CN111841614B - Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof - Google Patents
Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B01J35/394—
-
- B01J35/61—
Abstract
The invention discloses a nitrogen and boron co-doped graphene composite denitration and sulfur-resistant catalyst and a preparation method thereof, and the preparation method comprises the steps of growing an efficient denitration and sulfur-resistant ternary catalyst on self-made nitrogen-doped graphene oxide in situ, and reducing the graphene oxide while doping boron to prepare the nitrogen and boron co-doped graphene catalyst composite material. Due to the in-situ growth method, the three-way catalyst is uniformly and firmly loaded on the surface of the nitrogen and boron co-doped graphene. The whole synthesis is carried out in a low-temperature environment, the reaction synthesis method and the operation are simple, the reaction is rapid, no specific requirements are required on a reaction container, the synthetic substance has no pollution to the environment, the synthesized catalyst and the nitrogen and boron co-doped graphene are firmly combined, the service life is long, and the denitration rate is high.
Description
Technical Field
The invention belongs to the technical field of functional doped graphene composite catalysts, and particularly relates to a nitrogen-boron co-doped graphene composite denitration sulfur-resistant catalyst and a preparation method thereof.
Background
With the rapid development of the Chinese industrialization process, a lot of unavoidable pollution is generated, wherein the atmospheric pollution is the most serious and most concerned problem in a plurality of pollution, and the generation of the atmospheric pollution causes the life, health, work, nature and the like of people to be damaged more badly. At present, air pollution sources can be divided into fixed pollution sources and mobile pollution sources, pollutants of the pollution sources are mainly generated due to coal combustion, the pollution sources comprise PM2.5, PM10, sulfur dioxide, nitrogen oxide, nitrogen dioxide and the like, and the gases can cause harm to the environment such as haze, acid rain, photochemical smog, greenhouse effect and the like.
It is known that, because of the large power demand brought by the construction of infrastructure and the development of manufacturing industry which are greatly promoted in China, and the power demand needs to provide energy by the combustion of coal, the usage amount of coal resources in China is huge. Since 2011, in order to control the serious air pollution problem caused by the combustion of coal, environmental protection departments in China issue emission standards of atmospheric pollutants for thermal power plants (GBl3223-2011) in combination with the national quality supervision and quarantine bureau, aiming at controlling the emission of the atmospheric pollutants and the structure of the thermal power industry and promoting the healthy and sustainable development of the thermal power industry. Although emissions are still much higher than in many developed countries and other industries. But since the stipulation, the coal consumption proportion of China is obviously reduced, and the consumption proportion of the substituted crude oil, natural gas and the nuclear energy of wind power, water and electricity is increased. However, according to the energy consumption proportion in 2017 in China, the consumption of coal resources is still high, and the consumption proportion reaches about 60%. Among coal-fired equipment, the discharge amount of nitrogen oxides discharged by boilers of power plants is the most serious, and accounts for over 36.1 percent of the total discharge amount of the whole country, and the discharge amount of smoke dust accounts for over 40 percent. It is predicted that coal will still be the main source of energy supply in the next few years, and the requirements for pollution control by coal will become more and more strict in the future.
Graphene is a new two-dimensional carbon nano material, and carbon atoms are sp in a plane2The graphene is doped by heteroatoms (such as nitrogen, boron, fluorine and the like)The band gap can be opened to be an n-type or p-type material, the electronic structure and other intrinsic properties of the material can be adjusted, and the application of the material in various fields can be effectively improved or enlarged. At present, doped graphene has been widely studied in a supercapacitor, but no mature technology exists for improving the denitration and sulfur resistance performance of the doped graphene as a catalyst carrier.
The commercial vanadium-titanium system catalyst has high activation temperature (>300 deg.c) and is difficult to apply at the end of a flue gas treatment system and is expensive to install and operate. Therefore, low temperature SCR technology, which is economical and suitable for end treatment, has been a focus of attention by researchers. Unsupported MnOx-CeO2The catalyst has the highest activity of the medium-low temperature SCR reported at present, and NO is generated at the temperature of 120 DEG CxCan be almost completely converted into N2However, no suitable technique has been used to successfully grow the graphene in situ on the nitrogen-boron co-doped graphene.
Disclosure of Invention
The invention aims to provide a nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and a preparation method thereof, and the preparation method is used for preparing the nitrogen-boron-codoped graphene catalyst composite material by carrying out boron doping and reducing graphene oxide after a high-efficiency denitration sulfur-resistant ternary catalyst grows in situ on self-made nitrogen-doped graphene oxide. Due to the in-situ growth method, the three-way catalyst is uniformly and firmly loaded on the surface of the nitrogen and boron co-doped graphene.
The method comprises the steps of taking self-made nitrogen-doped graphene oxide as a catalyst carrier, adopting an in-situ growth method to firmly load a catalyst, carrying out boron doping and reducing the graphene oxide to prepare efficient Mn-Ce-CoOx/rGO-N,BA composite material of a denitration sulfur-resistant catalyst.
The technical scheme adopted by the invention is as follows:
the self-made nitrogen-doped graphene oxide can be prepared by the following method:
(1) 1g of graphite was added to a 150mL beaker, and 40mL of concentrated sulfuric acid (abbreviated as H) was added2SO4) And placing the mixture in a water bath kettle for stirring at room temperature until the mixture is fully dissolved. Then accurately weighing 5g of potassium permanganate (KMnO for short)4) 0.2g of KMnO is added every 10min4。
（2）KMnO4After all the melamine cyanurate is added, the temperature of the water is raised to 50 ℃, the water is stirred and reacted for 1 hour, then 0.5g of Cyanuric Acid (CA) is added to be fully dissolved and reacted for 1 hour, 0.5g of melamine (M) is added, the reaction is continued for 2 hours, and 80mL of deionized water is added.
(3) Placing the reaction solution added with deionized water in a water bath kettle at 90 deg.C, stirring for 10min, and dropwise adding H2O2Until no bubble is present. And finally, adding 20mL of hydrochloric acid, repeatedly centrifuging the obtained product to be neutral, and transferring the product to a freeze dryer for freeze drying for later use. The final product obtained was named CA-M-GO.
More specifically, the nitrogen-boron co-doped graphene loaded with the ternary efficient denitration sulfur-resistant catalyst can be prepared by the following method:
(1) accurately weighing a 0.1g CA-M-GO sample, dissolving in 50mL deionized water to prepare a CA-M-GO solution, and performing ultrasonic dispersion for 10 min. 0.06g of polyvinylpyrrolidone (PVP for short) was added to the above solution and the sonication was continued for 10 min.
(2) Adding a certain mass of cerium acetate (Ce (Ac) for short)3) Adding into the prepared solution, adding a stirrer, and stirring at room temperature for 1 hour until the solution is Ce (Ac)3Completely dissolving; at this time, Ce3+ was grafted to the surface of CA-M-GO through dehydration condensation reaction. Then weighing a certain mass of cobalt chloride (CoCl)2) Adding into the above solution, and stirring at room temperature for 1 hr until CoCl2And completely dissolving.
(3) KMnO with certain concentration4Adding the solution into the step (1). Continuously reacting for 1H at room temperature, and weighing a certain mass of boric acid (H for short) after the reaction is finished3BO3) And sodium borohydride (NaBH for short)4) Adding the mixture into a reaction solution, stirring until boric acid and sodium borohydride are dissolved, transferring the reaction solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 12 hours at 160 ℃, centrifugally washing obtained suspension for a plurality of times, and carrying out vacuum freeze drying to obtain the final nitrogen and boron co-doped graphene catalyst composite material marked as Mn-Ce-CoOx/rGO-N,B。
The invention has the beneficial effects that: firstly, cyanuric acid and cyanuric acid are used for grafting graphene oxide, so that more N functional groups and defects are obtained on the surface of the graphene oxide. Due to the existence of the oxygen-containing functional groups and defects, the cerium-containing cerium acetate can react with each other to react with Ce3+The nitrogen-doped graphene oxide is firmly bonded on the surface of the nitrogen-doped graphene oxide. In addition, the addition of cobalt chloride can well form a reaction between the surface of the nitrogen-doped graphene oxide and Ce3+Reaction is carried out, so that a large amount of Ce is accumulated on the surface of the nitrogen-doped graphene oxide3+And Co2+Ions. And finally, performing oxidation-reduction reaction on the surface of the nitrogen-doped graphene oxide by using potassium permanganate as an oxidant to enable the manganese-cerium-cobalt catalyst to grow on the surface of the nitrogen-doped graphene oxide in situ, and finally preparing the nitrogen-boron co-doped graphene composite material loaded with the catalyst with the efficient denitration and sulfur-resistant functions by a hydrothermal method.
The method has the advantages that:
1. the unitary high-efficiency denitration catalyst mainly based on Mn is easy to be SO2Can be poisoned to generate MnSO4Therefore, the catalyst is denatured and inactivated, so that the denitration rate is greatly reduced, and even the denitration and sulfur resistance performance is almost lost. The existence of heteroatom nitrogen boron and rare earth metal cerium cobalt makes it have better sulfur resistance.
2. Due to the addition of cyanuric acid, boric acid and sodium borohydride, the self-made nitrogen and boron co-doped graphene in-situ growth catalyst has a higher specific surface, surface defects and more nitrogen and boron elements, and the factors are greatly favorable for carrying out denitration and sulfur resistance reaction. Therefore, compared with a pure graphene catalyst product, the catalyst has higher denitration and sulfur resistance.
3. The addition of the polyvinylpyrrolidone improves the dispersibility of the high-performance catalyst on the surface of the graphene, so that the high-performance catalyst is not agglomerated on the surface of the graphene, and the porous graphene catalyst composite material is obtained, so that the denitration and sulfur resistance of the graphene catalyst composite material is greatly improved.
4. The whole synthesis is carried out in a low-temperature environment, the reaction synthesis method and the operation are simple, the reaction is rapid, no specific requirements are required on a reaction container, the synthetic substance has no pollution to the environment, the synthesized catalyst and the nitrogen and boron co-doped graphene are firmly combined, the service life is long, and the denitration rate is high.
Drawings
FIG. 1 is a diagram of a self-made tubular SCR reactor device in a catalyst activity test according to the present invention; in the figure, 1 is a steam source; 2 is a pressure reducing valve; 3 is a mass flow meter; 4 is a mixer; 5 is an air preheater; 6 is a catalyst bed; 7 is a composite material; 8 is a flue gas analyzer;
FIG. 2 shows CA-M-GO and Ce (Ac)3The mass ratio is 1:0.75 by scanning electron micrograph of the catalyst;
FIG. 3 is CA-M-GO and Ce (Ac)3The mass ratio is 1: catalytic stability analysis plot of 0.75 catalyst.
Detailed Description
Example 1
Accurately weighing 0.1g of the self-made nitrogen-doped graphene oxide sample, dissolving the sample in 50mL of deionized water, carrying out ultrasonic treatment for 10min, adding 0.06g of polyvinylpyrrolidone (PVP for short), and carrying out ultrasonic dissolution, and then adding 0.055g of cerium acetate (Ce (Ac) for short)3) Adding into the prepared solution, adding a stirrer, and stirring at room temperature for 1 hour until the Ce (Ac)3And completely dissolving. Then 0.022g of cobalt chloride (CoCl) was weighed out2) Adding into the above solution, and stirring at room temperature for 1 hr until CoCl2And completely dissolving. Then accurately weigh 0.100g KMnO4Dissolved in 50mL of deionized water, and added to the reaction solution. The reaction was continued at room temperature for 1 hour, and after the reaction was completed, 0.1g of boric acid (abbreviated as H) was weighed3BO3) And 0.1g of sodium borohydride (NaBH for short)4) Adding the mixture into a reaction solution, stirring until boric acid is dissolved, transferring the reaction solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 12 hours at 160 ℃, centrifugally washing the obtained suspension for several times, and carrying out vacuum freeze drying to obtain the final nitrogen and boron co-doped graphene composite denitration sulfur-resistant catalyst to be tested. The mass of cobalt chloride was calculated as follows: 0.055 ÷ 317 × 129.8=0.022g, the concentration of potassium permanganate is calculated as follows: 0.1 ÷ 317 × 2 × 158= 0.100.
The denitration and sulfur resistance of the nitrogen-boron-codoped graphene composite denitration and sulfur-resistant catalyst is evaluated in a self-made tubular SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is set to be 140 ℃, and the denitration rate measured by a British KM940 flue gas analyzer is 53 percent; the temperature is set to be 160 ℃, the denitration rate is 71 percent, the temperature is set to be 180 ℃, and the denitration sulfur resistance rate is 86 percent; introducing SO at 180 DEG C2The test is carried out at intervals of 30min, and finally the out-of-stock rate is basically stabilized at 66%.
Example 2
Accurately weighing 0.1g of the self-made nitrogen-doped graphene oxide sample, dissolving the sample in 50mL of deionized water, performing ultrasonic treatment for 10min, adding 0.06g of polyvinylpyrrolidone (PVP for short), performing ultrasonic dissolution, and then dissolving 0.065g of cerium acetate (Ce (Ac) for short)3) Adding into the prepared solution, adding a stirrer, and stirring at room temperature for 1 hour until the Ce (Ac)3And completely dissolving. 0.027g of cobalt chloride (CoCl) was then weighed out2) Adding into the above solution, and stirring at room temperature for 1 hr until CoCl2And completely dissolving. Then accurately weigh 0.199gKMnO4Dissolved in 50mL of deionized water, and added to the reaction solution. The reaction was continued at room temperature for 1 hour, and after the reaction was completed, 0.1g of boric acid (abbreviated as H) was weighed3BO3) And 0.1g of sodium borohydride (NaBH for short)4) Adding the mixture into a reaction solution, stirring until boric acid is dissolved, transferring the reaction solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 12 hours at 160 ℃, centrifugally washing the obtained suspension for several times, and carrying out vacuum freeze drying to obtain the final nitrogen and boron co-doped graphene composite denitration sulfur-resistant catalyst to be tested. The mass of cobalt chloride was calculated as follows: 0.065 ÷ 317 × 129.8=0.027g, the concentration of potassium permanganate is calculated as follows: 0.2 ÷ 317 × 2 × 158= 0.199.
The denitration and sulfur resistance of the nitrogen-boron-codoped graphene composite denitration and sulfur-resistant catalyst is evaluated in a self-made tubular SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1Setting the temperature to be 140 ℃, and measuring the denitration rate to be 62% by using a British KM940 flue gas analyzer; the temperature is set to be 160 ℃, the denitration rate is 81 percent, the temperature is set to be 180 ℃, and the denitration sulfur resistance rate is 94 percent; introducing SO at 180 DEG C2The test is carried out at intervals of 30min, and finally the out-of-stock rate is basically stabilized at 72 percent.
Example 3
Accurately weighing 0.1g of the self-made nitrogen-doped graphene oxide sample, dissolving the sample in 50mL of deionized water, carrying out ultrasonic treatment for 10min, adding 0.06g of polyvinylpyrrolidone (PVP for short), and dissolving 0.075g of cerium acetate (Ce (Ac) for short) by ultrasonic treatment3) Adding into the prepared solution, adding a stirrer, and stirring at room temperature for 1 hour until the Ce (Ac)3And completely dissolving. Then 0.031g of cobalt chloride (CoCl) is weighed out2) Adding into the above solution, and stirring at room temperature for 1 hr until CoCl2And completely dissolving. Then accurately weigh 0.299g KMnO4Dissolved in 50mL of deionized water, and added to the reaction solution. The reaction was continued at room temperature for 1 hour, and after the reaction was completed, 0.1g of boric acid (abbreviated as H) was weighed3BO3) And 0.1g of sodium borohydride (NaBH for short)4) Adding the mixture into a reaction solution, stirring until boric acid is dissolved, transferring the reaction solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 12 hours at 160 ℃, centrifugally washing the obtained suspension for several times, and carrying out vacuum freeze drying to obtain the final nitrogen and boron co-doped graphene composite denitration sulfur-resistant catalyst to be tested. The mass of cobalt chloride was calculated as follows: 0.075/317 × 129.8=0.031g, the concentration of potassium permanganate is calculated as follows: 0.3 ÷ 317 × 2 × 158= 0.299.
The denitration and sulfur resistance of the nitrogen-boron-codoped graphene composite denitration and sulfur-resistant catalyst is evaluated in a self-made tubular SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is set to be 140 ℃, and the denitration rate is 74 percent measured by a British KM940 flue gas analyzer; the temperature is set to be 160 ℃, the denitration rate is 89%, the temperature is set to be 180 ℃, and the denitration sulfur-resistant rate is 100%; introducing SO at 180 DEG C2The test is carried out at intervals of 30min, and finally the out-of-stock rate is basically stabilized at 80 percent.
Example 4
Accurately weighing 0.1g of the self-made nitrogen-doped graphene oxide sample, dissolving the sample in 50mL of deionized water, carrying out ultrasonic treatment for 10min, adding 0.06g of polyvinylpyrrolidone (PVP for short), and dissolving 0.085g of cerium acetate (Ce (Ac) for short) by ultrasonic treatment3) Adding into the prepared solution, adding a stirrer, and stirring at room temperature for 1 hour until the Ce (Ac)3And completely dissolving. 0.035g of cobalt chloride (CoCl) was then weighed out2) Adding into the above solution, and stirring at room temperature for 1 hr until CoCl2And completely dissolving. Then accurately weigh 0.398g KMnO4Dissolved in 50mL of deionized water, and added to the reaction solution. The reaction was continued at room temperature for 1 hour, and after the reaction was completed, 0.1g of boric acid (abbreviated as H) was weighed3BO3) And 0.1g of sodium borohydride (NaBH for short)4) Adding the mixture into a reaction solution, stirring until boric acid is dissolved, transferring the reaction solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 12 hours at 160 ℃, centrifugally washing the obtained suspension for several times, and carrying out vacuum freeze drying to obtain the final nitrogen and boron co-doped graphene composite denitration sulfur-resistant catalyst to be tested. The mass of cobalt chloride was calculated as follows: 0.085 ÷ 317 × 129.8=0.035g, the concentration of potassium permanganate is calculated as follows: 0.4 ÷ 317 × 2 × 158= 0.398.
The denitration and sulfur resistance of the nitrogen-boron-codoped graphene composite denitration and sulfur-resistant catalyst is evaluated in a self-made tubular SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1Setting the temperature to be 140 ℃, and measuring the denitration rate to be 62% by using a British KM940 flue gas analyzer; the temperature is set to be 160 ℃, the denitration rate is 77%, the temperature is set to be 180 ℃, and the denitration sulfur resistance rate is 90%; introducing SO at 180 DEG C2The test is carried out at intervals of 30min, and finally the out-of-stock rate is basically stabilized at 73 percent.
Activity evaluation: the catalyst was evaluated in a self-made tubular SCR reactor. The reactor is electrically heated externally, a thermocouple is arranged beside a catalyst bed layer of the reaction tube to measure the temperature, and the flow of the experimental device is shown in figure 1. Simulating the composition of flue gas by using a steel gas cylinder, wherein the flue gas comprises NO and O2、N2、NH3To reduce gas, NO and NH3Volume fraction of 0.04-0.06%, O2The volume fraction is 4-6%, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is controlled between 120 ℃ and 200 ℃, and the gas flow and the gas composition are regulated and controlled by a mass flow meter. Gas analysis adopts a British KM940 smoke gas analyzer, and each working condition is stable for at least 30min in order to ensure the stability and accuracy of data.
Table 1 influence of various factors on the denitration sulfur resistance of the composite material (reaction temperature is 180 ℃):
as can be seen from the data in Table 1, the denitration sulfur resistance rate at 180 ℃ tends to increase and decrease with the increase of the mass ratio, and the maximum value appears at a mass ratio of 1: 0.75. And the sulfur resistance reaches the maximum.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. The utility model provides a compound denitration anti sulphur catalyst of nitrogen boron codope graphite alkene which characterized in that: the catalyst takes novel modified nitrogen-boron co-doped graphene as a catalyst carrier, and ternary Mn-Ce-CoO is prepared by usingxThe catalyst grows on the surface of the nitrogen-boron-codoped graphene in situ to obtain the nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst;
the nitrogen and boron co-doped graphene is obtained by preparing graphene oxide as a reaction precursor by a self-improved Hummers method according to the following method:
(1) adding 1g of graphite into a 150mL beaker, adding 33mL of concentrated sulfuric acid, placing the beaker in a water bath kettle, stirring the beaker at room temperature until the graphite is fully dissolved, accurately weighing 4g of potassium permanganate, and adding 0.2g of KMnO every 10min4；
（2）KMnO4After all the water is added, the temperature of the water is raised to 50 DEG CStirring and reacting for 1h, then adding 0.5g of cyanuric acid to fully dissolve and reacting for 1h, adding 0.5g of melamine and continuing to react for 2h, and then adding 80mL of deionized water;
(3) placing the reaction solution added with deionized water in a water bath kettle at 90 deg.C, stirring for 10min, and dropwise adding H2O2Until no bubble exists, finally adding 20mL of hydrochloric acid, repeatedly centrifuging the obtained product to be neutral, transferring the product to a freeze dryer for freeze drying for later use, and naming the finally obtained product as CA-M-GO;
the preparation method of the nitrogen and boron co-doped graphene composite denitration sulfur-resistant catalyst comprises the following steps:
1) accurately weighing a 0.1g CA-M-GO sample, dissolving the sample in 50mL deionized water to prepare a CA-M-GO solution, carrying out ultrasonic dispersion for 10min, adding 0.06g polyvinylpyrrolidone into the solution, and continuing to carry out ultrasonic treatment for 10 min;
2) thereafter, Ce (Ac) is added3Adding into the solution of the step 1), stirring for 1 hour at room temperature until the solution is Ce (Ac)3Completely dissolving;
3) adding CoCl2Adding the solution obtained in the step 2), and continuing stirring at room temperature for 1 hour till CoCl2Completely dissolving;
4) configuring KMnO4Adding the solution into the step 3), continuing to react for 1H at room temperature, and adding H after the reaction is finished3BO3And NaBH4Adding the mixture into a reaction solution, stirring the mixture until the mixture is dissolved, transferring the reaction solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction for 12 hours at 160 ℃, centrifugally washing the obtained suspension, and carrying out vacuum freeze drying to obtain the nitrogen-boron co-doped graphene composite denitration sulfur-resistant catalyst marked as Mn-Ce-CoOx/rGO-N,B。
2. The nitrogen-boron co-doped graphene composite denitration sulfur-resistant catalyst of claim 1, which is characterized in that: CA-M-GO and Ce (Ac)3The mass ratio of (A) to (B) is 1:0.55-1: 0.85.
3. The nitrogen-boron co-doped graphene composite denitration sulfur-resistant catalyst of claim 1, which is characterized in that: ce (Ac)3With CoCl2Is 1: 1.
4. The nitrogen-boron co-doped graphene composite denitration sulfur-resistant catalyst of claim 1, which is characterized in that: ce (Ac)3And KMnO4In a molar ratio of 1: 2.
5. The nitrogen-boron co-doped graphene composite denitration sulfur-resistant catalyst of claim 1, which is characterized in that: ce (Ac)3And H3BO3The mass ratio of (A) to (B) is 1: 1.
6. The nitrogen-boron co-doped graphene composite denitration sulfur-resistant catalyst of claim 1, which is characterized in that: h3BO3With NaBH4The mass ratio of (A) to (B) is 1: 1.
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