CN110961138A - Nitrogen-doped graphene grown in situ by self-assembled denitration sulfur-resistant catalyst and preparation method thereof - Google Patents
Nitrogen-doped graphene grown in situ by self-assembled denitration sulfur-resistant catalyst and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 35
- 239000011593 sulfur Substances 0.000 title claims abstract description 35
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- 239000012286 potassium permanganate Substances 0.000 claims description 10
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- 238000001354 calcination Methods 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 7
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- 230000007547 defect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 3
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
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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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J35/613—
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- B01J35/615—
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- B01J35/633—
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- B01J35/647—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
Abstract
The invention discloses nitrogen-doped graphene grown in situ by a self-assembled denitration sulfur-resistant catalyst and a preparation method thereof, wherein graphene oxide is used as a precursor, 2,4, 6-triaminopyrimidine and cyanuric acid are used for preparing modified nitrogen-doped graphene, and then the modified nitrogen-doped graphene is used as a catalyst carrier, and ternary Mn-Ce-SnO is grown in situ on the surface of the catalyst carrierxCatalyst is prepared. Self-assembled ternary Mn-Ce-SnO in the inventionxThe catalyst is uniformly and firmly loaded on the surface of the modified nitrogen-doped graphene in a surface in-situ growth mode, so that the obtained composite material has high-efficiency denitration capability and good sulfur resistance.
Description
Technical Field
The invention belongs to the technical field of graphene composite catalytic materials, and particularly relates to a surface in-situ growth self-assembly ternary denitration sulfur-resistant catalyst Mn-Ce-SnOxThe N-doped graphene and a preparation method thereof.
Background
With the rapid development of the industrialization process in China, a lot of unavoidable pollution is generated, wherein the atmospheric pollution is the most serious and most concerned problem in a plurality of pollutants. The generation of air pollution has relatively bad influence on life, health, work, nature and the like of people. At present, the air pollution source is mainly pollutants generated by coal combustion, including PM2.5, PM10, sulfur dioxide, nitrogen oxide, nitrogen dioxide and the like, and the gases can cause damages such as haze, acid rain, photochemical smog, greenhouse effect and the like.
It is known that, because a large amount of electric power demand brought by the strong promotion of infrastructure construction and manufacturing development in China needs to provide energy by means of coal combustion, the usage amount of coal resources in China is huge. 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.
Researchers have observed that incorporation of small amounts of graphene or graphene oxide into certain catalysts can accelerate the oxidation reaction rate. In research, the use of H in graphene oxide catalytic reaction is found2O2As an oxidizing agent, benzene can be oxidized in one step to phenol. In some researches, reduced graphene oxide is used as a catalyst, and the reduction reaction of nitrobenzene at room temperature is researched, so that the research result shows higher reaction activity and stability. Further experiments have shown that carbon atoms that are not saturated at the edges of graphene oxide or defects on the surface of graphene oxide may be the centre of catalytic activity.
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, there is no suitable technique for successful in-situ growth of graphene。
Disclosure of Invention
The invention aims to provide nitrogen-doped graphene grown in situ by a self-assembled denitration sulfur-resistant catalyst and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the nitrogen-doped graphene prepared by in-situ growth of the self-assembled denitration sulfur-resistant catalyst is prepared by taking graphene oxide as a precursor, preparing modified nitrogen-doped graphene by using 2,4, 6-triaminopyrimidine and cyanuric acid, and then taking the modified nitrogen-doped graphene as a catalyst carrier to in-situ grow ternary Mn-Ce-SnO on the surface of the modified nitrogen-doped graphenexCatalyst to prepare high-efficiency Mn-Ce-SnOxthe/rGO @ TAP-CA denitration sulfur-resistant catalyst composite material. The ternary catalyst in the composite material can be firmly combined on the surface of graphene, and has better sulfur resistance while denitration.
The preparation method of the nitrogen-doped graphene grown in situ by the self-assembled denitration sulfur-resistant catalyst comprises the following steps:
preparation of modified nitrogen-doped graphene
(1) Adding 1g graphite into 150mL beaker, adding 40mL concentrated sulfuric acid, stirring in water bath at room temperature, dissolving completely, and adding 0.2g KMnO every 10min4To KMnO4The addition amount of (2) is 5 g;
（2）KMnO4after all the materials are added, heating the water to 50 ℃, stirring and reacting for 1h, then adding 0.5g of 2,4, 6-Triaminopyrimidine (TAP), fully dissolving and continuing to react for 1h, adding 0.5g of Cyanuric Acid (CA), fully dissolving and continuing to react for 1h, and then adding 80ml of deionized water;
(3) placing the reaction solution obtained in the step 2) in a water bath kettle at 90 ℃ for stirring for 10min, and then dropwise adding H2O2Adding 20mL of hydrochloric acid until no bubbles are generated, repeatedly centrifuging and washing the obtained product to be neutral, and transferring the product to a freeze dryer for freeze drying to obtain GO @ TAP-CA;
in-situ growth of two-way and three-way catalysts
(4) Accurately weighing 0.1g of GO @ TAP-CA, dissolving the GO @ TAP-CA in 50mL of N, N-Dimethylformamide (DMF) to prepare a GO @ TAP-CA solution, performing ultrasonic dispersion for 10min, accurately adding 0.06g of polyvinylpyrrolidone (PVP), and continuing performing ultrasonic treatment for 10 min;
(5) a certain mass of cerium acetate (Ce (Ac)3) Adding into the solution obtained in the step (4), adding a stirrer, and stirring at room temperature for 1 hour until the Ce (Ac)3Completely dissolving; ce (Ac)3The addition amount of the compounds is determined according to GO @ TAP-CA and Ce (Ac)3Is obtained by conversion of (1), (2-5) (preferably 1: 4), in which case Ce is present3+Grafted to the surface of GO @ TAP-CA through a dehydration condensation reaction;
(6) mixing a certain mass of tin tetrachloride (SnCl)4) Adding the solution obtained in the step (5), and continuing stirring at room temperature for 1 hour till SnCl4Completely dissolving; SnCl4In an amount of Ce (Ac)3With SnCl4Is obtained by conversion of 1:1, at this time, the surface of GO @ TAP-CA is filled with Sn4+And Ce3+The product of the reaction;
(7) mixing KMnO of 0.03-0.08mol/L4Adding the solution into the solution obtained in the step (6), continuously reacting for 1h at room temperature, transferring the reaction solution to a watch glass after the reaction is finished, drying the watch glass in a drying oven at 102 ℃, adding the dried product into a concentrated sulfuric acid solution with the concentration of 1M for dissolving, transferring the product into a polytetrafluoroethylene liner, carrying out hydrothermal reaction for 10h at 160 ℃, repeatedly centrifuging and washing the obtained product to be neutral, and drying the product in the drying oven at 102 ℃, thus obtaining the GO @ TAP-CA (manganese-cerium-stannic oxide) of the surface in-situ growth self-assembled ternary denitration sulfur-resistant catalyst, which is marked as Mn-Ce-SnO-CAx/GO@TAP-CA；KMnO4In an amount of Ce (Ac)3And KMnO4The molar ratio of (A) to (B) is obtained by conversion of 1: 1;
(8) the obtained Mn-Ce-SnOxPutting the/GO @ TAP-CA in a high-temperature tube furnace, and calcining for 2h at 800 ℃ to obtain Mn-Ce-SnOx/rGO@TAP-CA。
The method comprises the steps of firstly taking graphene oxide as a precursor, and utilizing 2,4, 6-triaminopyrimidine andcyanuric acid is modified to enable the surface of the obtained modified graphene to have more nitrogen-containing functional groups and defects, the obtained modified graphene is used as a catalyst carrier, the functional groups and defects contained in the modified graphene are utilized to react with cerium acetate, and Ce is reacted with cerium acetate3+Firmly combined on the surface of the N-doped graphene oxide, and then tin chloride is added to ensure that the tin chloride is mixed with Ce on the surface of the graphene oxide3+Carrying out oxidation-reduction reaction to ensure that a large amount of Ce is accumulated on the surface of the graphene oxide3+、Ce4+、Sn3+And Sn4+Ions, finally, taking potassium permanganate as an oxidant, carrying out redox reaction on the surface of the graphene oxide, and enabling Mn-Ce-SnO to react by using a hydrothermal methodxThe catalyst grows on the surface of the N-doped graphene oxide in situ after self-assembly, and the final N-doped graphene composite material with the denitration and sulfur-resistant catalyst growing in situ is generated through one-time calcination.
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 MnSO4Thereby causing the denaturation and inactivation of the catalyst, causing the denitration rate to be greatly reduced, even almost losing the denitration and sulfur resistance performance, the invention grows the ternary catalyst Mn-Ce-SnO containing rare earth elements Ce and Sn on the surface of the graphene in situxSo that the sulfur-resistant rubber has better sulfur resistance.
2. Due to the addition of the 2,4, 6-triaminopyrimidine and the cyanuric acid, the N-doped graphene prepared by the invention has higher specific surface, surface defects and more N elements, and the factors are favorable for the denitration and sulfur-resistant reaction. Therefore, compared with a pure graphene catalyst product, the nitrogen-doped graphene grown in situ by the self-assembled denitration sulfur-resistant catalyst prepared by the invention has higher denitration sulfur-resistant performance.
3. Due to the self-assembly of the catalyst on the surface of the graphene, the catalyst agglomeration phenomenon on the surface of the graphene is reduced, and the reaction contact chance of the catalyst and gas is increased, so that the denitration and sulfur resistance of the catalyst on the surface of the graphene is further improved.
4. 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 cannot agglomerate on the surface of the graphene, and thus, a porous graphene catalyst composite material can be obtained, and the denitration and sulfur resistance of the porous graphene catalyst composite material is greatly improved.
5. The whole synthesis of the invention 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 for a reaction vessel, the synthetic substance has no pollution to the environment, the synthesized catalyst is firmly combined with the graphene, the service life is long, and the denitration rate is high.
Drawings
Fig. 1 is a schematic diagram of an apparatus for a tubular SCR reactor used in a catalyst activity test. In the figure, 1 is a gas 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; and 8 is a smoke analyzer.
FIG. 2 is an SEM photograph of the composite material prepared in example 3.
FIG. 3 is a graph showing the analysis of catalytic stability of the composite material prepared in example 3.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The modified nitrogen-doped graphene is prepared by taking Graphene Oxide (GO) prepared by an improved Hummers method as a reaction precursor, and the specific preparation method is as follows:
(1) adding 1g graphite into 150mL beaker, adding 40mL concentrated sulfuric acid, stirring in water bath at room temperature, dissolving completely, and adding 0.2g KMnO every 10min4To KMnO4The addition amount of (2) is 5 g;
（2）KMnO4after all the materials are added, heating the water to 50 ℃, stirring and reacting for 1h, then adding 0.5g of 2,4, 6-Triaminopyrimidine (TAP), fully dissolving and continuing to react for 1h, adding 0.5g of Cyanuric Acid (CA), fully dissolving and continuing to react for 1h, and then adding 80ml of deionized water;
(3) placing the reaction liquid obtained in the step 2) into a water bath kettle at 90 DEG CStirring for 10min, then adding H dropwise2O2And adding 20mL of hydrochloric acid until no bubbles are generated, repeatedly centrifuging and washing the obtained product to be neutral, and transferring the product to a freeze dryer for freeze drying to obtain GO @ TAP-CA.
Activity evaluation: the catalyst was evaluated in a 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 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.
Example 1
Accurately weighing 0.1g of GO @ TAP-CA, dissolving the GO @ TAP-CA in 50mL of DMF, carrying out ultrasonic treatment for 10min, adding PVP, carrying out ultrasonic treatment for 10min, and then adding 0.2g of Ce (Ac)3Stirring with a stirrer at room temperature for 1 hour to obtain Ce (Ac)3Completely dissolving; then 0.221g of SnCl was added4Stirring is continued at room temperature for 1 hour until SnCl4Completely dissolving; then, 0.099g of KMnO was accurately weighed4Dissolving in 20mL of DMF, adding the DMF into the solution, continuously reacting at room temperature for 4h, transferring the reaction solution to a watch glass after the reaction is finished, drying in an oven at 102 ℃, adding the dried product into a concentrated sulfuric acid solution with the concentration of 1M for dissolving, transferring to a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 160 ℃ for 10h, repeatedly centrifuging and washing the obtained product to be neutral, and drying in the oven at 102 ℃; and (3) placing the dried sample in a high-temperature tube furnace, and calcining for 2h at 800 ℃ to obtain the final composite material.
The denitration and sulfur resistance of the composite material is evaluated in a 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-1. The results show that the denitration rate at 140 ℃ is 69%; the denitration rate is 78% when the temperature is set to be 160 ℃, and the denitration rate is 85% when the temperature is set to be 180 ℃; then SO is introduced at 180 DEG C2And testing at intervals of 30min, wherein the final denitration rate is basically stabilized at 60%.
Example 2
Accurately weighing 0.1g of GO @ TAP-CA, dissolving the GO @ TAP-CA in 50mL of DMF, carrying out ultrasonic treatment for 10min, adding PVP, carrying out ultrasonic treatment for 10min, and then adding 0.3g of Ce (Ac)3Stirring with a stirrer at room temperature for 1 hour to obtain Ce (Ac)3Completely dissolving; then 0.331g of SnCl is added4Stirring is continued at room temperature for 1 hour until SnCl4Completely dissolving; thereafter, 0.149g of KMnO was accurately weighed4Dissolving in 20mL of DMF, adding the DMF into the solution, continuously reacting at room temperature for 4h, transferring the reaction solution to a watch glass after the reaction is finished, drying in an oven at 102 ℃, adding the dried product into a concentrated sulfuric acid solution with the concentration of 1M for dissolving, transferring to a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 160 ℃ for 10h, repeatedly centrifuging and washing the obtained product to be neutral, and drying in the oven at 102 ℃; and (3) placing the dried sample in a high-temperature tube furnace, and calcining for 2h at 800 ℃ to obtain the final composite material.
The denitration and sulfur resistance of the composite material is evaluated in a 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-1. The results show that the denitration rate at the temperature set at 140 ℃ is 77%; the denitration rate is 80% when the temperature is set to be 160 ℃, and the denitration rate is 87% when the temperature is set to be 180 ℃; then SO is introduced at 180 DEG C2And testing at intervals of 30min, wherein the final denitration rate is basically stabilized at 62%.
Example 3
Accurately weighing 0.1g of GO @ TAP-CA, dissolving the GO @ TAP-CA in 50mL of DMF, carrying out ultrasonic treatment for 10min, adding PVP, carrying out ultrasonic treatment for 10min, and then adding 0.4g of Ce (Ac)3Stirring with a stirrer at room temperature for 1 hour to obtain Ce (Ac)3Completely dissolving; then 0.442g of SnCl was added4Stirring is continued at room temperature for 1 hour until SnCl4Completely dissolving;then, 0.198g of KMnO was accurately weighed4Dissolving in 20mL of DMF, adding the DMF into the solution, continuously reacting at room temperature for 4h, transferring the reaction solution to a watch glass after the reaction is finished, drying in an oven at 102 ℃, adding the dried product into a concentrated sulfuric acid solution with the concentration of 1M for dissolving, transferring to a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 160 ℃ for 10h, repeatedly centrifuging and washing the obtained product to be neutral, and drying in the oven at 102 ℃; and (3) placing the dried sample in a high-temperature tube furnace, and calcining for 2h at 800 ℃ to obtain the final composite material.
The denitration and sulfur resistance of the composite material is evaluated in a 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-1. The results show that the denitration rate at the temperature set at 140 ℃ is 77%; the denitration rate is 85% when the temperature is set to be 160 ℃, and 92% when the temperature is set to be 180 ℃; then SO is introduced at 180 DEG C2And testing at intervals of 30min, and finally, basically stabilizing the denitration rate at 70%.
Example 4
Accurately weighing 0.1g of GO @ TAP-CA, dissolving the GO @ TAP-CA in 50mL of DMF, carrying out ultrasonic treatment for 10min, adding PVP, carrying out ultrasonic treatment for 10min, and then adding 0.5g of Ce (Ac)3Stirring with a stirrer at room temperature for 1 hour to obtain Ce (Ac)3Completely dissolving; 0.553g of SnCl were then added4Stirring is continued at room temperature for 1 hour until SnCl4Completely dissolving; then 0.248g KMnO was accurately weighed4Dissolving in 20mL of DMF, adding the DMF into the solution, continuously reacting at room temperature for 4h, transferring the reaction solution to a watch glass after the reaction is finished, drying in an oven at 102 ℃, adding the dried product into a concentrated sulfuric acid solution with the concentration of 1M for dissolving, transferring to a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 160 ℃ for 10h, repeatedly centrifuging and washing the obtained product to be neutral, and drying in the oven at 102 ℃; and (3) placing the dried sample in a high-temperature tube furnace, and calcining for 2h at 800 ℃ to obtain the final composite material.
The denitration and sulfur resistance of the composite material is evaluated in a tubular SCR reactor. NO and NH3The volume fractions are all 0.05 percent,O2the volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1. The results show that the denitration rate at 140 ℃ is 68%; the denitration rate is 70% when the temperature is set to be 160 ℃, and the denitration rate is 86% when the temperature is set to be 180 ℃; then SO is introduced at 180 DEG C2And testing at intervals of 30min, wherein the final denitration rate is basically stabilized at 61%.
Comparative example
Accurately weighing 0.1g of graphene oxide prepared by the improved Hummers method, dissolving the graphene oxide in 50mL of DMF, carrying out ultrasonic treatment for 10min, adding PVP, carrying out ultrasonic treatment for 10min, and adding 0.4g of Ce (Ac)3Stirring with a stirrer at room temperature for 1 hour to obtain Ce (Ac)3Completely dissolving; then 0.442g of SnCl was added4Stirring is continued at room temperature for 1 hour until SnCl4Completely dissolving; then, 0.198g of KMnO was accurately weighed4Dissolving in 20mL of DMF, adding the DMF into the solution, continuously reacting at room temperature for 4h, transferring the reaction solution to a watch glass after the reaction is finished, drying in an oven at 102 ℃, adding the dried product into a concentrated sulfuric acid solution with the concentration of 1M for dissolving, transferring to a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 160 ℃ for 10h, repeatedly centrifuging and washing the obtained product to be neutral, and drying in the oven at 102 ℃; and (3) placing the dried sample in a high-temperature tube furnace, and calcining for 2h at 800 ℃ to obtain the final composite material.
The denitration and sulfur resistance of the composite material is evaluated in a 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-1. The results show that the denitration rate at 140 ℃ is 70%; the denitration rate at 160 ℃ is 76%, and the denitration rate at 180 ℃ is 82%; then SO is introduced at 180 DEG C2And testing at intervals of 30min, wherein the final denitration rate is basically stabilized at 60%.
TABLE 1 specific surface area, pore volume and mean pore diameter of different composites
Table 2 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 2, at 180 ℃, the denitration sulfur-resistant rate tends to increase and then decrease along with the continuous increase of the mass ratio, the maximum value appears at the mass ratio of 1:4, and the sulfur-resistant performance also reaches the maximum value, namely the best effect can be achieved at the ratio.
FIG. 3 is a graph showing the analysis of catalytic stability of the composite material prepared in example 3. As can be seen from FIG. 3, the denitration effect of the catalyst is not obviously reduced and is stabilized at about 90% with the increase of the catalytic reaction time, which indicates that the catalyst has good catalytic stability.
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 (5)
1. A preparation method of nitrogen-doped graphene grown in situ by a self-assembled denitration sulfur-resistant catalyst is characterized by comprising the following steps: preparing modified nitrogen-doped graphene by using graphene oxide as a precursor and 2,4, 6-triaminopyrimidine and cyanuric acid, and then growing ternary Mn-Ce-SnO on the surface of the modified nitrogen-doped graphene in situ by using the modified nitrogen-doped graphene oxide as a catalyst carrierxAnd (3) the catalyst is used, so that the nitrogen-doped graphene grown in situ by the self-assembled denitration sulfur-resistant catalyst is obtained.
2. The preparation method of the nitrogen-doped graphene grown in situ by the self-assembled denitration sulfur-resistant catalyst as claimed in claim 1, characterized by comprising the following steps: the method comprises the following steps:
preparation of modified nitrogen-doped graphene
(1) Adding 1g graphite into a beaker, adding 40mL concentrated sulfuric acid, placing in a water bath kettle, stirring at room temperature until the graphite is fully dissolved, and then adding 0.2g KMnO every 10min4To KMnO4The addition amount of (2) is 5 g;
（2）KMnO4after all the materials are added, heating the water to 50 ℃, stirring and reacting for 1h, then adding 0.5g of 2,4, 6-triaminopyrimidine, fully dissolving and continuing to react for 1h, adding 0.5g of cyanuric acid, fully dissolving and continuing to react for 1h, and then adding 80ml of deionized water;
(3) placing the reaction solution obtained in the step 2) in a water bath kettle at 90 ℃ for stirring for 10min, and then dropwise adding H2O2Adding 20mL of hydrochloric acid until no bubbles are generated, repeatedly centrifuging and washing the obtained product to be neutral, and transferring the product to a freeze dryer for freeze drying to obtain GO @ TAP-CA;
in-situ growth of two-way and three-way catalysts
(4) Accurately weighing 0.1g of GO @ TAP-CA, dissolving the GO @ TAP-CA in 50mL of N, N-dimethylformamide to prepare a GO @ TAP-CA solution, accurately adding 0.06g of polyvinylpyrrolidone after ultrasonic dispersion for 10min, and continuing ultrasonic treatment for 10 min;
(5) a certain mass of Ce (Ac)3Adding the solution obtained in the step (4), and stirring the solution at room temperature for 1 hour till Ce (Ac)3Completely dissolving;
(6) adding a certain mass of SnCl4Adding the solution obtained in the step (5), and continuing stirring at room temperature for 1 hour till SnCl4Completely dissolving;
(7) 50Ml of KMnO with a certain concentration4Adding the solution into the solution obtained in the step (6), continuously reacting for 1h at room temperature, transferring the reaction solution to a watch glass after the reaction is finished, drying the watch glass in a drying oven at 102 ℃, adding the dried product into a concentrated sulfuric acid solution with the concentration of 1M for dissolving, transferring the product into a polytetrafluoroethylene liner, carrying out hydrothermal reaction for 10h at 160 ℃, repeatedly centrifuging and washing the obtained product to be neutral, and drying the product in the drying oven at 102 ℃, thus obtaining the GO @ TAP-CA (labeled as Mn-Ce-SnO-CA) of the surface in-situ growth self-assembled ternary denitration sulfur-resistant catalystx/GO@TAP-CA；
(8) The obtained Mn-Ce-SnOxPutting the/GO @ TAP-CA in a high-temperature tube furnace, and calcining for 2h at 800 ℃ to obtain Mn-Ce-SnOx/rGO@TAP-CA。
3. The preparation method of the nitrogen-doped graphene grown in situ by the self-assembled denitration sulfur-resistant catalyst according to claim 2, characterized by comprising the following steps: ce (Ac) in step (5)3The addition amount of the compounds is determined according to GO @ TAP-CA and Ce (Ac)3The mass ratio of (1) to (2-5) is obtained by conversion.
4. The preparation method of the nitrogen-doped graphene grown in situ by the self-assembled denitration sulfur-resistant catalyst according to claim 2, characterized by comprising the following steps: SnCl in step (6)4In an amount of Ce (Ac)3With SnCl4Is obtained in terms of 1: 1.
5. The preparation method of the nitrogen-doped graphene grown in situ by the self-assembled denitration sulfur-resistant catalyst according to claim 2, characterized by comprising the following steps: KMnO in step (7)4In an amount of Ce (Ac)3And KMnO4The molar ratio of (A) to (B) is obtained by conversion of 1: 1;
the KMnO used4The concentration of the solution is 0.03-0.08 mol/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841614A (en) * | 2020-08-18 | 2020-10-30 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
| CN111939959A (en) * | 2020-08-18 | 2020-11-17 | 福州大学 | Nitrogen-sulfur co-doped graphene composite material loaded with ternary efficient denitration sulfur-resistant catalyst and preparation method thereof |
| CN113058618A (en) * | 2021-03-25 | 2021-07-02 | 福州大学 | Polyphenylene sulfide composite material with sulfur-doped graphene denitration sulfur-resistant catalyst loaded in situ and preparation method thereof |
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5932943A (en) * | 1982-08-17 | 1984-02-22 | Chobe Taguchi | Agent for desulfurization-denitration in combination |
| CN103183341A (en) * | 2013-04-02 | 2013-07-03 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN103381369A (en) * | 2013-07-10 | 2013-11-06 | 清华大学 | Nitrogen doped carbon material loaded catalyst |
| CN103736481A (en) * | 2014-01-15 | 2014-04-23 | 广东电网公司电力科学研究院 | CeO2-MoO3/graphene low-temperature denitration catalyst and preparation method |
| CN104759277A (en) * | 2015-03-18 | 2015-07-08 | 华南理工大学 | CeOx-MnOx/graphene low-temperature SCR flue gas denitration catalyst and preparation method thereof |
| CN104843693A (en) * | 2015-05-07 | 2015-08-19 | 常州大学 | Preparation method of N-doped graphene sheet |
| JP5858572B2 (en) * | 2011-12-13 | 2016-02-10 | 国立研究開発法人日本原子力研究開発機構 | Method for producing regenerated catalyst metal-supported carbon catalyst using spent catalyst metal-supported carbon catalyst |
| CN105363451A (en) * | 2015-12-04 | 2016-03-02 | 中国天辰工程有限公司 | Efficient catalyst for decomposition of N2O and preparation method and application thereof |
| CN106732729A (en) * | 2016-12-28 | 2017-05-31 | 山东理工大学 | Polybenzimidazoles with pyridine groups prepares the three-dimensional nitrogen-doped graphene of high nitrogen-containing |
| CN107570142A (en) * | 2017-08-31 | 2018-01-12 | 中国建筑材料科学研究总院 | Low-temperature denitration catalyst and preparation method thereof |
| CN107837606A (en) * | 2017-11-21 | 2018-03-27 | 福州大学 | A kind of lignin modification composite filtering material for loading ternary denitration sulfur resistant catalyst and preparation method thereof |
| CN109046441A (en) * | 2018-09-14 | 2018-12-21 | 中国海洋大学 | A kind of titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalyst and preparation method thereof |
| CN110152677A (en) * | 2019-05-20 | 2019-08-23 | 宁波大学 | A kind of difunctional compound VPO catalysts of perovskite/cerium oxide with biomimetic features |
-
2019
- 2019-12-25 CN CN201911358676.7A patent/CN110961138B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5932943A (en) * | 1982-08-17 | 1984-02-22 | Chobe Taguchi | Agent for desulfurization-denitration in combination |
| JP5858572B2 (en) * | 2011-12-13 | 2016-02-10 | 国立研究開発法人日本原子力研究開発機構 | Method for producing regenerated catalyst metal-supported carbon catalyst using spent catalyst metal-supported carbon catalyst |
| CN103183341A (en) * | 2013-04-02 | 2013-07-03 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN103381369A (en) * | 2013-07-10 | 2013-11-06 | 清华大学 | Nitrogen doped carbon material loaded catalyst |
| CN103736481A (en) * | 2014-01-15 | 2014-04-23 | 广东电网公司电力科学研究院 | CeO2-MoO3/graphene low-temperature denitration catalyst and preparation method |
| CN104759277A (en) * | 2015-03-18 | 2015-07-08 | 华南理工大学 | CeOx-MnOx/graphene low-temperature SCR flue gas denitration catalyst and preparation method thereof |
| CN104843693A (en) * | 2015-05-07 | 2015-08-19 | 常州大学 | Preparation method of N-doped graphene sheet |
| CN105363451A (en) * | 2015-12-04 | 2016-03-02 | 中国天辰工程有限公司 | Efficient catalyst for decomposition of N2O and preparation method and application thereof |
| CN106732729A (en) * | 2016-12-28 | 2017-05-31 | 山东理工大学 | Polybenzimidazoles with pyridine groups prepares the three-dimensional nitrogen-doped graphene of high nitrogen-containing |
| CN107570142A (en) * | 2017-08-31 | 2018-01-12 | 中国建筑材料科学研究总院 | Low-temperature denitration catalyst and preparation method thereof |
| CN107837606A (en) * | 2017-11-21 | 2018-03-27 | 福州大学 | A kind of lignin modification composite filtering material for loading ternary denitration sulfur resistant catalyst and preparation method thereof |
| CN109046441A (en) * | 2018-09-14 | 2018-12-21 | 中国海洋大学 | A kind of titanium dioxide/carbonitride/Cu-ZSM-5 photochemical catalyst and preparation method thereof |
| CN110152677A (en) * | 2019-05-20 | 2019-08-23 | 宁波大学 | A kind of difunctional compound VPO catalysts of perovskite/cerium oxide with biomimetic features |
Non-Patent Citations (1)
| Title |
|---|
| PENG LI ET.AL: ""N-doped graphene/CoFe2O4 catalysts for the selective catalytic reduction of NOx by NH3"", 《RSC ADV.》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841614A (en) * | 2020-08-18 | 2020-10-30 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
| CN111939959A (en) * | 2020-08-18 | 2020-11-17 | 福州大学 | Nitrogen-sulfur co-doped graphene composite material loaded with ternary efficient denitration sulfur-resistant catalyst and preparation method thereof |
| CN111841614B (en) * | 2020-08-18 | 2021-10-29 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
| CN111939959B (en) * | 2020-08-18 | 2021-11-30 | 福州大学 | Nitrogen-sulfur co-doped graphene composite material loaded with ternary efficient denitration sulfur-resistant catalyst and preparation method thereof |
| CN113058618A (en) * | 2021-03-25 | 2021-07-02 | 福州大学 | Polyphenylene sulfide composite material with sulfur-doped graphene denitration sulfur-resistant catalyst loaded in situ and preparation method thereof |
| CN113101746A (en) * | 2021-05-06 | 2021-07-13 | 福州大学 | Sandwich-shaped graphene aerogel-based catalyst filter material and preparation method thereof |
| CN113368898A (en) * | 2021-06-16 | 2021-09-10 | 福州大学 | Method for preparing high-water-resistance filter material by ball milling method |
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