CN112044175A - Composite catalytic filter material for degrading dioxin at low temperature and preparation method thereof - Google Patents
Composite catalytic filter material for degrading dioxin at low temperature and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite catalytic filter material for degrading dioxin at low temperature and a preparation method thereof, belonging to the technical field of waste incineration tail gas treatmentx‑MnCeOxA composite catalytic filter material of a three-way catalyst. The invention has the advantages that: (1) has excellent low-temperature activity on the catalytic degradation of dioxinAnd selectivity; (2) an active component V with high activity and excellent chlorine poisoning resistance is added into the filter material, and the active component V is effectively oxidized by low-temperature plasma, so that the catalytic activity and the chlorine poisoning resistance are improved; (3) the catalyst is uniformly and firmly loaded on the surface of the filter material by an in-situ precipitation method, the preparation conditions are mild, the original performance and stability of the filter material are maintained, and the service life is long.
Description
Technical Field
The invention belongs to the technical field of waste incineration tail gas treatment, and particularly relates to a composite catalytic filter material for degrading dioxin at a low temperature and a preparation method thereof.
Background
In recent years, the domestic waste incineration industry in China is greatly developed, the waste incineration disposal rate is continuously increased, the scale of the waste incineration power plants built and proposed to be built is continuously enlarged, the problem of waste enclosure is solved, the brought 'proximity effect' is not ignored, and particularly, trace dioxin pollutants discharged from incineration smoke pose serious threats to the environment and human health, so that the national high attention is paid. The national dioxin emission standard is regulated to be 0.1ngTEQ/Nm in 20143(GB 18485-2014)。
At present, the garbage incineration plants mainly adopt a method of combining activated carbon injection and bag-type dust removal to implement tail end control of dioxin emission, and a small amount of incineration plants also adopt an SCR system to assist in controlling the dioxin emission. However, the activated carbon adsorption technology only realizes the transfer of dioxin from gas-phase flue gas to solid-phase fly ash, and the treatment burden of the fly ash is increased. The catalytic degradation technology can thoroughly mineralize organic pollutants such as dioxin and the like to generate CO2、H2Inorganic small molecules such as O and HCl, and the like, do not cause secondary pollution, and are considered to be a more potential dioxin end control technology. Due to the characteristics of high content of acid gas components, strong bonding property and the like in waste incineration flue gas, a catalytic reaction system tends to be arranged after cloth bag dust removal, such as an SCR system. However, the smoke temperature after cloth bag dust removal is only about 150 ℃ and 170 ℃, and researches show that the activity temperature of the vanadium-based catalyst with better activity for degrading dioxin is more than 200 ℃. If a reheater is added before the catalytic reaction system, the equipment cost and the operation cost are greatly increasedThe method is as follows. Therefore, a catalyst capable of efficiently degrading dioxin at low temperature is developed and applied to a filter material in a bag-type dust collector, so that the cost can be greatly reduced while the environmental protection index is reached.
The dedusting filter materials such as the polyphenylene sulfide filter material, the polytetrafluoroethylene filter material, the polyimide filter material and the like have the performances of high temperature resistance, acid-base resistance, hydrolysis resistance and high flame retardance, and are the preferred filter bag materials of waste incineration plants. Due to these properties, it is difficult for the filter media to effectively bind the catalyst particles, and the filter bags are often impacted by the airflow during actual operation in the flue gas treatment system. In the common preparation method of the composite catalytic filter material, the ultrasonic impregnation method only enables the catalyst to be attached to the surface of the filter material through physical adsorption force, the bonding strength is low, and the catalyst is easy to fall off; the methods such as a membrane cracking method, a coating method and the like ensure high-strength combination of the catalyst and the filter material, but have the problem that active sites of the catalyst are covered, so that the utilization efficiency of the catalyst is greatly reduced.
Chinese patent CN103212245A discloses a composition containing MnO2The method is to make acidic potassium permanganate and pyrrole monomer produce oxidation-reduction reaction on the surface of filter material, and the potassium permanganate is reduced into MnO2The catalyst is dispersed in the polypyrrole molecule. The catalytic filter material is prepared by an in-situ oxidation method, so that the bonding strength of the catalyst and the filter material is improved, and the PM2.5 and NO are simultaneously removedxThe function of (c). The method has the defects that the loaded low-temperature Mn-based catalyst is easy to be poisoned and inactivated by chlorine, and incineration flue gas contains HCl acid gas and chlorinated organic pollutants with certain concentration, so that research and development of a catalytic filter material with excellent chlorine poisoning resistance are necessary.
Disclosure of Invention
The invention aims to provide a composite catalytic filter material for degrading dioxin at low temperature and a preparation method thereof. The composite catalytic filter material with excellent poisoning resistance is obtained by effectively oxidizing V active components by low-temperature plasma.
In order to achieve the purpose, the invention provides the following technical scheme:
high-temperature resistant filter material is taken as a catalyst carrier, and the loaded VO is prepared through the steps of filter material activation, in-situ precipitation, V active component impregnation and low-temperature plasma oxidationx-MnCeOxA composite catalytic filter material of a three-way catalyst.
Preferably, the high-temperature-resistant filter material is one of a polyphenylene sulfide needled felt filter material, a polytetrafluoroethylene needled felt filter material and a polyimide needled felt filter material.
Preferably, the high-temperature-resistant filter material is prepared by opening, compounding, carding, lapping, needling, heat setting, singeing and press polishing short fibers of the filter material.
Preferably, the specific steps are as follows:
(1) activation of a filter material: completely immersing the high-temperature-resistant filter material in 0.001-0.004mol/L sodium dodecyl sulfate solution, and performing ultrasonic activation for 1-2 h;
(2) in-situ precipitation: a) impregnation of Ce active: adding cerium chloride heptahydrate into the sodium dodecyl sulfate solution in the step (1), and stirring at room temperature for 12-16 h;
b).KMnO4and (3) oxidation: dropwise adding 0.08-0.17mol/L potassium permanganate solution into the solution obtained in the step a), stirring and reacting in a water bath at 80 ℃ for 4-6h, taking out the filter material after the reaction is finished, cleaning the filter material with deionized water and absolute ethyl alcohol, and drying the filter material at 105 ℃ for 12h to obtain the MnCeO loaded carrierxA catalytic filter material of the catalyst;
(3) impregnating V active component: preparing a mixed solution of ammonium metavanadate and oxalic acid dihydrate according to a molar ratio of 1:2, soaking the catalytic filter material obtained in the step b) in the mixed solution at normal temperature, standing for 10-12h, and then drying in an oven at 105 ℃ for 12 h;
(4) low-temperature plasma oxidation: placing the filter material obtained in the step (3) in a dielectric barrier discharge plasma reactor, introducing a reaction atmosphere, turning on a power supply, setting an effective voltage at 9-15 kV, a discharge frequency of 7-12 kHz and a continuous discharge time of 30-60min to obtain a load VOx-MnCeOxA composite catalytic filter material of a three-way catalyst.
Preferably, in the step (4), the reaction atmosphere is O2And N2Mixed gas of (2), or O2And Ar.
Preferably, in the reaction atmosphere, O2The volume fraction is 10-30%.
Composite catalytic filter material prepared by using preparation method of composite catalytic filter material for degrading dioxin at low temperature, wherein VO in composite catalytic filter materialx-MnCeOxThe molar ratio of the components of the ternary catalyst is Mn to Ce to V is 1: 0.1-0.5: 0.06-0.2.
Preferably, VO of the composite catalytic filter materialx-MnCeOxThe load of the three-way catalyst is 80-160g/m2。
Compared with the prior art, the invention has the beneficial effects that:
(1) has excellent low-temperature activity and selectivity on the catalytic degradation of dioxin.
(2) The filter material is added with an active component V with high activity and excellent chlorine poisoning resistance, and the active component V is effectively oxidized by low-temperature plasma, so that the catalytic activity and the chlorine poisoning resistance are improved.
(3) The catalyst is uniformly and firmly loaded on the surface of the filter material by an in-situ precipitation method, the preparation conditions are mild, the original performance and stability of the filter material are maintained, and the service life is long.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Fig. 2 is an SEM image of the composite catalytic filter prepared in example 2.
FIG. 3 is an XPS plot of a composite catalytic filter prepared in example 2.
FIG. 4 is a diagram of a catalytic degradation experimental apparatus in the present invention.
In the figure: 1-dioxin generating source system, 2-catalytic degradation reaction system and 3-tail gas collecting system.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention takes a high-temperature resistant filter material as a catalyst carrier, and prepares the loaded VO through the steps of filter material activation, in-situ precipitation, V active component impregnation and low-temperature plasma oxidationx-MnCeOxA composite catalytic filter material of a three-way catalyst.
The high-temperature-resistant filter material is one of a polyphenylene sulfide needled felt filter material, a polytetrafluoroethylene needled felt filter material and a polyimide needled felt filter material, and is prepared by opening, compounding, carding, lapping, needling, heat setting, singeing and press polishing short fibers of the filter material. The high temperature resistant filter materials in the following examples all used polyphenylene sulfide needle felt filter materials.
Example 1
As shown in fig. 1, the preparation method of the present invention is as follows:
(1) activation of a filter material: firstly, cutting a polyphenylene sulfide needle felt filter material wafer with the diameter of 20mm, cleaning the polyphenylene sulfide needle felt filter material wafer for three times by using deionized water, drying the polyphenylene sulfide needle felt filter material wafer in an oven at 105 ℃ for 6 hours, and weighing the polyphenylene sulfide needle felt filter material wafer; 0.0577g of sodium dodecyl sulfate powder is weighed, deionized water is used as a solvent to prepare 200mL of 0.001mol/L sodium dodecyl sulfate solution, and the dried polyphenylene sulfide wafer is immersed in the solution and activated by ultrasonic for 1 h.
(2) In-situ precipitation: a) impregnation of Ce active: 0.3251g of cerium chloride heptahydrate is weighed and added into the solution obtained in the step (1), and stirred for 12 hours at normal temperature.
b).KMnO4And (3) oxidation: weighing 1.3790g of potassium permanganate powder, dissolving in 100mL of deionized water to prepare 0.08mol/L potassium permanganate solution, dropwise adding 100mL of 0.08mol/L potassium permanganate solution into the solution obtained in the step a), stirring in a water bath to react for 4 hours, taking out a filter material, respectively washing with deionized water and absolute ethyl alcohol for three times, drying in an oven at 105 ℃ for 12 hours to obtain the carrier loaded with MnCeOxThe catalyst is a catalytic filter material.
(3) Impregnating V active component: 0.0612g of ammonium metavanadate and 0.1320g of oxalic acid dihydrate are weighed and dissolved in 10mL of deionized water, and then the solution is put into the catalytic filter material obtained in the step b), and the solution is kept stand and dipped for 10 hours and dried for 12 hours at 105 ℃.
(4) Low-temperature plasma oxidation: placing the filter material obtained in the step (3) in a dielectric barrier discharge plasma reactor, and introducing O with the volume fraction of oxygen of 10%2And N2Or O with an oxygen volume fraction of 10%2And starting a plasma power supply by using the mixed gas of Ar, setting the effective voltage at 9kV, setting the discharge frequency to 7KHz and setting the continuous discharge time to 30 min. To prepare loaded VOx-MnCeOxA composite catalytic filter material of a three-way catalyst, wherein VOx-MnCeOxThe molar ratio of the components of the three-way catalyst is Mn: Ce: V ═ 1:0.1: 0.06. VO of the composite catalytic filter material is obtained by weighing calculationx-MnCeOxThe load capacity of the three-way catalyst is 80g/m2。
Example 2
(1) Activation of a filter material: firstly, cutting a polyphenylene sulfide needle felt filter material wafer with the diameter of 20mm, cleaning the polyphenylene sulfide needle felt filter material wafer for three times by using deionized water, drying the polyphenylene sulfide needle felt filter material wafer in an oven at 105 ℃ for 6 hours, and weighing the polyphenylene sulfide needle felt filter material wafer; 0.2307g of sodium dodecyl sulfate powder is weighed, deionized water is used as a solvent to prepare 200mL of 0.004mol/L sodium dodecyl sulfate solution, and the dried polyphenylene sulfide wafer is immersed in the solution and activated by ultrasonic for 2 hours.
(2) In-situ precipitation: a) the method comprises the following steps Impregnation of Ce active component: 0.6502g of cerium chloride heptahydrate are weighed into the solution obtained in the step (1), and stirred for 16h at normal temperature.
b):KMnO4And (3) oxidation: weighing 2.7580g of potassium permanganate powder, dissolving the potassium permanganate powder in 100mL of deionized water to prepare 0.17mol/L potassium permanganate solution, dropwise adding 100mL of 0.17mol/L potassium permanganate solution into the solution obtained in the step a), stirring in a water bath to react for 6 hours, taking out a filter material, respectively washing the filter material with deionized water and absolute ethyl alcohol for three times, and drying the filter material in an oven at 105 ℃ for 12 hours to obtain the carrier loaded with MnCeOxThe catalyst is a catalytic filter material.
(3) Impregnating V active component: 0.1225g of ammonium metavanadate and 0.2640g of oxalic acid dihydrate are weighed and dissolved in 10mL of deionized water, and the solution is placed into the catalytic filter material obtained in the step b), and the catalytic filter material is kept stand, soaked for 12 hours and dried for 12 hours at 105 ℃.
(4) Low-temperature plasma oxidation: placing the filter material obtained in the step (3) in a dielectric barrier discharge plasma reactor, and introducing O with the oxygen volume fraction of 30%2And N2Or oxygen gas of 30% by volume2And turning on a plasma power supply by using the mixed gas of Ar, setting the effective voltage at 15kV, the discharge frequency at 12kHz and the continuous discharge time at 60 min. To prepare loaded VOx-MnCeOxA composite catalytic filter material of a three-way catalyst, wherein VOx-MnCeOxThe molar ratio of the components of the three-way catalyst is Mn to Ce to V which is 1:0.5: 0.2. VO of the composite catalytic filter material is obtained by weighing calculationx-MnCeOxThe loading of the three-way catalyst is 160g/m2。
FIG. 2 is an SEM image of the composite catalytic filter of example 2, showing that the filter is loaded with white particles; taking a small amount of ternary catalyst powder on the surface of the composite catalytic filter material sample prepared in the example 2, carrying out XPS test, and analyzing V2 p3/2The energy spectrum of (1). As shown in fig. 3, catalyst surface V generally exists in two valence states: v5+、V4+In which V is5+The highest content, 68%, indicates that part of the low-valence vanadium is oxidized into high-valence vanadium by low-temperature plasma treatment.
The catalytic degradation performance of the composite catalytic filter material is evaluated in a self-made catalytic degradation experimental device. As shown in fig. 4, the catalytic degradation experimental apparatus mainly includes a dioxin generating source system 1, a catalytic degradation reaction system 2, and a tail gas collecting system 3. The dioxin generating source system comprises a micro-injection pump CMA400(CMA Microphysiology AB, USA), a micro-injector (0.5mL), an atomizer (Meinhard USA), an airflow preheating section, a mass flowmeter and the like. In the experiment, a dioxin solution (also called as dioxin stock solution) in a microinjector is injected into an atomizer at a constant speed (1 mu L/min) by a microinjection pump, and carrier gas (N)2:O2About 9:1) carrying stock solution, fully atomizing by an atomizer at a carrier gas flow rate of 1L/min, then entering a preheating section to fully volatilize and remove the solvent, and finally discharging at the preheating sectionThe mouth continuously produces a steady stream of dioxin. The preheating section of the quartz tube of the dioxin generation source device has a certain adsorption effect on dioxin, so that the generation source device must be transported by air for a period of time (4-12 hours) before a catalytic degradation experiment is started, and the quartz tube wall achieves dynamic balance of dioxin adsorption. And adsorbing and collecting dioxin in the tail gas through XAD-2 resin and a toluene gas washing bottle, mixing the dioxin and the tail gas, and preprocessing the mixture by adopting a U.S. EPA 1613 method, wherein 13C is added in the preprocessing process for internal standard. The dioxin samples adsorbed on the catalytic filter material were individually pretreated using the us EPA 1613 method to calculate the degradation efficiency. The sample is concentrated to a sample bottle after a series of pretreatment processes such as soxhlet, acid washing, column passing, nitrogen blowing and the like, and finally the dioxin content in the sample is detected by adopting JMS-800D high-resolution chromatography and high-resolution mass spectrometry (HRGC/HRMS) of Japanese JEOL company.
The composite catalytic filter material prepared in example 2 was used in a home-made catalytic degradation experimental apparatus for testing. The reaction temperature is respectively set to be 140 ℃, 160 ℃, 180 ℃, 200 ℃, the gas flow is 500mL/min, O2Volume fraction of 11%, N2As balance gas, the generation concentration of dioxin is 5.5ng/Nm3. The test results are shown in table 1.
Performance indexes are as follows: removing efficiency:
degradation efficiency:
in the formula: cinIs the concentration of dioxin at the inlet, CoutIs the concentration of dioxin at the outlet, CcatalystIs dioxin adsorbed on the catalytic filter material in unit time.
Table 1: the catalytic performance of the composite catalytic filter prepared in example 2 on dioxin.
Temperature (. degree.C.) | Removal efficiency (%) | Degradation efficiency (%) |
140 | 90.50 | 26.50 |
160 | 94.77 | 59.47 |
180 | 94.04 | 67.47 |
200 | 94.70 | 78.01 |
From the test results, it can be seen that the load VO prepared in example 2x-MnCeOxThe composite catalytic filter material of the three-way catalyst has the dioxin removal efficiency of over 90 percent at the temperature of 140-200 ℃, and has excellent dioxin low-temperature catalytic activity.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (8)
1. A preparation method of a composite catalytic filter material for degrading dioxin at low temperature is characterized by comprising the following steps: high-temperature resistant filter material is taken as a catalyst carrier, and the loaded VO is prepared through the steps of filter material activation, in-situ precipitation, V active component impregnation and low-temperature plasma oxidationx-MnCeOxA composite catalytic filter material of a three-way catalyst.
2. The preparation method of the composite catalytic filter material for degrading dioxin at low temperature according to claim 1, is characterized in that: the high-temperature resistant filter material is one of a polyphenylene sulfide needled felt filter material, a polytetrafluoroethylene needled felt filter material and a polyimide needled felt filter material.
3. The preparation method of the composite catalytic filter material for degrading dioxin at low temperature according to claim 1, is characterized in that: the high-temperature-resistant filter material is prepared by opening, compounding, carding, lapping, needling, heat setting and singeing and press polishing short fibers of the filter material.
4. The preparation method of the composite catalytic filter material for degrading dioxin at low temperature according to claim 1 is characterized by comprising the following specific steps:
(1) activation of a filter material: completely immersing the high-temperature-resistant filter material in 0.001-0.004mol/L sodium dodecyl sulfate solution, and performing ultrasonic activation for 1-2 h;
(2) in-situ precipitation: a) impregnation of Ce active: adding cerium chloride heptahydrate into the sodium dodecyl sulfate solution in the step (1), and stirring at room temperature for 12-16 h;
b).KMnO4and (3) oxidation: dropwise adding 0.08-0.17mol/L potassium permanganate solution into the solution obtained in the step a), stirring and reacting in water bath at 80 ℃ for 4-6h, and reactingTaking out the filter material after finishing reaction, cleaning the filter material by using deionized water and absolute ethyl alcohol, and drying the filter material at 105 ℃ for 12 hours to obtain the MnCeO loaded materialxA catalytic filter material of the catalyst;
(3) impregnating V active component: preparing a mixed solution of ammonium metavanadate and oxalic acid dihydrate according to a molar ratio of 1:2, soaking the catalytic filter material obtained in the step b) into the mixed solution at normal temperature, standing for 10-12h, and then drying at 105 ℃ for 12 h;
(4) low-temperature plasma oxidation: placing the filter material obtained in the step (3) in a dielectric barrier discharge plasma reactor, introducing a reaction atmosphere, turning on a power supply, setting an effective voltage at 9-15 kV, a discharge frequency of 7-12 kHz and a continuous discharge time of 30-60min to obtain a load VOx-MnCeOxA composite catalytic filter material of a three-way catalyst.
5. The preparation method of the composite catalytic filter material for degrading dioxin at low temperature according to claim 4, is characterized in that: in the step (4), the reaction atmosphere is O2And N2Mixed gas of (2), or O2And Ar.
6. The preparation method of the composite catalytic filter material for degrading dioxin at low temperature according to claim 5, is characterized in that: in the reaction atmosphere, O2The volume fraction is 10-30%.
7. A composite catalytic filter material prepared by the preparation method of the composite catalytic filter material for degrading dioxin at low temperature according to any one of claims 1 to 6, which is characterized in that: in the composite catalytic filter material, VOx-MnCeOxThe molar ratio of the components of the ternary catalyst is Mn to Ce to V is 1: 0.1-0.5: 0.06-0.2.
8. The composite catalytic filter material for degrading dioxin at low temperature according to claim 7, characterized in that: VO of the composite catalytic filter materialx-MnCeOxThe load of the three-way catalyst is 80-160g/m2。
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CN114749016A (en) * | 2022-03-04 | 2022-07-15 | 安徽元琛环保科技股份有限公司 | Preparation method of dust removal and VOCS removal collaborative photocatalytic filter material and prepared filter material |
CN115445324A (en) * | 2022-08-19 | 2022-12-09 | 河北钢铁集团矿业有限公司 | High-performance filter cloth for bag-type dust remover and preparation method thereof |
CN116251599A (en) * | 2022-09-09 | 2023-06-13 | 南京信息工程大学 | Dioxin removal catalyst and preparation method thereof |
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