A high-performance RCO catalyst

Abstract

The invention relates to the field of RCO catalysts, and specifically to a high-performance RCO catalyst, which is used to solve the problems of low activity and poor stability of existing RCO catalysts, and the problem that they cannot meet increasingly stringent exhaust gas emission standards. The high-performance RCO catalyst uses activated carbon as a carrier, which has excellent adsorption properties and can adsorb organic waste gas into the interior of the activated carbon, so that the organic waste gas can fully contact with the metal oxide, catalyze the redox reaction of harmful gases in the organic waste gas, and significantly improve the activity of the activated carbon in removing harmful gases in the organic waste gas, resulting in excellent purification effect. In addition, the introduced nitrogen and fluorine elements can further increase the active sites of the activated carbon, and the addition of fluorine can greatly improve its pollution resistance, thereby preventing dust in the organic waste gas from clogging the micropores of the activated carbon, so that the activated carbon has a long-lasting and high purification effect.

Description

Technical Field

[0001] The present invention relates to the field of RCO catalysts, and in particular to a high-performance RCO catalyst. Background Art

[0002] With the rapid development of industrialization, waste gas emissions are becoming increasingly serious. More and more toxic and hazardous gases are being released into the air, posing a serious threat to the environment and human health. To address this issue, various waste gas treatment technologies have been developed, among which RCO catalysts play a key role. The principle of RCO catalysts is to convert organic waste gas into harmless substances through a redox reaction under the action of a catalyst. However, existing RCO catalysts suffer from low activity and poor stability, making them unable to meet increasingly stringent waste gas emission standards. Therefore, the development of a high-performance RCO catalyst has become an urgent issue to be addressed. Summary of the Invention

[0003] In order to overcome the above technical problems, the present invention aims to provide a high-performance RCO catalyst. Activated carbon is used as a carrier. The activated carbon is first treated and ultrasonically washed with deionized water to fully clean it. The activated carbon is then treated with concentrated nitric acid to oxidatively modify the activated carbon, thereby increasing its specific surface area and enriching its pore structure. Manganese sulfate monohydrate, cerium nitrate hexahydrate, and zirconium nitrate pentahydrate are then dissolved to form a metal ion solution. The nitric acid-oxidized activated carbon is then impregnated. The water is then evaporated to dryness, and the metal elements are fully attached to the nitric acid-oxidized activated carbon. The activated carbon is then calcined to form manganese, cerium, and zirconium doped activated carbon. Copper elements are then attached again and calcined again to incorporate the copper elements into the activated carbon. Finally, the activated carbon is calcined and oxidized at high temperature with ammonium fluoride. This not only allows the metal elements to interpenetrate to form oxides, but also allows nitrogen and fluorine to be fully incorporated, ultimately forming a high-performance RCO catalyst. This solves the problems of low activity and poor stability of existing RCO catalysts, which cannot meet increasingly stringent exhaust emission standards.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A high-performance RCO catalyst is prepared by the following steps:

[0006] Step 1: Grind the activated carbon to form activated carbon particles with a particle size of 0.25-0.75 mm;

[0007] Step 2: Add the activated carbon particles to deionized water, then ultrasonically wash them for 30-60 minutes at an ultrasonic frequency of 35-45 kHz, then centrifuge them, place the precipitate in a vacuum drying oven, and dry it at a temperature of 100-105° C. for 8-10 hours to obtain washed activated carbon;

[0008] Step 3: Add the washed activated carbon and nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 200-300 r / min, then heat to 80-85°C and continue stirring and reacting for 1.5-2 hours. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with distilled water 2-3 times, and then place it in a vacuum drying oven and dry it at a temperature of 100-105°C for 5-6 hours to obtain nitric acid-oxidized activated carbon;

[0009] Step 4: Add manganese sulfate monohydrate, cerium nitrate hexahydrate, zirconium nitrate pentahydrate and deionized water to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30-40 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min, then add nitric acid to oxidize the activated carbon and continue stirring and reacting for 3-3.5 hours, then heat to 80-85°C and continue stirring and reacting for 1.5-2 hours, after which the reaction is completed, cool the reaction product to room temperature, let it stand for 8-10 hours, then place it in a vacuum drying oven, dry it at a temperature of 100-105°C for 4-5 hours, then place it in a tubular furnace, introduce nitrogen protection, and calcine it at a temperature of 300-320°C for 2-2.5 hours to obtain primary metal-doped activated carbon;

[0010] Step 5: Add copper nitrate trihydrate and deionized water to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30-40 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min, then add primary metal-doped activated carbon and continue stirring and reacting for 3-3.5 hours, then place in a vacuum drying oven, dry at a temperature of 100-105°C for 4-5 hours, then place in a tubular furnace, pass nitrogen protection, and calcine at a temperature of 300-320°C for 2-2.5 hours to obtain secondary metal-doped activated carbon;

[0011] Step 6: The secondary metal-doped activated carbon and ammonium fluoride are mixed evenly, and then placed in a tubular furnace, calcined at a temperature of 750-850°C and air-flowed for 2-2.5 hours, and then cooled with the furnace to obtain a high-performance RCO catalyst.

[0012] As a further solution of the present invention: the ratio of the activated carbon particles to deionized water in step 2 is 5g:70-80mL.

[0013] As a further solution of the present invention: the usage ratio of the washed activated carbon and the nitric acid solution in step three is 5g:55-60mL.

[0014] As a further solution of the present invention: the mass fraction of the nitric acid solution is 40-45%.

[0015] As a further solution of the present invention: the usage ratio of the manganese sulfate monohydrate, cerium nitrate hexahydrate, zirconium nitrate pentahydrate, deionized water and nitric acid oxidized activated carbon in step 4 is 10 mmol: 10 mmol: 10 mmol: 120-150 mL: 10 g.

[0016] As a further solution of the present invention: the usage ratio of the copper nitrate trihydrate, deionized water and primary metal-doped activated carbon in step five is 10-20 mmol: 120-150 mL: 10 g.

[0017] As a further solution of the present invention: the usage ratio of the secondary metal-doped activated carbon and ammonium fluoride in step six is 10g:1-5g.

[0018] Beneficial effects of the present invention:

[0019] The present invention discloses a high-performance RCO catalyst. The catalyst uses activated carbon as a carrier. The activated carbon is first treated and ultrasonically washed with deionized water to fully clean it. The activated carbon is then treated with concentrated nitric acid to oxidatively modify the activated carbon, thereby increasing its specific surface area and enriching its pore structure. Manganese sulfate monohydrate, cerium nitrate hexahydrate, and zirconium nitrate pentahydrate are then dissolved to form a metal ion solution. The nitric acid-oxidized activated carbon is then impregnated. The water is evaporated to dryness, and the metal elements are fully attached to the nitric acid-oxidized activated carbon. The activated carbon is then calcined to form manganese-cerium-zirconium doped activated carbon. Copper elements are then attached again, and the activated carbon is calcined again to dope the copper elements into the activated carbon. The activated carbon is finally calcined and oxidized at high temperature with ammonium fluoride. The metal elements are not only infiltrated into each other to form oxides, but also nitrogen and fluorine elements are fully incorporated, thereby ultimately forming a high-performance RCO catalyst.

[0020] The high-performance RCO catalyst uses activated carbon as a carrier, which makes it have excellent adsorption performance and can adsorb organic waste gas into the interior of the activated carbon, so that the organic waste gas can fully contact with the metal oxide. The metal oxide supported on the activated carbon has excellent redox performance, catalyzes the redox reaction of harmful gases in the organic waste gas, and can also significantly improve the activity of the activated carbon in removing harmful gases in the organic waste gas, with excellent purification effect. Moreover, the introduced nitrogen and fluorine elements can further enhance the active sites of the activated carbon, and the addition of fluorine can give the activated carbon low surface energy, greatly improving its pollution resistance, thereby preventing dust in the organic waste gas from clogging the micropores of the activated carbon, and achieving the purpose of long-term high purification effect. The high-performance RCO catalyst prepared by the present invention has the characteristics of high activity, high stability, high heat resistance, etc., can effectively improve the treatment effect of waste gas, and reduce energy consumption and cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present invention will be further described below with reference to the accompanying drawings.

[0022] Figure 1 This is a process flow chart of a high-performance RCO catalyst preparation process in the present invention;

[0023] Figure 2 It is a line graph showing the detection structure of the NO removal rate of a high-performance RCO catalyst in the present invention. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0025] Example 1:

[0026] See also Figure 1 As shown, this embodiment is a method for preparing a high-performance RCO catalyst, comprising the following steps:

[0027] Step 1: Grind the 20-mesh activated carbon from Dalin Environmental Protection Technology Co., Ltd. into activated carbon particles with a particle size of 0.75 mm;

[0028] Step 2: 5 g of activated carbon particles were added to 70 mL of deionized water, and then ultrasonically washed for 30 min at an ultrasonic frequency of 35 kHz, followed by centrifugation. The precipitate was placed in a vacuum drying oven and dried at a temperature of 100 ° C for 8 h to obtain washed activated carbon;

[0029] Step 3: Add 5 g of washed activated carbon and 55 mL of 40% nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 20 minutes at a temperature of 25°C and a stirring rate of 200 r / min, then heat to 80°C and continue stirring and reacting for 1.5 hours. After the reaction is completed, the reaction product is cooled to room temperature and then centrifuged. The precipitate is washed twice with distilled water and then placed in a vacuum drying oven and dried at a temperature of 100°C for 5 hours to obtain nitric acid-oxidized activated carbon;

[0030] Step 4: 10 mmol manganese sulfate monohydrate, 10 mmol cerium nitrate hexahydrate, 10 mmol zirconium nitrate pentahydrate and 150 mL deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 25 ° C and a stirring rate of 200 r / min for 30 minutes. Then, 10 g of nitric acid was added to oxidize the activated carbon and the stirring reaction was continued for 3 hours. Then, the temperature was raised to 80 ° C and the stirring reaction was continued for 1.5 hours. After the reaction, the reaction product was cooled to room temperature and then allowed to stand for 8 hours. It was then placed in a vacuum drying oven and dried at a temperature of 100 ° C for 4 hours. It was then placed in a tubular furnace, nitrogen protection was introduced, and calcined at a temperature of 300 ° C for 2 hours to obtain primary metal-doped activated carbon;

[0031] Step 5: Add 10 mmol copper nitrate trihydrate and 120 mL deionized water to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30 minutes at a temperature of 25°C and a stirring rate of 200 r / min, then add 10 g of primary metal-doped activated carbon and continue stirring and reacting for 3 hours, then place in a vacuum drying oven, dry at a temperature of 100°C for 4 hours, then place in a tubular furnace, pass nitrogen protection, and calcine at a temperature of 300°C for 2 hours to obtain secondary metal-doped activated carbon;

[0032] Step 6: Mix 10g of secondary metal-doped activated carbon and 1g of ammonium fluoride evenly, then place in a tubular furnace, calcine at a temperature of 750°C and with air for 2h, and then cool with the furnace to obtain a high-performance RCO catalyst.

[0033] Example 2:

[0034] See also Figure 1 As shown, this embodiment is a method for preparing a high-performance RCO catalyst, comprising the following steps:

[0035] Step 1: Grind the 20-mesh activated carbon from Dalin Environmental Protection Technology Co., Ltd. into activated carbon particles with a particle size of 0.50 mm;

[0036] Step 2: 5 g of activated carbon particles were added to 75 mL of deionized water, and then ultrasonically washed for 45 min at an ultrasonic frequency of 40 kHz, followed by centrifugation. The precipitate was placed in a vacuum drying oven and dried at a temperature of 102 ° C for 9 h to obtain washed activated carbon;

[0037] Step 3: Add 5 g of washed activated carbon and 58 mL of 42% nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 25 minutes at a temperature of 28 ° C and a stirring rate of 250 r / min, then heat to 82 ° C and continue stirring and reacting for 1.8 hours. After the reaction is completed, the reaction product is cooled to room temperature and then centrifuged. The precipitate is washed twice with distilled water and then placed in a vacuum drying oven and dried at a temperature of 102 ° C for 5.5 hours to obtain nitric acid oxidized activated carbon;

[0038] Step 4: 10 mmol manganese sulfate monohydrate, 10 mmol cerium nitrate hexahydrate, 10 mmol zirconium nitrate pentahydrate and 135 mL deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 28 ° C and a stirring rate of 250 r / min for 35 minutes. Then, 10 g of nitric acid was added to oxidize the activated carbon and the stirring reaction was continued for 3.2 hours. After that, the temperature was raised to 82 ° C and the stirring reaction was continued for 1.8 hours. After the reaction was completed, the reaction product was cooled to room temperature and then allowed to stand for 9 hours. It was then placed in a vacuum drying oven and dried at a temperature of 102 ° C for 4.5 hours. It was then placed in a tubular furnace, nitrogen protection was introduced, and calcined at a temperature of 310 ° C for 2.2 hours to obtain primary metal-doped activated carbon;

[0039] Step 5: Add 15 mmol copper nitrate trihydrate and 135 mL deionized water to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 35 minutes at a temperature of 28 ° C and a stirring rate of 250 r / min, then add 10 g of primary metal-doped activated carbon and continue stirring and reacting for 3.2 hours, then place in a vacuum drying oven, dry at a temperature of 102 ° C for 4.5 hours, then place in a tubular furnace, pass nitrogen protection, and calcine at a temperature of 310 ° C for 2.2 hours to obtain secondary metal-doped activated carbon;

[0040] Step 6: Mix 10g of secondary metal-doped activated carbon and 3g of ammonium fluoride evenly, then place in a tubular furnace, calcine at 800°C with air for 2.2h, and then cool with the furnace to obtain a high-performance RCO catalyst.

[0041] Example 3:

[0042] See also Figure 1As shown, this embodiment is a method for preparing a high-performance RCO catalyst, comprising the following steps:

[0043] Step 1: Grind the 20-mesh activated carbon from Dalin Environmental Protection Technology Co., Ltd. into activated carbon particles with a particle size of 0.25 mm;

[0044] Step 2: 5 g of activated carbon particles were added to 80 mL of deionized water, and then ultrasonically washed for 60 min at an ultrasonic frequency of 45 kHz, followed by centrifugation. The precipitate was placed in a vacuum drying oven and dried at a temperature of 105 ° C for 10 h to obtain washed activated carbon;

[0045] Step 3: Add 5 g of washed activated carbon and 60 mL of 45% nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 300 r / min, then heat to 85°C and continue stirring and reacting for 2 hours. After the reaction is completed, the reaction product is cooled to room temperature and then centrifuged. The precipitate is washed three times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 105°C for 6 hours to obtain nitric acid-oxidized activated carbon;

[0046] Step 4: 10 mmol manganese sulfate monohydrate, 10 mmol cerium nitrate hexahydrate, 10 mmol zirconium nitrate pentahydrate and 120 mL deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 30 ° C and a stirring rate of 300 r / min for 40 minutes. Then, 10 g of nitric acid was added to oxidize the activated carbon and the stirring reaction was continued for 3.5 hours. Then, the temperature was raised to 85 ° C and the stirring reaction was continued for 2 hours. After the reaction, the reaction product was cooled to room temperature and then allowed to stand for 10 hours. Then, the product was placed in a vacuum drying oven and dried at a temperature of 105 ° C for 5 hours. Then, the product was placed in a tubular furnace, nitrogen was introduced, and the product was calcined at a temperature of 320 ° C for 2.5 hours to obtain primary metal-doped activated carbon.

[0047] Step 5: Add 20 mmol copper nitrate trihydrate and 120 mL deionized water to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 40 min at a temperature of 30 ° C and a stirring rate of 300 r / min, then add 10 g of primary metal-doped activated carbon and continue stirring and reacting for 3.5 h. Then place it in a vacuum drying oven and dry it at a temperature of 105 ° C for 5 h. Then place it in a tubular furnace, pass nitrogen protection, and calcine it at a temperature of 320 ° C for 2.5 h to obtain secondary metal-doped activated carbon;

[0048] Step 6: Mix 10g of secondary metal-doped activated carbon and 5g of ammonium fluoride evenly, then place in a tubular furnace, calcine at 850°C with air for 2.5h, and then cool with the furnace to obtain a high-performance RCO catalyst.

[0049] Comparative Example 1:

[0050] This comparative example is a method for preparing a high-performance RCO catalyst, comprising the following steps:

[0051] Step 1: Grind the 20-mesh activated carbon from Dalin Environmental Protection Technology Co., Ltd. into activated carbon particles with a particle size of 0.25 mm;

[0052] Step 2: Add 5 g of activated carbon particles to 80 mL of deionized water, then ultrasonically wash for 60 minutes at an ultrasonic frequency of 45 kHz, then centrifuge, place the precipitate in a vacuum drying oven, and dry it at a temperature of 105°C for 10 hours to obtain a high-performance RCO catalyst.

[0053] Comparative Example 2:

[0054] This comparative example is a method for preparing a high-performance RCO catalyst, comprising the following steps:

[0055] Step 1: Grind the 20-mesh activated carbon from Dalin Environmental Protection Technology Co., Ltd. into activated carbon particles with a particle size of 0.25 mm;

[0056] Step 2: 5 g of activated carbon particles were added to 80 mL of deionized water, and then ultrasonically washed for 60 min at an ultrasonic frequency of 45 kHz, followed by centrifugation. The precipitate was placed in a vacuum drying oven and dried at a temperature of 105 ° C for 10 h to obtain washed activated carbon;

[0057] Step 3: Add 5 g of washed activated carbon and 60 mL of 45% nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 300 r / min, then heat to 85°C and continue stirring and reacting for 2 hours. After the reaction is completed, the reaction product is cooled to room temperature and then centrifuged. The precipitate is washed three times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 105°C for 6 hours to obtain a high-performance RCO catalyst.

[0058] Comparative Example 3:

[0059] This comparative example is a method for preparing a high-performance RCO catalyst, comprising the following steps:

[0060] Step 1: Grind the 20-mesh activated carbon from Dalin Environmental Protection Technology Co., Ltd. into activated carbon particles with a particle size of 0.25 mm;

[0061] Step 2: 5 g of activated carbon particles were added to 80 mL of deionized water, and then ultrasonically washed for 60 min at an ultrasonic frequency of 45 kHz, followed by centrifugation. The precipitate was placed in a vacuum drying oven and dried at a temperature of 105 ° C for 10 h to obtain washed activated carbon;

[0062] Step 3: Add 5 g of washed activated carbon and 60 mL of 45% nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 300 r / min, then heat to 85°C and continue stirring and reacting for 2 hours. After the reaction is completed, the reaction product is cooled to room temperature and then centrifuged. The precipitate is washed three times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 105°C for 6 hours to obtain nitric acid-oxidized activated carbon;

[0063] Step 4: 10 mmol manganese sulfate monohydrate, 10 mmol cerium nitrate hexahydrate, 10 mmol zirconium nitrate pentahydrate and 120 mL deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at a temperature of 30 ° C and a stirring rate of 300 r / min for 40 minutes. Then, 10 g of nitric acid-oxidized activated carbon was added and the stirring reaction was continued for 3.5 hours. Then, the temperature was raised to 85 ° C and the stirring reaction was continued for 2 hours. After the reaction, the reaction product was cooled to room temperature and then allowed to stand for 10 hours. It was then placed in a vacuum drying oven and dried at a temperature of 105 ° C for 5 hours. It was then placed in a tubular furnace, nitrogen protection was introduced, and calcined at a temperature of 320 ° C for 2.5 hours to obtain a high-performance RCO catalyst.

[0064] Comparative Example 4:

[0065] This comparative example is a method for preparing a high-performance RCO catalyst, comprising the following steps:

[0066] Step 1: Grind the 20-mesh activated carbon from Dalin Environmental Protection Technology Co., Ltd. into activated carbon particles with a particle size of 0.25 mm;

[0067] Step 2: 5 g of activated carbon particles were added to 80 mL of deionized water, and then ultrasonically washed for 60 min at an ultrasonic frequency of 45 kHz, followed by centrifugation. The precipitate was placed in a vacuum drying oven and dried at a temperature of 105 ° C for 10 h to obtain washed activated carbon;

[0068] Step 3: Add 5 g of washed activated carbon and 60 mL of 45% nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 300 r / min, then heat to 85°C and continue stirring and reacting for 2 hours. After the reaction is completed, the reaction product is cooled to room temperature and then centrifuged. The precipitate is washed three times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 105°C for 6 hours to obtain nitric acid-oxidized activated carbon;

[0069] Step 4: 10 mmol manganese sulfate monohydrate, 10 mmol cerium nitrate hexahydrate, 10 mmol zirconium nitrate pentahydrate and 120 mL deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 30 ° C and a stirring rate of 300 r / min for 40 minutes. Then, 10 g of nitric acid was added to oxidize the activated carbon and the stirring reaction was continued for 3.5 hours. Then, the temperature was raised to 85 ° C and the stirring reaction was continued for 2 hours. After the reaction, the reaction product was cooled to room temperature and then allowed to stand for 10 hours. Then, the product was placed in a vacuum drying oven and dried at a temperature of 105 ° C for 5 hours. Then, the product was placed in a tubular furnace, nitrogen was introduced, and the product was calcined at a temperature of 320 ° C for 2.5 hours to obtain primary metal-doped activated carbon.

[0070] Step 5: Add 20 mmol copper nitrate trihydrate and 120 mL deionized water to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 40 minutes at a temperature of 30°C and a stirring rate of 300 r / min, then add 10 g of primary metal-doped activated carbon and continue stirring and reacting for 3.5 hours. Then place it in a vacuum drying oven and dry it at a temperature of 105°C for 5 hours. Then place it in a tubular furnace, pass nitrogen protection, and calcine it at a temperature of 320°C for 2.5 hours to obtain a high-performance RCO catalyst.

[0071] Comparative Example 5:

[0072] This comparative example is a method for preparing a high-performance RCO catalyst, comprising the following steps:

[0073] Step 1: Grind the 20-mesh activated carbon from Dalin Environmental Protection Technology Co., Ltd. into activated carbon particles with a particle size of 0.25 mm;

[0074] Step 2: 5 g of activated carbon particles were added to 80 mL of deionized water, and then ultrasonically washed for 60 min at an ultrasonic frequency of 45 kHz, followed by centrifugation. The precipitate was placed in a vacuum drying oven and dried at a temperature of 105 ° C for 10 h to obtain washed activated carbon;

[0075] Step 3: Add 5 g of washed activated carbon and 60 mL of 45% nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 300 r / min, then heat to 85°C and continue stirring and reacting for 2 hours. After the reaction is completed, the reaction product is cooled to room temperature and then centrifuged. The precipitate is washed three times with distilled water and then placed in a vacuum drying oven and dried at a temperature of 105°C for 6 hours to obtain nitric acid-oxidized activated carbon;

[0076] Step 4: 10 mmol manganese sulfate monohydrate, 10 mmol cerium nitrate hexahydrate, 10 mmol zirconium nitrate pentahydrate and 120 mL deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 30 ° C and a stirring rate of 300 r / min for 40 minutes. Then, 10 g of nitric acid was added to oxidize the activated carbon and the stirring reaction was continued for 3.5 hours. Then, the temperature was raised to 85 ° C and the stirring reaction was continued for 2 hours. After the reaction, the reaction product was cooled to room temperature and then allowed to stand for 10 hours. Then, the product was placed in a vacuum drying oven and dried at a temperature of 105 ° C for 5 hours. Then, the product was placed in a tubular furnace, nitrogen was introduced, and the product was calcined at a temperature of 320 ° C for 2.5 hours to obtain primary metal-doped activated carbon.

[0077] Step 5: 10g of primary metal-doped activated carbon and 5g of ammonium fluoride were mixed evenly, and then placed in a tubular furnace, calcined at a temperature of 850°C and air-flowed for 2.5h, and then cooled in the furnace to obtain a high-performance RCO catalyst.

[0078] Performance testing:

[0079] The high-performance RCO catalysts in Examples 1-3 and Comparative Examples 1-5 were filled into a fixed-bed reaction system. The filling mass for each test was 1.0 g. The reaction temperature was 200-400° C. The composition of the introduced gas was as follows: the volume fractions of NO, NH 3 , O 2 , H 2 O, and SO 2 were 0.05%, 0.05%, 5%, 5%, and 0.005%, respectively, and the remainder was nitrogen. The gas flow rate was 590 mL / min.

[0080] The catalytic performance of high-performance RCO catalyst was evaluated by NO removal rate. NO The calculation formula is as follows:

[0081]

[0082] Where:

[0083] C 进口 is the inlet volume concentration of NO, %;

[0084] C 出口 is the inlet volume concentration of NO, %.

[0085] The test results of NO removal rate are as follows: Figure 2 As shown:

[0086]

[0087] See the table above and Figure 2 As shown, according to the comparison between Examples 1-3 and Comparative Examples 1-5, it can be seen that the activated carbon has an excellent NO removal rate by doping with metal oxides containing manganese, cerium, and zirconium elements, and the NO removal rate of the activated carbon is further improved by doping with metal oxides containing copper elements. Finally, the NO removal rate of the activated carbon can be further improved by doping with fluorine elements. The high-performance RCO catalyst finally obtained can achieve a NO removal rate of 96.8%, and the NO removal effect is excellent.

[0088] Based on the above embodiments and comparative examples, the working principle of the present invention is as follows:

[0089] The method comprises the following steps: crushing activated carbon to form activated carbon particles, adding the activated carbon particles to deionized water for ultrasonic washing, centrifuging, and drying the precipitate to obtain washed activated carbon, stirring the washed activated carbon and nitric acid solution, cooling the reaction product after the reaction is completed, centrifuging, washing, and drying the precipitate to obtain nitric acid oxidized activated carbon, stirring manganese sulfate monohydrate, cerium nitrate hexahydrate, zirconium nitrate pentahydrate, and deionized water, and then adding nitric acid oxidized activated carbon to continue stirring the reaction, cooling the reaction product after the reaction is completed, standing, drying, and calcining to obtain primary metal-doped activated carbon, and stirring copper nitrate trihydrate, deionized water, and nitric acid to react with each other. The reaction is stirred, and then the primary metal-doped activated carbon is added and the stirring reaction is continued, and then the secondary metal-doped activated carbon is obtained by drying and calcining. The secondary metal-doped activated carbon and ammonium fluoride are evenly mixed, and then placed in a tubular furnace for calcination, and then cooled with the furnace to obtain a high-performance RCO catalyst. The catalyst uses activated carbon as a carrier, and first the activated carbon is treated. After ultrasonic washing with deionized water, it can be fully cleaned, and then treated with concentrated nitric acid to oxidize and modify the activated carbon, increase its specific surface area and enrich its pore structure, and then manganese sulfate monohydrate, cerium nitrate hexahydrate, and zirconium nitrate pentahydrate are dissolved to form a metal ion solution, and then impregnated. Activated carbon is oxidized with nitric acid, and then the water is evaporated and the metal elements are fully attached to the nitric acid-oxidized activated carbon, which is then calcined to form activated carbon doped with manganese, cerium and zirconium. Copper elements are then attached again and calcined again to dope the copper elements into the activated carbon. Finally, it is calcined and oxidized at high temperature with ammonium fluoride, which not only allows the metal elements to penetrate each other to form oxides, but also fully incorporates nitrogen and fluorine elements, ultimately forming a high-performance RCO catalyst. The high-performance RCO catalyst uses activated carbon as a carrier, which gives it excellent adsorption properties and can adsorb organic waste gas into the interior of the activated carbon, so that the organic waste gas can fully contact with the metal oxide and is loaded on the activated carbon. The metal oxide has excellent redox properties, catalyzes the redox reaction of harmful gases in organic waste gas, and can also significantly improve the activity of activated carbon in removing harmful gases in organic waste gas, with excellent purification effect. Moreover, the introduced nitrogen and fluorine elements can further enhance the active sites of activated carbon, and the addition of fluorine element can give activated carbon low surface energy, greatly improving its pollution resistance, thereby preventing dust in organic waste gas from clogging the micropores of activated carbon, and achieving the purpose of long-term high purification effect. The high-performance RCO catalyst prepared by the present invention has the characteristics of high activity, high stability, high heat resistance, etc., which can effectively improve the treatment effect of waste gas and reduce energy consumption and cost.

[0090] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0091] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A high performance RCO catalyst, characterized in that: The high performance RCO catalyst is prepared by the following steps: Step 1: Grind the activated carbon to form activated carbon particles with a particle size of 0.25-0.75 mm; Step 2: Adding activated carbon particles to deionized water, then ultrasonically washing for 30-60 minutes at an ultrasonic frequency of 35-45 kHz, then centrifuging, placing the precipitate in a vacuum drying oven, and drying it at a temperature of 100-105° C. for 8-10 hours to obtain washed activated carbon; the ratio of the activated carbon particles to deionized water is 5 g:70-80 mL; Step 3: Add the washed activated carbon and nitric acid solution to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 200-300 r / min, then heat to 80-85°C and continue stirring and reacting for 1.5-2 hours. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with distilled water 2-3 times, and then place it in a vacuum drying oven and dry it at a temperature of 100-105°C for 5-6 hours to obtain nitric acid-oxidized activated carbon; the usage ratio of the washed activated carbon and the nitric acid solution is 5g:55-60mL; the mass fraction of the nitric acid solution is 40-45%; Step 4: Add manganese sulfate monohydrate, cerium nitrate hexahydrate, zirconium nitrate pentahydrate and deionized water to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30-40 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min, then add nitric acid oxidized activated carbon and continue stirring and reacting for 3-3.5 hours, then raise the temperature to 80-85°C and continue stirring and reacting for 1.5-2 hours, after which the reaction product is cooled to room temperature, then allowed to stand for 8-10 hours, then placed in a vacuum drying oven, dried at a temperature of 100-105°C for 4-5 hours, then placed in a tubular furnace, passed nitrogen protection, and calcined at a temperature of 300-320°C for 2-2.5 hours to obtain primary metal-doped activated carbon; the amount ratio of the manganese sulfate monohydrate, cerium nitrate hexahydrate, zirconium nitrate pentahydrate, deionized water and nitric acid oxidized activated carbon is 10mmo l:10mmo l: 10mmo l: 120-150mL: 10g; Step 5: Add copper nitrate trihydrate and deionized water to a three-necked flask equipped with a stirrer and a thermometer, stir and react for 30-40 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min, then add primary metal-doped activated carbon and continue stirring and reacting for 3-3.5 hours, then place in a vacuum drying oven, dry at a temperature of 100-105°C for 4-5 hours, then place in a tubular furnace, pass nitrogen protection, and calcine at a temperature of 300-320°C for 2-2.5 hours to obtain secondary metal-doped activated carbon; the amount ratio of the copper nitrate trihydrate, deionized water and primary metal-doped activated carbon is 10-20mmol:120-150mL:10g; Step 6: The secondary metal-doped activated carbon and ammonium fluoride are mixed evenly, and then placed in a tubular furnace, calcined at a temperature of 750-850°C and air-flowing for 2-2.5 hours, and then cooled with the furnace to obtain a high-performance RCO catalyst; the usage ratio of the secondary metal-doped activated carbon and ammonium fluoride is 10g:1-5g.

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