CN112495378B - Supported catalyst suitable for low-temperature plasma concerted catalysis process and preparation and application thereof - Google Patents
Supported catalyst suitable for low-temperature plasma concerted catalysis process and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 230000002153 concerted effect Effects 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 36
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000004744 fabric Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 5
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- 239000007789 gas Substances 0.000 claims description 38
- 229910003144 α-MnO2 Inorganic materials 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 20
- 239000002082 metal nanoparticle Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 238000005406 washing Methods 0.000 claims description 7
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- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
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- 239000000203 mixture Substances 0.000 abstract description 10
- 239000002105 nanoparticle Substances 0.000 description 27
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
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- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J35/60—
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a supported catalyst suitable for a low-temperature plasma concerted catalysis process, a preparation method thereof and application of the supported catalyst in low-temperature plasma concerted catalysis treatment of malodorous gas. The preparation method comprises the following steps: alpha-MnO modified with noble metal2Adding the mixture into a mixed solution of aluminum sol and absolute ethyl alcohol, uniformly mixing to obtain a suspension, uniformly coating the suspension on the surface of a porous carbon cloth carrier, and drying at 60-90 ℃ to obtain a supported catalyst; the noble metal is Au and/or Pt; alpha-MnO modified by noble metal2The ratio of the aluminum sol to the absolute ethyl alcohol is 0.5-2.5g, 30-100mL and 20-250 mL; the preparation method of the aluminum sol comprises the following steps: uniformly mixing pseudo-boehmite and deionized water according to the mass ratio of 1:10-50 to obtain a mixed solution, dropwise adding 0.2-2mol/L nitric acid solution into the mixed solution at the temperature of 60-80 ℃ under the condition of continuous stirring until the mixed solution becomes transparent colloid and the pH value is 2-5, continuously stirring at the temperature of 60-80 ℃ for 30-100min, and cooling to obtain the alumina sol.
Description
Technical Field
The invention relates to the field of supported catalysts, in particular to a supported catalyst suitable for a low-temperature plasma concerted catalysis process and preparation and application thereof.
Background
With the improvement of living standard of people, malodorous gas has become a serious social and environmental problem. Malodorous gases have different degrees of damage to the respiratory, circulatory, digestive, endocrine, and nervous systems of humans. The long-term life in the foul odor polluted environment can cause diseases such as anorexia, insomnia, memory decline, vexation and noise, etc.
Nitrogen-containing odors are typical representatives of odors and are the main sources of odors in sewage treatment plants, farms, toilets, refuse transfer stations, landfill sites, and the like. In addition, the nitrogen-containing odor is closely related to the industries such as biological pharmacy, petrochemical industry, food processing and the like, and is the research focus in the field of air pollution control under the current new situation.
Representative nitrogen-containing odors are mainly ammonia, organic amines, acrylonitrile, fatty nitriles, and the like, and their emissions are generally characterized by low-concentration, unstructured emissions. The low-temperature plasma technology ionizes substances by using a local strong electric field to generate hydroxyl radicals and superoxide radicals to oxidize low-concentration gaseous pollutants; but also can directly act on pollutant molecules to generate electron transfer, generate micromolecules by breaking bonds of macromolecules, can controllably mineralize pollutants in various scenes, and has great application potential in the treatment of low-concentration gaseous pollutants.
The catalyst and the low-temperature plasma cooperate to promote the degradation of low-concentration pollutants, alpha-MnO2Due to the efficient utilization of ozone, good energy efficiency is achieved in the synergistic low-temperature plasma catalytic degradation of toluene.
The carriers with different physical and chemical properties can change the position of the catalyst in an electric field excited by the plasma reaction device, influence the combination efficiency of the catalyst and target pollutants and change the utilization efficiency of the catalyst on ozone and electrons. Target gas in an actual production environment often has the characteristics of large air quantity, strong vibration, multiple impurities, unstable working condition, high humidity and the like. The proper carrier and the loading mode are necessary conditions for long-acting stable degradation of methylamine by the catalyst, so that the proper carrier is searched, the proper loading technology is developed, and the method has important significance for catalytic degradation of malodorous gas by the catalyst in cooperation with the low-temperature plasma technology.
However, most of the available catalysts are catalyst bodies, and the process of compounding the catalyst bodies with the carrier is required before practical application. The problems of low recombination efficiency, change of the microstructure of the catalyst in the recombination process, influence of the complexing agent on the catalytic activity and the like exist in the recombination process, the production environment with complex conditions is difficult to deal with, and the increasingly strict atmospheric environment standard and requirement and the requirement of the production environment on the supported catalyst cannot be met. Therefore, a compounding method with high compounding efficiency, without changing the microstructure of the catalyst in the compounding process, and without affecting the catalytic activity by the compounding agent is needed.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a supported catalyst suitable for a low-temperature plasma concerted catalysis process, which is characterized in that alpha-MnO modified by noble metal nano-particles (Au and Pt)2The special alumina sol is used as an adhesive and is attached to a porous carbon cloth carrier to prepare a molded supported catalyst, so that the catalyst can be directly used in a production environment for treating malodorous gas.
A kind ofThe preparation method of the supported catalyst suitable for the low-temperature plasma concerted catalysis process comprises the following steps: alpha-MnO modified with noble metal2Adding the mixed solution of the alumina sol and the absolute ethyl alcohol, uniformly mixing to obtain a suspension, uniformly coating the suspension on the surface of a porous carbon cloth carrier, and drying at 60-90 ℃ to obtain the supported catalyst;
the noble metal is Au and/or Pt;
the noble metal modified alpha-MnO2The ratio of the aluminum sol to the absolute ethyl alcohol is 0.5-2.5g, 30-100mL and 20-250 mL;
the preparation method of the aluminum sol comprises the following steps: uniformly mixing pseudo-boehmite and deionized water according to the mass ratio of 1:10-50 to obtain a mixed solution, then dropwise adding 0.2-2mol/L nitric acid solution into the mixed solution at the temperature of 60-80 ℃ under the condition of continuous stirring until the mixed solution becomes transparent colloid and the pH value is 2-5, then continuously stirring at the temperature of 60-80 ℃ for 30-100min, and cooling to obtain the aluminum sol.
The invention provides a preparation method of a supported catalyst. Aiming at the problems of low loading efficiency, change of catalytic microstructure in the loading process, influence of an adhesive on catalytic activity and the like in the existing preparation process of a loaded catalyst, alpha-MnO with excellent catalytic activity is prepared by self2The catalytic performance of the catalyst is further improved by modifying with noble metal nano particles, proper carrier porous carbon cloth is selected to ensure that the catalyst is uniformly loaded, meanwhile, the catalyst is fully contacted with polluted gas to provide guarantee, and self-made special alumina sol is selected as an adhesive to realize the preparation of the supported catalyst which is suitable for direct use on the basis of not influencing the catalytic performance. The finally prepared supported catalyst can be directly used for treating nitrogen-containing odor by a low-temperature plasma concerted catalysis process, and higher catalysis efficiency and stability in a complex environment are ensured.
Au, Pt nano-particle energy and alpha-MnO2The synergistic effect is generated, the capability of the catalyst for decomposing ozone to generate active oxygen species is enhanced, the specific surface area of the catalyst is increased, the adsorption capability on polluted gas is improved, and the preparation process does not damage alpha-MnO2Of the nano-structure of (A), ensuring the basis thereofBasic catalytic performance.
The specially-made aluminum sol can change the firmness of the catalyst attached to the carrier on the premise of not influencing the activity of the catalyst, so that the catalyst has stronger environment adaptability and shows good continuous degradation performance in the process of dealing with the production environment with large air volume, high humidity and large vibration strength.
The porous carbon cloth is woven by active carbon, the material has strong gas adsorption performance, and the complex and multidimensional surface is very suitable for loading the catalyst. The porous carbon cloth is used as a carrier, so that the interception capability of the system to gas can be improved, the reaction time and times of the catalyst and gas molecules are prolonged, and a better gas degradation effect is achieved. Meanwhile, the aluminium sol is matched with the aluminium sol, so that the firmness degree of the active component attached to the surface of the fiber can be improved, and the aluminium sol is suitable for complex and changeable production environments.
The whole set of preparation process comprises the preparation of noble metal nano particles and alpha-MnO2Preparation of (2), nanoparticles and alpha-MnO2The preparation of the alumina sol, and the composition of the catalyst and the carrier porous carbon cloth. The prepared molded supported catalyst can be used for the low-temperature plasma to synergistically catalyze and degrade nitrogen-containing malodorous gases.
alpha-MnO modified by noble metal2Loaded on porous carbon cloth. Modified alpha-MnO2The catalyst is dissolved in a mixed solution of aluminum sol and absolute ethyl alcohol, and is stirred to obtain a suspension with adhesive capacity, and then the suspension is coated on the surface layer of the porous carbon cloth. The porous carbon cloth has a three-dimensional porous structure with a large specific surface area, and has excellent effects on gas adsorption and catalytic decomposition.
Preferably, the noble metal-modified α -MnO is2The preparation method comprises the following steps: dispersing noble metal nano particles in deionized water to obtain dispersion liquid A, and adding alpha-MnO2Dispersing in deionized water, performing ultrasonic treatment to obtain dispersion liquid B, mixing the dispersion liquid A and the dispersion liquid B uniformly, stirring at 60-100 deg.C for 2-6h,after the reaction is finished, carrying out solid-liquid separation, washing the obtained solid, and drying at 60-80 ℃ to obtain the alpha-MnO modified by the noble metal2。
Noble metal nanoparticles and alpha-MnO2During compounding, the mixture needs to be stirred vigorously at 60-100 ℃ for 2-6h, and is washed with deionized water and ethanol for several times after stirring. Modified alpha-MnO thus obtained2The nano structure of the nano-particles can not be changed in the modification process, and the noble metal nano-particles are in alpha-MnO2The nano-structure has better surface dispersibility and uniform adhesion.
More preferably, the concentration of the noble metal nanoparticles in the dispersion A is 5-20mg/100mL, and the concentration of the alpha-MnO in the dispersion B is 5-20mg/100mL2In a concentration of 0.1 to 5g/50mL, the noble metal nanoparticles and alpha-MnO2The mass ratio of (1) to (5-20) mg to (0.1-5) g.
Preferably, the α -MnO2The preparation method comprises the following steps: mixing potassium permanganate (KMnO)4) Fully dissolving in glacial acetic acid solution, transferring to a reaction kettle for solvothermal reaction at the temperature of 100-160 ℃ for 12-48h, washing a precipitate obtained after the reaction is finished, and drying at the temperature of 60-90 ℃ to obtain the alpha-MnO2。
Further preferably, the concentration of the glacial acetic acid solution is 0.1-0.4mol/L, and the ratio of the potassium permanganate to the glacial acetic acid solution is 1-5g:150 mL.
Preferably, the method for preparing the noble metal nanoparticles comprises: continuously stirring PVP (polyvinylpyrrolidone) aqueous solution at 60-80 deg.C, adding dropwise chloroplatinic acid solution and/or chloroauric acid solution, stirring for 2-10min, and adding dropwise potassium borohydride (KBH)4) And continuously stirring the solution at the temperature of between 60 and 100 ℃ for 0.5 to 4 hours, and finally carrying out solid-liquid separation to obtain the noble metal nano-particles.
Application of chloroauric acid and chloroplatinic acid in KBH4Before reduction, a proper amount of PVP is added into a solution system for protection, and Au ions and Pt ions can be reduced into a noble metal nanoparticle solution with proper particle size and good dispersibility at a proper reaction rate under the protection of the PVP. The PVP plays a role in protecting in the reaction process, the reaction speed is slowed down, and the reduced noble metal nano particlesKeeping smaller particle size and higher dispersibility.
Further preferably, the ratio of PVP to water in the PVP aqueous solution is 0.1-5g:100-200mL, the concentration of the chloroplatinic acid solution is 10-60mg/mL, the concentration of the chloroauric acid solution is 10-60mg/mL, and the ratio of potassium borohydride to water in the potassium borohydride solution is 0.005-0.04g:10-40 mL;
the proportion of PVP in the PVP aqueous solution to potassium borohydride in the chloroplatinic acid solution, the chloroauric acid solution and the potassium borohydride solution is 0.1-5g, 0.2-5mL and 0.005-0.04 g.
Au and Pt are preferably adopted for simultaneous reduction, and Au similar to alloy can be formedxPt1-xComposite nanoparticles (x stands for Au)xPt1-xThe mass fraction of Au in the composite nano-particle alloy is more than 0 and less than 1). In the catalyst system, compared with the catalyst system which is respectively reduced to form Au nano-particles and Pt nano-particles and then modified together in alpha-MnO2Upper, AuxPt1-xThe composite nano-particle alloy is modified in alpha-MnO due to the tighter interaction between Au and Pt2When the Au-Pt-alpha-MnO is formed more easily2The three components act synergistically, and the obtained catalyst has better catalytic performance.
The invention also provides the supported catalyst prepared by the preparation method and suitable for the low-temperature plasma concerted catalysis process.
The invention also provides the application of the supported catalyst in low-temperature plasma concerted catalysis treatment of malodorous gas. The malodorous gas comprises nitrogen-containing malodorous gas, such as ammonia, organic amine, acrylonitrile, aliphatic nitrile, etc.
The invention also provides a method for treating the waste gas containing the malodorous gas by using the synergy of the sleeve type plasma reactor and the catalyst, wherein the sleeve type plasma reactor comprises a shell and an internal ceramic tube which are concentrically arranged, reticular metal electrodes are respectively attached to the inner surface and the outer surface of the ceramic tube, the internal reticular metal electrode and the external reticular metal electrode are respectively connected with the cathode and the anode of a high-voltage pulse power supply, and the internal reticular metal electrode and the external reticular metal electrode are both covered with the supported catalyst;
the input voltage of the sleeve type plasma reactor is 90-120V, and the residence time of the waste gas in the sleeve type plasma reactor is 3-6 s.
Compared with the prior art, the invention has the main advantages that: the invention provides alpha-MnO modified by noble metal nano particles (Au and Pt)2The supported catalyst prepared by loading porous carbon cloth overcomes the defects of long preparation process, low catalyst loading firmness and general degradation efficiency of the existing catalyst. The preparation method is simple and has good repeatability, and the obtained catalyst has excellent performance in the aspect of removing nitrogen-containing odor by the low-temperature plasma concerted catalysis process, has good adaptability to complex production environments, and has popularization and application values.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
A preparation method of a supported catalyst suitable for a low-temperature plasma concerted catalysis process comprises the following specific steps:
s1, preparing noble metal nano particles.
AuxPt1-xAnd (3) preparing the composite nano-particle alloy. Wherein the value of x is determined by the volume of chloroauric acid or chloroplatinic acid added. A typical formulation is as follows: 0.1-5g of PVP is dissolved in 100-200mL of deionized water and placed in a three-neck flask, and the mixture is continuously stirred under the hydrothermal environment of 60-80 ℃. Slowly dripping 0.2-5.0mL chloroplatinic acid (10-60mg/mL) and 0.2-5.0mL chloroauric acid (10-60mg/mL), and stirring for 2-10 min. Adding 0.005-0.04g of potassium borohydride into 10-40mL of deionized water, slowly dropping into a three-neck flask after completely dissolving, and continuously heating and stirring for 0.5-4h at 60-100 ℃ under hydrothermal condition. Thus obtaining AuxPt1-xComposite nanoparticle alloy, x represents AuxPt1-xThe mass fraction of Au in the composite nano-particle alloy is more than 0 and less than 1.
(100% -y) preparation of Au/yPt mixed nanoparticles, wherein y represents that the mass percent of Pt in the mixed nanoparticles is more than 0 and less than 100 percent. The Au nanoparticle mixed solution and the Pt nanoparticle mixed solution are prepared respectively according to the method similar to the method, then the suspension of the Au nanoparticle mixed solution and the Pt nanoparticle mixed solution are mixed according to different volume ratios, and the volume is adjusted to obtain (100% -y) Au/yPt mixed nanoparticle solutions with different y values.
And filtering the nanoparticle solution, washing the solution for several times by using deionized water and alcohol, and drying the solution to obtain the nanoparticles. The preparation process of Au nanoparticles and Pt nanoparticles is the same as above, and chloroplatinic acid or chloroauric acid is not added.
S2.α-MnO2And (4) preparation. alpha-MnO2: 2.45g KMnO were accurately weighed4Dissolving in 150ml glacial acetic acid solution (0.4mol/L), stirring at a set rotation speed for 60min, transferring to 200ml PTFE liner hydrothermal kettle, performing hydrothermal treatment at 120 deg.C for 48h, cooling to room temperature, washing the precipitate with distilled water and ethanol for several times, filtering, and oven drying at 80 deg.C.
S3, nano-particles and alpha-MnO2And (4) compounding. Dissolving 5-20mg of prepared noble metal nano particles in 100mL of deionized water, pouring into a three-neck flask, and then adding 0.1-5g of alpha-MnO2Dissolving in 50mL of deionized water, performing ultrasonic treatment, pouring into a three-neck flask, continuing to perform water bath at 80-100 ℃ and stirring, and continuing to react for 4-6 h. The residue in the three-necked flask was filtered and washed repeatedly several times with deionized water and anhydrous ethanol. Drying in a drying oven at 60-80 ℃ for 12-48h to obtain noble metal/alpha-MnO2A catalyst.
S4, preparing the aluminum sol. Mixing and stirring pseudo-boehmite and deionized water in a mass ratio of 1:30 for 45 min. Heating in water bath at 75 deg.C, and slowly adding 0.5mol/L nitric acid solution while stirring until the liquid becomes transparent gel and pH is 3. And (4) continuing heating in the water bath for 90min, then cooling and refluxing, and collecting for later use after natural cooling.
And S5, compounding the catalyst and the carrier. 0.5-2.5g of prepared noble metal/alpha-MnO is taken2Putting the catalyst into a beaker, adding 30-100mL of alumina sol and 20-250mL of absolute ethyl alcohol, and stirring for 30 min. Uniformly coating the suspension obtained after stirring on the cut suspension by using a brushOn the porous carbon cloth, the size of the carbon cloth is two pieces with different sizes, and the sizes are 250mm by 240mm and 250mm by 150mm respectively. Drying for 6-12 hours at 70-90 ℃ to obtain the target supported catalyst.
The loaded shaped catalyst can be placed in a sleeve type plasma reactor for catalytic degradation of nitrogen-containing odor.
The sleeve type plasma reactor comprises a PVC circular tube shell and an internal ceramic circular tube which are concentrically arranged. The PVC round pipe shell is internally provided with a reactor main body space, and gas passes through the reactor from the inner space of the ceramic round pipe and a gap between the ceramic round pipe and the shell. The inner and outer surfaces of the ceramic round tube are respectively attached with a reticular metal electrode, and the inner and outer reticular metal electrodes are respectively connected with the negative electrode and the positive electrode of a high-voltage pulse power supply. The supported catalyst is rolled into a cylinder along the short edge and covers the inner and outer meshed metal electrodes.
Unless otherwise specified, the following examples and comparative examples were carried out under the above condition parameters.
Example 1
The sleeve type plasma reactor is used for treating low-concentration malodorous gas. The simulated waste gas contains trimethylamine, the concentration of the trimethylamine is 500ppm, the rest is air, the gas flow is controlled to be 20L/min (the retention time is 3s), and the input voltage is 90V (the energy density is 199J/L). The catalyst adopts Au0.5Pt0.5/α-MnO2，Au0.5Pt0.5The mass fraction of alloy nano-particle modification is 2 percent (by alpha-MnO)2For reference), 0.5g of prepared Au0.5Pt0.5/α-MnO2The catalyst is put into a beaker, 50mL of alumina sol and 100mL of absolute ethyl alcohol are added, and the mixture is stirred for 30 min. The suspension obtained after stirring was uniformly coated with a brush on two cut carbon cloths of 250mm by 240mm and 250mm by 150mm, respectively. Drying for 6 hours at 80 ℃ to obtain the target supported catalyst. Finally, the removal rate of trimethylamine gas is 95%, the mineralization rate of the trimethylamine is 85%, and the selectivity of carbon monoxide and the selectivity of carbon dioxide are 15% and 80% respectively.
Comparative example 1
The only difference from example 1 is that 200mL of alumina sol and 30mL of absolute ethanol were added, and the conditions were the same in the remaining steps. The final trimethylamine gas removal rate was 65.2%, the trimethylamine mineralization rate was 68.6%, and the carbon monoxide selectivity and the carbon dioxide selectivity were 17.3% and 75.3%, respectively.
Comparative example 2
The only difference from example 1 is that the catalyst used was 50% Au/50% Pt/α -MnO2The mass fraction of the 50% Au/50% Pt mixed nano-particle modification is 2% (by alpha-MnO)2For reference), the conditions of the rest steps are the same. Finally, the removal rate of trimethylamine gas is 92.3 percent, the mineralization rate of the trimethylamine is 84.1 percent, and the selectivity of carbon monoxide and carbon dioxide are respectively 16.2 percent and 78.4 percent.
Example 2
The sleeve type plasma reactor is used for treating low-concentration malodorous gas, the simulated waste gas contains methylamine, the balance is air, the concentration of the methylamine is 100ppm, the gas flow is controlled to be 10L/min (the retention time is 6s), and the input voltage is 90V (the energy density is 199J/L). The catalyst adopts 50% Au/50% Pt/alpha-MnO2The mass fraction of the 50% Au/50% Pt mixed nano-particle modification is 4% (by alpha-MnO)2As a reference). 1.0g of the prepared 50% Au/50% Pt/alpha-MnO2The catalyst is put into a beaker, 50mL of alumina sol and 120mL of absolute ethyl alcohol are added, and the mixture is stirred for 60 min. The suspension obtained after stirring was uniformly coated on two pieces of carbon cloth cut to 250mm by 240mm and 250mm by 150mm, respectively, with a brush. Drying for 8 hours at 70 ℃ to obtain the target supported catalyst. Finally, the removal rate of methylamine gas is 85.6%, the mineralization rate of methylamine is 65.2%, and the selectivity of carbon monoxide and carbon dioxide are respectively 15.3% and 77.3%.
Example 3
The sleeve type plasma reactor is used for treating low-concentration malodorous gas, the simulated waste gas contains methylamine and trimethylamine, the concentration of the methylamine and the trimethylamine is 100ppm and 200ppm respectively, the rest is air, the gas flow is controlled to be 10L/min (the retention time is 6s), and the input voltage is 120V (the energy density is 334J/L). The catalyst adopts Au0.75Pt0.25/α-MnO2，Au0.75Pt0.25Alloy (I)The mass fraction of nano-particle modification is 1% (by alpha-MnO)2As a reference). 0.4g of prepared Au was taken0.75Pt0.25/α-MnO2The catalyst is put into a beaker, 60mL of aluminum sol and 60mL of absolute ethyl alcohol are added, and the mixture is stirred for 80 min. The suspension obtained after stirring was uniformly coated on two pieces of carbon cloth cut to 250mm by 240mm and 250mm by 150mm, respectively, with a brush. Drying for 8 hours at 70 ℃ to obtain the target supported catalyst. Finally, the removal rate of the mixed gas is 93.7%, the mineralization rate is 72.6%, and the selectivity of carbon monoxide and carbon dioxide are 12.3% and 81.3% respectively.
Comparative example 3
The difference from example 3 is only that glass fiber cloth is used instead of carbon cloth, and the conditions are the same in the remaining steps. Finally, the removal rate of the mixed gas is 85.7%, the mineralization rate is 68.9%, and the selectivity of carbon monoxide and carbon dioxide is 25.8% and 71.3% respectively.
Comparative example 4
The difference from example 3 is only the aluminium sol used, specifically: pseudo-boehmite and deionized water are mixed according to the mass ratio of 1:5, stirring is continuously carried out at room temperature, 0.05mol/L nitric acid solution is dropwise added into the mixture until the mixture becomes transparent and colloidal and the pH value is 6, and then stirring is carried out for 20min at 50 ℃ to obtain the aluminum sol. The remaining process conditions were the same as in example 3. Finally, the removal rate of the mixed gas is 67.5%, the mineralization rate is 52.9%, and the selectivity of carbon monoxide and carbon dioxide are 24.5% and 66.2% respectively.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (5)
1. A method for treating waste gas containing malodorous gas by using a sleeve type plasma reactor in cooperation with catalysis is characterized in that the sleeve type plasma reactor comprises a shell and an internal ceramic tube which are concentrically arranged, reticular metal electrodes are respectively attached to the inner surface and the outer surface of the ceramic tube, the internal reticular metal electrode and the external reticular metal electrode are respectively connected with a negative electrode and a positive electrode of a high-voltage pulse power supply, and a load type catalyst is covered on the internal reticular metal electrode and the external reticular metal electrode;
the input voltage of the sleeve type plasma reactor is 90-120V, and the residence time of the waste gas in the sleeve type plasma reactor is 3-6 s;
the preparation method of the supported catalyst comprises the following steps: alpha-MnO modified with noble metal2Adding the mixed solution of the alumina sol and the absolute ethyl alcohol, uniformly mixing to obtain a suspension, uniformly coating the suspension on the surface of a porous carbon cloth carrier, and drying at 60-90 ℃ to obtain the supported catalyst;
the noble metal is Au and/or Pt;
the noble metal modified alpha-MnO2The ratio of the aluminum sol to the absolute ethyl alcohol is 0.5-2.5g, 30-100mL and 20-250 mL;
the preparation method of the aluminum sol comprises the following steps: uniformly mixing pseudo-boehmite and deionized water according to the mass ratio of 1:10-50 to obtain a mixed solution, then dropwise adding 0.2-2mol/L nitric acid solution into the mixed solution at the temperature of 60-80 ℃ under the condition of continuous stirring until the mixed solution becomes transparent colloid and the pH value is 2-5, then continuously stirring at the temperature of 60-80 ℃ for 30-100min, and cooling to obtain the alumina sol;
the noble metal modified alpha-MnO2The preparation method comprises the following steps: dispersing noble metal nano particles in deionized water to obtain dispersion liquid A, and adding alpha-MnO2Dispersing in deionized water, performing ultrasonic treatment to obtain dispersion liquid B, mixing the dispersion liquid A and the dispersion liquid B uniformly, continuously stirring at 60-100 ℃ for reaction for 2-6h, performing solid-liquid separation after the reaction is finished, washing the obtained solid, and drying at 60-80 ℃ to obtain the alpha-MnO modified by the noble metal2；
The concentration of the noble metal nano particles in the dispersion liquid A is 5-20mg/100mL, and the concentration of the alpha-MnO in the dispersion liquid B is2In a concentration of 0.1 to 5g/50mL, the noble metal nanoparticles and alpha-MnO2The mass ratio of (1) to (5-20) mg to (0.1-5) g.
2. The method as set forth in claim 1, wherein the plasma is generated by a sleeve type plasma reactionThe method for treating the waste gas containing the malodorous gas by the reactor concerted catalysis is characterized in that the alpha-MnO is2The preparation method comprises the following steps: fully dissolving potassium permanganate in glacial acetic acid solution, then transferring to a reaction kettle for solvothermal reaction at the temperature of 100-160 ℃ for 12-48h, washing a precipitate obtained after the reaction is finished, and drying at the temperature of 60-90 ℃ to obtain the alpha-MnO2。
3. The method for treating the waste gas containing the malodorous gas by using the double-pipe plasma reactor in cooperation with the catalyst as claimed in claim 2, wherein the concentration of the glacial acetic acid solution is 0.1-0.4mol/L, and the ratio of the potassium permanganate to the glacial acetic acid solution is 1-5g:150 mL.
4. The method for treating malodorous gas-containing exhaust gas by means of coordinated catalysis with a tube-in-tube plasma reactor as claimed in claim 1, wherein the preparation method of the noble metal nanoparticles comprises: continuously stirring PVP aqueous solution at 60-80 ℃, then dropwise adding a chloroplatinic acid solution and/or a chloroauric acid solution, continuously stirring for 2-10min after dropwise adding is finished, dropwise adding a potassium borohydride solution, continuously stirring for 0.5-4h at 60-100 ℃, and finally carrying out solid-liquid separation and washing to obtain the noble metal nano-particles.
5. The method for treating exhaust gas containing malodorous gas by using the cannula-type plasma reactor in cooperation with catalysis as claimed in claim 4, wherein the ratio of PVP to water in the PVP aqueous solution is 0.1-5g:100-200mL, the concentration of the chloroplatinic acid solution is 10-60mg/mL, the concentration of the chloroauric acid solution is 10-60mg/mL, and the ratio of potassium borohydride to water in the potassium borohydride solution is 0.005-0.04g:10-40 mL;
the proportion of PVP in the PVP aqueous solution to potassium borohydride in the chloroplatinic acid solution, the chloroauric acid solution and the potassium borohydride solution is 0.1-5g, 0.2-5mL and 0.005-0.04 g.
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