Conductive catalytic membrane, preparation method thereof and method for purifying flue gas by coupling conductive catalytic membrane with ozone
阅读说明：本技术 一种导电催化膜及其制备方法和利用导电催化膜耦合臭氧净化烟气的方法 (Conductive catalytic membrane, preparation method thereof and method for purifying flue gas by coupling conductive catalytic membrane with ozone ) 是由 齐立强 王铮 于哲 李泽鹏 王吻 于 2021-09-30 设计创作，主要内容包括：本发明提供了一种导电催化膜及其制备方法和利用导电催化膜耦合臭氧净化烟气的方法,属于气相有机污染物净化技术领域。本发明通过过量浸渍法制备导电催化膜,将导电催化膜耦合电除尘器中的臭氧,通过利用这部分臭氧用于降解烟气中的VOCs可以极大的节约经济成本,同时还避免了过量臭氧进入大气造成污染,达到臭氧和VOCs协同处理的目的。(The invention provides a conductive catalytic membrane, a preparation method thereof and a method for purifying flue gas by coupling the conductive catalytic membrane with ozone, and belongs to the technical field of gas-phase organic pollutant purification. The invention prepares the conductive catalytic membrane by an excessive impregnation method, couples the conductive catalytic membrane with ozone in an electric dust collector, and can greatly save the economic cost by using the ozone to degrade VOCs in flue gas, simultaneously avoid the pollution caused by excessive ozone entering the atmosphere and achieve the purpose of cooperatively treating the ozone and the VOCs.)
1. A conductive catalytic membrane, comprising a conductive support and an active component attached to the conductive support;
the active component is metal salt, and the conductive carrier is carbon nano tube.
2. The conductive catalytic film of claim 1 wherein the metal salt comprises CoO, Co3O4、MnO2、Mn2O3、Mn3O4、PtCl2And PtCl4One or more of them.
3. A method of preparing an electrically conductive catalytic membrane as claimed in claim 1 or 2, comprising the steps of:
mixing the metal salt solution with the carbon nano tube dispersion liquid to obtain a mixed liquid, and carrying out vacuum filtration on the mixed liquid to obtain a solid mixture;
and (3) refining the solid mixture into mixed powder, and mixing and coating the mixed powder and the N-methyl pyrrolidone to obtain the conductive catalytic membrane.
4. The preparation method of the conductive catalytic membrane as claimed in claim 3, wherein a metal salt is dissolved in deionized water to obtain a metal salt solution, and the mass concentration of the metal salt solution is 1-20%; and dispersing the carbon nanotubes in deionized water to obtain a carbon nanotube dispersion liquid, wherein the mass fraction of the carbon nanotubes in the carbon nanotube dispersion liquid is 10-30%.
5. The preparation method of the conductive catalytic film according to claim 3, wherein the volume ratio of the metal salt solution to the carbon nanotube dispersion liquid is 1-2: 1.
6. the method for preparing the conductive catalytic membrane according to claim 3, wherein the refinement is to dry and grind the solid mixture, the temperature for drying the solid mixture is 60-70 ℃, and the time for drying is 10-20 h.
7. The preparation method of the conductive catalytic membrane as claimed in claim 3, wherein the mass-to-volume ratio of the mixed powder to the azomethidone is 2-5 g: 10 mL.
8. The preparation method of the conductive catalytic membrane as claimed in claim 3, wherein the temperature of mixing the mixed powder with the nitrogen methyl pyrrolidone is 40-60 ℃, and the mixing time is 5-8 h;
the thickness of the conductive catalytic film is 150-300 mu m.
9. A method for purifying flue gas by coupling the conductive catalytic membrane of claim 1 or 2 with ozone, comprising the steps of:
the conductive catalytic membrane is attached to a polar plate of the electric dust collector, ozone is generated after the electric dust collector is electrified, and the ozone reacts with organic gas in the flue gas under the action of the conductive catalytic membrane, so that the organic gas can be degraded.
10. The method for purifying the flue gas as claimed in claim 9, wherein the power of the electric dust remover is 200-800W, the current is 30-200 mA, and the concentration of the generated ozone is 300-2000 ppm;
the reaction temperature is 130-150 ℃, and the reaction time is 5-20 min.
Technical Field
The invention relates to the technical field of gas-phase organic pollutant purification, in particular to a conductive catalytic membrane, a preparation method thereof and a method for purifying flue gas by coupling the conductive catalytic membrane with ozone.
Background
Volatile Organic Compounds (VOCs) are a class of organic compounds with boiling points below 250 ℃, and are also important precursors of PM2.5 and ozone, mainly including alcohols, esters, ketones, aromatic hydrocarbons, alkanes, aldehydes and other organic compounds, and the high toxicity and carcinogenicity of the volatile organic compounds pose serious threats to the living health and natural environment of human beings. With the enhancement of atmospheric environment treatment in China, the air quality in China is obviously improved, the concentration of fine particulate matters (PM2.5) is obviously reduced, but the pollution of ozone and VOCs is not effectively solved. Therefore, the cooperative treatment of the ozone and the VOCs has important practical significance for improving the air quality in China in the future.
In order to meet increasingly stringent environmental regulations and related emission standards, various technologies for degrading and treating VOCs are widely studied, and the technologies can be mainly classified into the following two types: 1) recovery techniques (mainly including adsorption, absorption, membrane separation, condensation, etc.); 2) oxidative degradation (mainly including catalytic oxidation, thermal incineration, biodegradation, photocatalytic decomposition, non-thermal plasma oxidation, and the like). The above techniques have certain limitations due to the wide variety of VOCs and conditions associated with different emissions sources. The adsorption technology is suitable for treating highly diluted VOCs, the absorption and membrane separation technology has high cost, the biodegradation has certain selectivity and temperature sensitivity, the photocatalytic activity is influenced by quantum efficiency, and the thermal incineration has higher energy requirement (more than or equal to 800 ℃).
Catalytic degradation of VOCs to CO2And H2O is currently one of the most efficient and economically feasible techniques for treating low concentrations of VOCs. The method is mainly characterized in that VOCs pollutants are catalytically degraded by a proper catalyst at a temperature far lower than the thermal incineration temperature (usually 200-500 ℃). The common catalytic degradation is mainly carried out by using two basic types of catalysts: supported Noble Metal Catalysts (SNMC) and Transition Metal Oxides (TMO). General SNMC ActivityThe performance is high, and the mineralization effect on VOCs is good; TMO has the advantages of low cost, excellent reducibility and thermal stability, poisoning resistance and the like, and both TMO and TMO have good catalytic performance for degrading VOCs. Meanwhile, the ozone catalytic oxidation technology is also one of effective methods for treating and degrading VOCs. Ozone is a strong oxidant, which can oxidize pollutants in a short time, and the catalyst promotes the rapid decomposition of ozone to generate active substances which react with organic matters, thereby achieving the purpose of rapidly degrading the organic matters. Conventional ozone generators produce ozone by high voltage ionization, which has a large energy consumption. How to obtain a method for purifying flue gas by utilizing catalytic degradation and ozone coupling is a problem which is urgently needed to be solved at present.
Disclosure of Invention
The invention aims to provide a conductive catalytic membrane, a preparation method thereof and a method for purifying flue gas by coupling the conductive catalytic membrane with ozone.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a conductive catalytic membrane, which comprises a conductive carrier and an active component attached to the conductive carrier;
the active component is metal salt, and the conductive carrier is carbon nano tube.
Further, the metal salt comprises CoO and Co3O4、MnO2、Mn2O3、Mn3O4、PtCl2And PtCl4One or more of them.
The invention provides a preparation method of a conductive catalytic membrane, which comprises the following steps:
mixing the metal salt solution with the carbon nano tube dispersion liquid to obtain a mixed liquid, and carrying out vacuum filtration on the mixed liquid to obtain a solid mixture;
and (3) refining the solid mixture into mixed powder, and mixing and coating the mixed powder and the N-methyl pyrrolidone to obtain the conductive catalytic membrane.
Further, dissolving a metal salt in deionized water to obtain a metal salt solution, wherein the mass concentration of the metal salt solution is 1-20%; and dispersing the carbon nanotubes in deionized water to obtain a carbon nanotube dispersion liquid, wherein the mass fraction of the carbon nanotubes in the carbon nanotube dispersion liquid is 10-30%.
Furthermore, the volume ratio of the metal salt solution to the carbon nano tube dispersion liquid is 1-2: 1.
Further, the refinement is to dry and grind the solid mixture, wherein the drying temperature of the solid mixture is 60-70 ℃, and the drying time is 10-20 hours.
Further, the mass volume ratio of the mixed powder to the azomethyl pyrrolidone is 2-5 g: 10 mL.
Further, the mixing temperature of the mixed powder and the N-methyl pyrrolidone is 40-60 ℃, and the mixing time is 5-8 hours;
the thickness of the conductive catalytic film is 150-300 mu m.
The invention provides a method for purifying flue gas by coupling conductive catalytic membrane with ozone, which comprises the following steps:
the conductive catalytic membrane is attached to a polar plate of the electric dust collector, ozone is generated after the electric dust collector is electrified, and the ozone reacts with organic gas in the flue gas under the action of the conductive catalytic membrane, so that the organic gas can be degraded.
Further, the electrifying power of the electric dust collector is 200-800W, the electrifying current is 30-200 mA, and the concentration of generated ozone is 300-2000 ppm;
the reaction temperature is 130-150 ℃, and the reaction time is 5-20 min.
The invention has the beneficial effects that:
1. the method is unique, and realizes the SO in the coal-fired flue gas by utilizing the ozone generated in the electric dust collector2、NOx、Hg0And VOCs catalytic degradation with high efficiency, does not need an additional ozone generating device, and effectively reduces economic cost. Does not need to be disassembled from the prior flue gas purification equipmentBesides or after modification, the process cost is greatly reduced.
2. The catalytic degradation process of the VOCs by coupling the conductive catalytic membrane with the ozone is provided, on one hand, the catalytic degradation of the VOCs in a reaction system is promoted, on the other hand, the ozone generated by the electric dust remover is effectively utilized and consumed, and the cooperative control of the ozone and the VOCs is realized.
3. In the system, ozone is used for catalyzing and degrading VOCs and residual SO in flue gas2NOx and Hg0The heavy metals are equal, SO that the concentration of pollutants in the flue gas can easily reach the ultralow emission standard, and SO is realized2、NOx、Hg0、O3And the synergistic control of multiple pollutants in flue gas such as VOCs and the like.
4. According to the method for purifying the flue gas, the degradation rate of VOCs under different ozone concentrations (300-2000 ppm) is as high as 98-100%.
Detailed Description
The invention provides a conductive catalytic membrane, which comprises a conductive carrier and an active component attached to the conductive carrier;
the active component is metal salt, and the conductive carrier is carbon nano tube.
In the present invention, the metal salt comprises CoO, Co3O4、MnO2、Mn2O3、Mn3O4、PtCl2And PtCl4Preferably MnO is selected from one or more of2、Mn2O3、Mn3O4、PtCl2And PtCl4More preferably Mn2O3、Mn3O4And PtCl2One or more of them.
The invention provides a preparation method of a conductive catalytic membrane, which comprises the following steps:
mixing the metal salt solution with the carbon nano tube dispersion liquid to obtain a mixed liquid, and carrying out vacuum filtration on the mixed liquid to obtain a solid mixture;
and (3) refining the solid mixture into mixed powder, and mixing and coating the mixed powder and the N-methyl pyrrolidone to obtain the conductive catalytic membrane.
In the invention, the metal salt is preferably dissolved in deionized water to obtain a metal salt solution, and the mass concentration of the metal salt solution is 1-20%, preferably 5-15%, and further preferably 10%; the carbon nanotubes are preferably dispersed in deionized water to obtain a carbon nanotube dispersion liquid, and the mass fraction of the carbon nanotubes in the carbon nanotube dispersion liquid is 10-30%, preferably 15-25%, and more preferably 20%.
In the invention, the volume ratio of the metal salt solution to the carbon nanotube dispersion liquid is 1-2: 1, preferably 1-1.5: 1, and more preferably 1: 1.
In the invention, the refinement is to dry and grind the solid mixture, wherein the drying temperature of the solid mixture is 60-70 ℃, and the drying time is 10-20 h; preferably, the drying temperature is 62-68 ℃, and the drying time is 12-18 h; more preferably, the drying temperature is 65 ℃ and the drying time is 15 h.
In the invention, the mass-volume ratio of the mixed powder to the azomethylpyrrolidone is 2-5 g: 10mL, preferably 3-4 g: 10mL, and more preferably 3 g: 10 mL.
In the invention, the temperature for mixing the mixed powder and the N-methyl pyrrolidone is 40-60 ℃, and the mixing time is 5-8 h; preferably, the mixing temperature is 45-55 ℃, and the mixing time is 6-7 h; further preferably, the mixing temperature is 50 ℃ and the mixing time is 7 hours.
In the invention, the thickness of the conductive catalytic film is 150-300 μm, preferably 180-280 μm, and more preferably 250 μm.
In the invention, the loading amount of the active component in the conductive catalytic membrane is 1-20%, preferably 5-15%, and more preferably 10%.
The invention provides a method for purifying flue gas by coupling conductive catalytic membrane with ozone, which comprises the following steps:
the conductive catalytic membrane is attached to a polar plate of the electric dust collector, ozone is generated after the electric dust collector is electrified, and the ozone reacts with organic gas in the flue gas under the action of the conductive catalytic membrane, so that the organic gas can be degraded.
In the invention, the electrified power of the electric dust collector is 200-800W, the electrified current is 30-200 mA, and the concentration of generated ozone is 300-2000 ppm; preferably, the electrifying power of the electric dust collector is 300-700W, the electrifying current is 50-150 mA, and the concentration of ozone is 500-1800 ppm; more preferably, the electrifying power of the electric dust collector is 400-600W, the electrifying current is 100-120 mA, and the concentration of ozone is 1000-1500 ppm.
In the invention, the reaction temperature is 130-150 ℃, and the reaction time is 5-20 min; preferably, the reaction temperature is 135-145 ℃, and the reaction time is 10-15 min; further preferably, the reaction temperature is 140 ℃ and the reaction time is 12 min.
The reaction mechanism of the invention for purifying the flue gas is as follows:
the conductive catalytic membrane coupled with the ozone process can completely oxidize the toluene to generate CO2And H2And O. Taking manganese salt, platinum salt and cobalt salt as active components as examples, the conductive catalytic film can realize higher toluene conversion rate at lower reaction temperature. The addition of ozone can induce the formation of active oxygen species on the catalyst surface, lowering the temperature required for oxidation of toluene, thereby improving energy efficiency. Compared with the single catalyst for degrading the toluene, the presence of the ozone can greatly improve the oxidation activity of the toluene, so that the toluene degradation rate is higher. In addition, the overall catalytic activity of VOCs can also be enhanced by the combination of Transition Metal Oxides (TMO) and noble metals. Meanwhile, the degradation efficiency of the toluene can be improved by adding manganese salt and noble metal Pt, Pt atoms are increased in a dispersion mode due to the existence of Mn, the electron occupancy rate of a Mn 3d rail is increased due to the interaction of the Pt atoms and the Mn, the decomposition of ozone is facilitated, and the toluene destruction is facilitated. Other pollutants SO in flue gas2NOx and Hg0The reaction with ozone proceeds as follows:
O3+SO2→SO3+O2
O3+NO→NO2+O2
NO+O·→NO2
O3+NO2→NO3+O2
O3+NO2→NO+2O2
O3+O·→2O2
Hg+O3→HgO+O2
Hg+O·→HgO
the technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing a conductive catalytic film:
will contain MnO2And Mn2O3The mixed solution is mixed with 20 percent of carbon nano tube dispersion liquid, the volume ratio of the mixed solution to the carbon nano tube dispersion liquid is 1: 1, and a solid mixture is obtained after the mixed solution is vacuumized;
drying the solid mixture at 60 ℃ for 10h, grinding to obtain solid powder, uniformly mixing the solid powder with N-methyl pyrrolidone (the input mass-volume ratio is 2 g: 10mL), and coating the mixture on a simulated electric field substrate, wherein the thickness of the conductive catalytic film is 200 mu m.
Conducting catalytic membrane coupling ozone purification flue gas:
electrifying the simulated electric field substrate, wherein the current is 100mA, the power is 300W, the ozone output concentration is 500ppm, simultaneously introducing 500ppm of toluene gas, and recording the degradation effect of the catalyst on the toluene in the flue gas when the catalyst reaches a stable catalysis stage (5min) at the temperature of 130 ℃, wherein the results are shown in the following table 1:
TABLE 1
Volume ratio of the mixed solution
Effect of toluene degradation
(1wt％)MnO2∶(1wt％)Mn2O3＝2∶1
78％
(5wt％)MnO2∶(5wt％)Mn2O3＝2∶1
84％
(10wt％)MnO2∶(10wt％)Mn2O3＝2∶1
88％
(15wt％)MnO2∶(15wt％)Mn2O3＝2∶1
85％
(20wt％)MnO2∶(20wt％)Mn2O3＝2∶1
84％
Purifying the flue gas according to the conditions, and detecting to obtain: the toluene degradation efficiency reaches 78-88%.
Example 2
Preparing a conductive catalytic film:
will contain PtCl2And PtCl4The mixed solution is mixed with 30 percent of carbon nano tube dispersion liquid, the volume ratio of the mixed solution to the carbon nano tube dispersion liquid is 2: 1, and a solid mixture is obtained after the mixed solution is vacuumized;
and drying the solid mixture at 70 ℃ for 12h, grinding to obtain solid powder, uniformly mixing the solid powder with azomethyl pyrrolidone (the input mass-volume ratio is 3 g: 10mL), and coating the mixture on a simulated electric field substrate, wherein the thickness of the conductive catalytic film is 150 micrometers.
Conducting catalytic membrane coupling ozone purification flue gas:
electrifying the simulated electric field substrate, wherein the current is 200mA, the power is 500W, the ozone output concentration is 1000ppm, simultaneously introducing 500ppm of toluene gas, and recording the degradation effect of the catalyst on the toluene in the flue gas when the catalyst reaches a stable catalysis stage (10min) at the temperature of 140 ℃, wherein the results are shown in the following table 2:
TABLE 2
Condition
Effect of toluene degradation
(1wt％)PtCl2∶(1wt％)PtCl4＝1∶1
80％
(5wt％)PtCl2∶(5wt％)PtCl4＝1∶1
88％
(10wt％)PtCl2∶(10wt％)PtCl4＝1∶1
93％
(15wt％)PtCl2∶(15wt％)PtCl4＝1∶1
89％
(20wt％)PtCl2∶(20wt％)PtCl4＝1∶1
88％
Purifying the flue gas according to the conditions, and detecting to obtain: the degradation efficiency of toluene reaches 80-93%.
Example 3
Preparing a conductive catalytic film:
will containPtCl2And Mn2O3The mixed solution is mixed with 15% of carbon nano tube dispersion liquid, the volume ratio of the mixed solution to the carbon nano tube dispersion liquid is 1: 1, and a solid mixture is obtained after the mixed solution is vacuumized;
drying the solid mixture at 65 ℃ for 15h, grinding to obtain solid powder, uniformly mixing the solid powder with N-methyl pyrrolidone (the input mass-volume ratio is 2 g: 10mL), and coating the mixture on a simulated electric field substrate, wherein the thickness of the conductive catalytic film is 220 mu m.
Conducting catalytic membrane coupling ozone purification flue gas:
electrifying the simulated electric field substrate, wherein the current is 150mA, the power is 600W, the ozone output concentration is 1500ppm, simultaneously introducing 1000ppm of toluene gas, and recording the degradation effect of the catalyst on the toluene in the flue gas when the catalyst reaches a stable catalysis stage (8min) at the temperature of 142 ℃, wherein the results are shown in the following table 3:
TABLE 3
Volume ratio of the mixed solution
Effect of toluene degradation
(5wt％)Pt∶(5wt％)Mn＝1∶1
90％
(5wt％)Pt∶(10wt％)Mn＝1∶1
93％
(10wt％)Pt∶(5wt％)Mn＝1∶1
98％
(10wt％)Pt∶(10wt％)Mn＝1∶1
95％
Purifying the flue gas according to the conditions, and detecting to obtain: the toluene degradation efficiency reaches 90-98%.
Example 4
Preparing a conductive catalytic film:
will contain MnO2And PtCl2The mixed solution is mixed with 10% of carbon nano tube dispersion liquid, the volume ratio of the mixed solution to the carbon nano tube dispersion liquid is 1: 1, and a solid mixture is obtained after the mixed solution is vacuumized;
and drying the solid mixture at 70 ℃ for 10h, grinding to obtain solid powder, uniformly mixing the solid powder with azomethyl pyrrolidone (the input mass-volume ratio is 3 g: 10mL), and coating the mixture on a simulated electric field substrate, wherein the thickness of the conductive catalytic film is 240 mu m.
Conducting catalytic membrane coupling ozone purification flue gas:
electrifying the simulated electric field substrate, wherein the current is 200mA, the power is 300W, the ozone output concentration is 500ppm, and simultaneously introducing 300mg/m3At 150 ℃, when the catalyst reaches the stable catalysis stage (5min), the degradation effect of the catalyst on NOx in the flue gas is recorded, and the results are shown in the following table 4:
TABLE 4
Volume ratio of the mixed solution
NOx removal Effect
(5wt％)MnO2
80％
(10wt％)MnO2
85％
(5wt％)PtCl2
87％
(10wt％)PtCl2
89％
(5wt％)MnO2∶(5wt％)PtCl2＝1∶1
95％
Purifying the flue gas according to the conditions, and detecting to obtain: the NOx removal efficiency reaches 80-95%.
Example 5
Preparing a conductive catalytic film:
will contain MnO2And PtCl2The mixed solution is mixed with 30 percent of carbon nano tube dispersion liquid, the volume ratio of the mixed solution to the carbon nano tube dispersion liquid is 2: 1, and a solid mixture is obtained after the mixed solution is vacuumized;
the solid mixture is dried for 15h at 65 ℃, solid powder is obtained after grinding, the solid powder and nitrogen methyl pyrrolidone (the input mass-volume ratio is 5 g: 10mL) are uniformly mixed and coated on a simulated electric field substrate, and the thickness of the conductive catalytic membrane is 300 mu m.
Conducting catalytic membrane coupling ozone purification flue gas:
electrifying the simulated electric field substrate, wherein the current is 150mA, the power is 300W, the ozone output concentration is 500ppm, and simultaneously introducing 2000mg/m3SO of (A)2Recording SO in the flue gas by the catalyst when the catalyst reaches a stable catalysis stage (10min) at 130 DEG C2The results are shown in table 5 below:
TABLE 5
Volume ratio of the mixed solution
SO2Removal effect
(5wt％)MnO2
97％
(10wt％)MnO2
99％
(5wt％)PtCl2
99％
(10wt％)PtCl2
100％
(5wt％)MnO2∶(5wt％)PtCl2＝1∶1
100％
Purifying the flue gas according to the conditions, and detecting to obtain: SO (SO)2The removal efficiency reaches 97-100%.
Example 6
Preparing a conductive catalytic film:
will contain MnO2And PtCl2The mixed solution is mixed with 20 percent of carbon nano tube dispersion liquid, the volume ratio of the mixed solution to the carbon nano tube dispersion liquid is 1: 1, and a solid mixture is obtained after the mixed solution is vacuumized;
and drying the solid mixture at 70 ℃ for 15h, grinding to obtain solid powder, uniformly mixing the solid powder with azomethyl pyrrolidone (the input mass-volume ratio is 2 g: 10mL), and coating the mixture on a simulated electric field substrate, wherein the thickness of the conductive catalytic film is 280 microns.
Conducting catalytic membrane coupling ozone purification flue gas:
electrifying the simulated electric field substrate, wherein the current is 200mA, the power is 300W, the ozone output concentration is 500ppm, and simultaneously introducing 1000mg/m3Hg of0At 150 ℃, when the catalyst reaches the stable catalysis stage (10min), recording Hg in the flue gas by the catalyst0The results are shown in table 6 below:
TABLE 6
Volume ratio of the mixed solution
Hg0Removal effect
(5wt％)MnO2
80％
(10wt％)MnO2
86％
(5wt％)PtCl2
89％
(10wt％)PtCl2
90％
(5wt％)MnO2∶(5wt％)PtCl2＝1∶1
92％
Purifying the flue gas according to the conditions, and detecting to obtain: hg is a mercury vapor0The removal efficiency reaches 80-92%.
Example 7
Preparing a conductive catalytic film:
will contain CoO and Co3O4The mixed solution is mixed with 20 percent of carbon nano tube dispersion liquid, the volume ratio of the mixed solution to the carbon nano tube dispersion liquid is 1: 1, and a solid mixture is obtained after the mixed solution is vacuumized;
and drying the solid mixture at 60 ℃ for 15h, grinding to obtain solid powder, uniformly mixing the solid powder with N-methyl pyrrolidone (the input mass-volume ratio is 4 g: 10mL), and coating the mixture on a simulated electric field substrate, wherein the thickness of the conductive catalytic film is 240 mu m.
Conducting catalytic membrane coupling ozone purification flue gas:
electrifying the simulated electric field substrate, wherein the current is 100mA, the power is 500w, the ozone output concentration is 1000ppm, and simultaneously introducing 500mg/m3NOx of 2000mg/m3SO of (A)2And 1000. mu.g/m3Hg of0The effect of the catalyst on the degradation of pollutants in the flue gas was recorded when the catalyst reached a stable catalytic phase (8min) at 150 ℃ and the results are given in table 7 below:
TABLE 7
The flue gas is purified according to the conditions, and the detection result shows that the conductive catalytic membrane still has good catalytic effect on the cooperative control of multiple pollutants.
Example 8
Preparing a conductive catalytic film:
will contain MnO2And PtCl2The mixed solution is mixed with 20 percent of carbon nano tube dispersion liquid, the volume ratio of the mixed solution to the carbon nano tube dispersion liquid is 1: 1, and a solid mixture is obtained after the mixed solution is vacuumized;
and drying the solid mixture at 70 ℃ for 15h, grinding to obtain solid powder, uniformly mixing the solid powder with N-methyl pyrrolidone (the input mass-volume ratio is 2 g: 10mL), and coating the mixture on a simulated electric field substrate, wherein the thickness of the conductive catalytic film is 250 micrometers.
Conducting catalytic membrane coupling ozone purification flue gas:
electrifying the simulated electric field substrate, wherein the current is 200mA, the power is 800W, the ozone output concentration is 2000ppm, and simultaneously introducing 500mg/m3NOx of 2000mg/m3SO of (A)2And 1000. mu.g/m3Hg of0At 150 ℃, when the catalyst reaches the stable catalysis stage (8min), recording Hg in the flue gas by the catalyst0The results are shown in table 8 below:
TABLE 8
The flue gas is purified according to the conditions, and the detection result shows that the conductive catalytic membrane still has good catalytic effect on the cooperative control of multiple pollutants.
Comparative example
Electrifying the simulated electric field substrate without the attached conductive catalytic film, wherein the power is 500W, the ozone output concentration is respectively 300ppm, 500ppm, 1000ppm and 2000ppm, simultaneously introducing 500ppm of toluene, and recording Hg in flue gas by the catalyst when the catalyst reaches a stable catalysis stage (8min) at the temperature of 150 DEG C0The results are shown in table 9 below:
TABLE 9
Condition
Effect of toluene degradation
O3-300ppm
60％
O3-500ppm
65％
O3-1000ppm
70％
O3-2000ppm
69％
Purifying the flue gas according to the conditions, and detecting to obtain: the toluene degradation efficiency can only reach 60-70%.
The embodiment of the invention provides a conductive catalytic membrane, a preparation method thereof and a method for purifying flue gas by coupling ozone with the conductive catalytic membrane. Meanwhile, the ozone is used for treating NOx and SO in the flue gas2And Hg0The pollutants also have a certain degradation effect, so that the deep purification of the multiple pollutants in the flue gas can be realized, and a new idea is provided for the gas-phase pollutant degradation technology in the future.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.