier.

7. The method for preparing a manganese-based catalyst according to claim 6, characterized in that: The samarium salt is selected from Sm(NO3)3·6H2O; the manganese salt is selected from Mn(CH3COO)2·4H2O or Mn(NO3)2·4H2O; and the precipitant is selected from any one of ammonia water, NaOH or KOH.

8. The method for preparing a manganese-based catalyst according to claim 6, characterized in that: The molar ratio of the samarium salt to the manganese salt is (0.5-1):2; the calcination temperature is 500-800°C, and the calcination time is 2-3 hours.

9. A manganese-based catalyst, characterized in that The manganese-based catalyst is obtained by the preparation method according to any one of claims 1 to 8, and the transition metal loading in the manganese-based catalyst is 0.05 wt.% to 5 wt.%.

10. Use of the manganese-based catalyst as claimed in claim 9 in synergistic degradation of chlorobenzene with ozone in a low-temperature and humid environment.

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