CN117599778A - Mullite type composite catalyst applicable to low-temperature plasma and preparation method and application thereof - Google Patents
Mullite type composite catalyst applicable to low-temperature plasma and preparation method and application thereof Download PDFInfo
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- CN117599778A CN117599778A CN202311617115.0A CN202311617115A CN117599778A CN 117599778 A CN117599778 A CN 117599778A CN 202311617115 A CN202311617115 A CN 202311617115A CN 117599778 A CN117599778 A CN 117599778A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 238000000034 method Methods 0.000 claims abstract description 40
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- 229940071125 manganese acetate Drugs 0.000 claims abstract description 17
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 14
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- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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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
- B01D53/32—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 by electrical effects other than those provided for in group B01D61/00
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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
- B01D53/8603—Removing sulfur compounds
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/818—Employing electrical discharges or the generation of a plasma
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Abstract
The invention belongs to the technical field of catalysts, and discloses a mullite composite catalyst suitable for low-temperature plasmas, a preparation method and application thereof, wherein yttrium nitrate, manganese acetate and citric acid with certain molar ratio are jointly dissolved in deionized water to form metal salt, and then the metal salt is stirred and evaporated to dryness at proper temperature, and then YMn is obtained after calcination 2 O 5 /MnO x A composite catalyst. YMn of the invention 2 O 5 And MnO x The two components are generated in situ by a one-step method, and have strong interface interaction, so that electron transmission can be accelerated in the reaction process. The activity, stability and energy efficiency of the composite catalyst in the low-temperature plasma-catalytic degradation typical malodor pollution process are all superior to those of the prior art.
Description
Technical Field
The invention belongs to the technical field of gaseous pollutant treatment, and particularly relates to a mullite composite catalyst suitable for low-temperature plasma, and a preparation method and application thereof.
Background
H is inevitably produced in industrial production, sludge treatment, municipal sewage, garbage disposal facilities and the like 2 S、NH 3 Malodorous gases such as mercaptan and the like poison respiratory, digestive, nervous, cardiovascular and endocrine systems of human bodies, and even cause distortion and canceration in severe cases. The Chinese ecological environment department promulgates the malodor pollutant emission standard, further strengthens the emission concentration limitation of eight key malodor pollutants, and thus, the effective detection and the high-efficiency treatment of malodor pollution are urgent.
The traditional malodor pollution treatment technology comprises an adsorption method, an absorption method, an oxidation method, a low-temperature plasma method and the like, wherein the adsorption method needs to periodically replace an adsorbent and is easy to produce secondary pollution; the absorption method has the defects of subsequent treatment of absorption waste liquid, easy corrosion of equipment and the like; oxidation processes are typically costly to operate. Compared with other treatment technologies, the low-temperature plasma method has the advantages of low investment and operation cost, convenient start and stop, quick response, high degradation efficiency, no liquid pollution, small occupied area and the like, and is particularly suitable for the treatment of malodorous gas with large air volume, low concentration and strong odor. The low-temperature plasma technology is also considered by various governments as an effective technology suitable for malodorous gas treatment, but the technology has low energy efficiency and secondary pollution at present. The development of a functional catalyst in combination with plasma is an effective means to solve this bottleneck problem, where the choice of catalyst is the core of the synergistic system.
The Chinese patent (publication No. CN 115055204A) discloses a catalyst applicable to low-temperature plasma, a preparation method and application thereof, and the process provides a composite catalyst with a molecular sieve as a carrier and a transition metal oxide as an active component, wherein a porous structure of the molecular sieve has stronger surface discharge and aperture micro discharge in a plasma discharge system, the active component can promote the formation of active oxygen free radicals through a metal combination effect and a multistage reaction mass transfer strengthening effect, and a synergistic system shows good degradation performance of toluene, trichlorobenzene and mixed malodor under 21KV voltage. However, the energy consumption required by the synergistic system is higher, the starting voltage is 13KV, 21KV is required when the purification performance is more than 90%, the practical application process is easily limited by economy, and the stability of the catalyst is still to be improved.
Through the above analysis, the problems and defects existing in the prior art are as follows: the existing plasma catalyst has very limited reduction of energy consumption of a synergistic process, and the stability of the catalyst is poor when the catalyst is used cooperatively.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a mullite composite catalyst suitable for low-temperature plasma and a preparation method thereof, and is applied to plasma-catalysis synergistic purification of typical malodor pollution.
The invention is realized by the way, firstly, the invention provides a low-temperature plasma catalyst which is mullite composite metal oxide with the chemical formula of YMn 2 O 5 /MnO x Wherein YMn 2 O 5 And MnO x The interface composite structure is formed in situ by a one-step process.
The preparation method of the mullite composite catalyst suitable for the low-temperature plasma comprises the following steps:
yttrium nitrate, manganese acetate and citric acid with a certain molar ratio are dissolved in ultrapure water together to form a metal salt solution, and then stirred and evaporated to dryness at a proper temperature, and then calcined to obtain YMn 2 O 5 /MnO x A composite catalyst.
Further, in the preparation method, the molar ratio of yttrium nitrate to manganese acetate is 2:1-1:10, and the molar ratio directly determines the component content ratio of the composite metal oxide. Further, the molar ratio of yttrium nitrate to manganese acetate is 1:2-1:6.
Further, the amount of citric acid used in the preparation method is 1.5 to 3 times of the molar total amount of the metal salt. Citric acid is used as a complexing agent, so that two metal salts are fully mixed together in the stirring and evaporating process to form strong interaction. However, when the concentration of the citric acid is too high, the citric acid can expand and overflow rapidly at high temperature, and even the citric acid can be fried due to the excessive instantaneous heat, so that the use amount of the citric acid needs to be careful. Further, the amount of citric acid is 1.5 to 2 times the molar total amount of the metal salt.
Further, in the preparation method, three medicines are dissolved in ultrapure water, and the concentration of the formed metal salt solution is 10-200M; further, the concentration of the metal salt solution is 40 to 100M.
Further, in the preparation method, the stirring temperature is 80-150 ℃, the mixed solution is foamed under the action of citric acid and gradually forms a viscous gel substance in the process of stirring and evaporating at a certain temperature, and finally the mixed solution is loose sponge-like after being completely evaporated; further, the stirring temperature is 90 to 120 ℃.
Further, in the preparation method, the calcination process is air atmosphere calcination, the calcination temperature is 400-1000 ℃, the calcination time is 4-12 h, and the calcination process is to decompose the mixed metal salt into oxide at high temperature; further, the calcination temperature is 600-800 ℃, and the calcination time is 6-9 h.
Further, the mullite composite metal oxide can be used for treating O in plasma when being cooperated with the plasma in situ or in two stages 3 Active species such as active oxygen, hydroxyl free radicals and the like are fully utilized, and typical malodorous gases are efficiently purified.
Another object of the invention is to provide the use of mullite-type composite metal oxides for low temperature plasma catalytic oxidative degradation of typical malodor pollution.
In combination with the technical scheme and the technical problems to be solved, the technical scheme to be protected has the following advantages and positive effects:
in order to solve the problems of high energy consumption, serious secondary pollution, poor catalyst stability and the like in the low-temperature plasma process, the mullite composite metal oxide catalyst applicable to the low-temperature plasma is synthesized by a one-step sol-gel method, and the catalyst can react with O in the plasma in situ or in two sections 3 Active species such as active oxygen, hydroxyl free radicals and the like are fully utilized to generate strong oxidizing species, so that the decomposition and mineralization of typical malodorous molecules are promoted, and the energy consumption and secondary pollution of a plasma-catalysis synergistic process are reduced.
Next, in the present invention, YMn 2 O 5 /MnO x The composite oxide is generated in situ through a one-step method, the two components are tightly combined, an obvious interface effect is achieved, and the catalytic benefit of the two components can be enhanced through electron transmission in the reaction process.
In addition, in the present invention, YMn is formed 2 O 5 /MnO x The composite oxide is a mullite composite material, and the catalyst has super-strong stability in the cooperative use process due to the special microstructure of the composite oxide, and has good tolerance and stability even in a high-humidity environment.
The composite catalyst has better catalytic activity, stability and energy efficiency in a low-temperature plasma-catalytic system than the prior art.
As inventive supplementary evidence of the claims of the present invention, the following important aspects are also presented:
the expected benefits and commercial values after the technical scheme of the invention is converted are as follows: the mullite composite metal oxide provided by the invention can improve the degradation performance and the energy utilization efficiency of a plasma-catalytic process, and can be widely applied to malodorous pollution purification in industrial production, sludge treatment, municipal sewage, garbage disposal and other processes after conversion, and the commercial value is remarkable.
The technical scheme of the invention fills the technical blank in the domestic and foreign industries: YMn according to the invention 2 O 5 /MnO x The mullite composite catalyst and the preparation method and application thereof have not been reported in related researches and patents, but the composite catalyst can form good synergistic enhancement with plasma, and fills the technical blank of the functional catalyst suitable for plasma characteristics in the domestic and foreign industries.
Whether the technical scheme of the invention solves the technical problems that people want to solve all the time but fail to obtain success all the time is solved: in the plasma-catalysis cooperative process, the problem of long-term stability of the catalyst is always a key bottleneck for realizing industrial application of the process, but related breakthrough is still difficult. The mullite composite material provided by the invention has the advantages that the special microstructure is beneficial, the catalyst has super-strong stability in the cooperative use process, and good tolerance and stability are also shown even in a high-humidity environment, so that the application breakthrough is expected to be realized.
Drawings
FIG. 1 shows YM synthesized in example 1 of the present invention 2 O 5 /M 3 O 4 XRD pattern of the composite catalyst (XRD is an abbreviation for X-ray diffraction);
FIG. 2 shows YM synthesized in example 1 of the present invention 2 O 5 /M 3 O 4 Microcosmic morphology map (SEM and TEM images) of the composite catalyst;
FIG. 3 is a YM synthesized in example 1 of the present invention 2 O 5 /M 3 O 4 The composite catalyst is typically degraded by plasma-catalysis while in situ co-operating with the plasmaPerformance diagram of malodorous gas.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to fully understand how the invention may be embodied by those skilled in the art, this section is an illustrative embodiment in which the claims are presented for purposes of illustration.
The preparation method of the mullite composite catalyst suitable for low-temperature plasma provided by the embodiment of the invention comprises the following steps:
s101, yttrium nitrate, manganese acetate and a proper amount of citric acid in a certain molar ratio are dissolved in ultrapure water together;
s102, stirring the mixed solution at a proper temperature until the mixed solution is completely evaporated to dryness;
s103, calcining the evaporated solid powder to obtain YMn 2 O 5 /MnO x A composite catalyst. In the embodiment of the invention, in the step S101, the molar ratio of yttrium nitrate to manganese acetate is 2:1-1:10. Preferably, the molar ratio of yttrium nitrate to manganese acetate is 1:2-1:6.
The amount of citric acid used in step S101 in the embodiment of the present invention is 1.5 to 3 times the molar total amount of the metal salt. Preferably, the amount of citric acid is 1.5 to 2 times the molar total amount of the metal salt.
The concentration of the metal salt solution formed in step S101 in the embodiment of the present invention is 10 to 200M. Preferably, the concentration of the metal salt solution is 40 to 100M.
In the step S102 of the embodiment of the invention, the stirring temperature is 80-150 ℃. Preferably, the stirring temperature is 90 to 120 ℃.
In the embodiment of the invention, the calcination atmosphere in the step S103 is an air atmosphere, the calcination temperature is 400-1000 ℃, and the calcination time is 4-12 h. Preferably, the calcination temperature is 600-800 ℃ and the calcination time is 6-9 h.
In order to prove the inventive and technical value of the technical solution of the present invention, this section is an application example on specific products or related technologies of the claim technical solution.
The mullite composite catalyst suitable for low-temperature plasma provided by the embodiment of the invention can be used for in-situ or two-stage synergistic degradation of typical malodor pollution with plasma.
The embodiment of the invention has a great advantage in the research and development or use process, and has the following description in combination with data, charts and the like of the test process.
Example 1
Preparation of a composite catalyst: the molar ratio of the raw materials is yttrium nitrate: manganese acetate = 1:4, the amount of citric acid is 1.5 times of the molar total amount of the metal salt. Yttrium nitrate, manganese acetate and citric acid were dissolved together in 100mL deionized water and stirred overnight at 120 ℃ until completely evaporated to dryness. Grinding the foam solid matter formed after evaporating to dryness into powder, calcining at 800 ℃ for 8 hours in air atmosphere to obtain YMn 2 O 5 /M 3 O 4 A composite catalyst.
Catalyst performance test: the composite catalyst is coated on the surface of frosted glass beads and filled in the discharge area of the dielectric barrier discharge reactor for typical malodorous gas (NH) 3 、H 2 S, methyl mercaptan). In the embodiment, the plasma reactor is a coaxial cylinder type double-medium barrier discharge reactor, the inner medium and the outer medium are quartz, the outer diameter of the quartz outer tube is 25mm, the thickness is 2.5mm, the outer diameter of the quartz inner tube is 14mm, the thickness is 2mm, the surface of the quartz outer tube is tightly wound with a metal mesh as a ground electrode, the quartz inner tube is tightly filled with metal powder as an anode, the discharge length of the reactor is 100mm, and the discharge gap is 3mm; the power supply adopts a modulated pulse power supply; simulation of industrial waste gas from N 2 、O 2 、NH 3 、H 2 S, methyl mercaptan composition, wherein O 2 20% of malodorous gas 100ppm, and the flow rate is 1L/min; gas chromatography is adopted to measure foul gas, CO and CO at the inlet and outlet of the reactor 2 Concentration. NH when the energy density is 350J/L 3 、H 2 Typical malodor components such as S and methyl mercaptanThe removal rate of the seeds can reach 99 percent.
FIG. 1 shows YM synthesized in example 1 of the present invention 2 O 5 /M 3 O 4 XRD pattern of the composite catalyst (XRD is an abbreviation for X-ray diffraction);
as shown in FIG. 1, YM is clearly visible when compared with the PDF standard card 2 O 5 And Mn of 3 O 4 The two components exist simultaneously, the diffraction peak shape is good, which indicates that the composite catalyst is successfully synthesized and has good crystallinity.
FIG. 2 shows YM synthesized in example 1 of the present invention 2 O 5 /M 3 O 4 Microcosmic morphology map (SEM and TEM images) of the composite catalyst;
SEM can show that the synthesized composite catalyst has a fluffy porous structure, which is beneficial to enhancing the discharge intensity of plasma and promoting the adsorption and activation of pollutants; TEM results can see YM 2 O 5 And Mn of 3 O 4 The close combination of the two components has exposed crystal planes (201) and (103), respectively.
FIG. 3 is a YM synthesized in example 1 of the present invention 2 O 5 /M 3 O 4 The performance diagram of the composite catalyst for plasma-catalytic degradation of typical malodorous gases while in situ co-operating with the plasma.
It can be seen that when the composite catalyst provided by the invention is used together with plasma, NH is obtained when the energy density is 350J/L 3 、H 2 The removal rate of typical malodorous molecules such as S, methyl mercaptan and the like can reach 99%, and the performance is obviously higher than that of a single plasma process, which shows that the catalyst provided by the invention can obviously improve the degradation performance of the plasma-catalytic process on typical malodorous gas molecules.
Example 2
Preparation of a composite catalyst: the molar ratio of the raw materials is yttrium nitrate: manganese acetate = 1:3, the amount of citric acid is 2 times of the molar total amount of the metal salt. Yttrium nitrate, manganese acetate and citric acid were dissolved together in 60mL deionized water and stirred overnight at 100 ℃ until completely evaporated to dryness. Grinding the foam solid substance formed after evaporating to dryness into powder, andcalcining at 700 deg.C in air atmosphere for 10 hr to obtain YMn 2 O 5 /M 3 O 4 A composite catalyst.
Catalyst performance test: the composite catalyst is coated on the surface of frosted glass beads and filled in the discharge area of the dielectric barrier discharge reactor for typical malodorous gas (NH) 3 Carbon disulphide, styrene). In the embodiment, the plasma reactor is a coaxial cylinder type double-medium barrier discharge reactor, the inner medium and the outer medium are quartz, the outer diameter of the quartz outer tube is 25mm, the thickness is 2.5mm, the outer diameter of the quartz inner tube is 14mm, the thickness is 2mm, the surface of the quartz outer tube is tightly wound with a metal mesh as a ground electrode, the quartz inner tube is tightly filled with metal powder as an anode, the discharge length of the reactor is 100mm, and the discharge gap is 3mm; the power supply adopts a modulated pulse power supply; simulation of industrial waste gas from N 2 、O 2 、NH 3 Is composed of carbon disulfide and styrene, wherein O 2 20% of malodorous gas 80ppm, and the flow rate is 1L/min; gas chromatography is adopted to measure foul gas, CO and CO at the inlet and outlet of the reactor 2 Concentration. NH when the energy density is 350J/L 3 The removal rate of carbon disulfide and styrene molecules can reach 98 percent.
Example 3
Preparation of a composite catalyst: the molar ratio of the raw materials is yttrium nitrate: manganese acetate = 1: and 6, the amount of the citric acid is 2 times of the molar total amount of the metal salt. Yttrium nitrate, manganese acetate and citric acid were dissolved together in 60mL deionized water and stirred overnight at 150 ℃ until completely evaporated to dryness. Grinding the foam solid matter formed after evaporating to dryness into powder, calcining at 600deg.C in air atmosphere for 6 hr to obtain YMn 2 O 5 /M 3 O 4 A composite catalyst.
Catalyst performance test: the composite catalyst is coated on the surface of frosted glass beads and filled in the discharge area of the dielectric barrier discharge reactor for typical malodorous gas (NH) 3 、H 2 S, styrene). In the example, the plasma reactor is a coaxial cylinder type double-medium barrier discharge reactor, the inner medium and the outer medium are quartz, the outer diameter of the quartz outer tube is 25mm, the thickness is 2.5mm, and the outer diameter of the quartz inner tube is 14mmThe thickness is 2mm, the surface of the quartz outer tube is tightly wound with a metal net to serve as a ground electrode, metal powder is tightly filled in the quartz inner tube to serve as a positive electrode, the discharge length of the reactor is 100mm, and the discharge gap is 3mm; the power supply adopts a modulated pulse power supply; simulation of industrial waste gas from N 2 、O 2 、NH 3 、H 2 S, styrene composition, wherein O 2 20% of malodorous gas 80ppm, and the flow rate is 1L/min; gas chromatography is adopted to measure foul gas, CO and CO at the inlet and outlet of the reactor 2 Concentration. NH at an energy density of 400J/L 3 、H 2 The removal rate of S and styrene molecules can reach 95 percent.
Example 4
Preparation of a composite catalyst: the molar ratio of the raw materials is yttrium nitrate: manganese acetate = 1:3, the amount of the citric acid is 1.5 times of the molar total amount of the metal salt. Yttrium nitrate, manganese acetate and citric acid were dissolved together in 100mL deionized water and stirred overnight at 110 ℃ until completely evaporated to dryness. Grinding the foam solid matter formed after evaporating to dryness into powder, calcining at 800 ℃ for 10 hours in air atmosphere to obtain YMn 2 O 5 /M 3 O 4 A composite catalyst.
Catalyst performance test: the composite catalyst is coated on the surface of the frosted glass beads and is filled in the discharge area of the dielectric barrier discharge reactor, so that the catalyst is used for degradation experiments of typical malodorous gas methyl mercaptan. In the embodiment, the plasma reactor is a coaxial cylinder type double-medium barrier discharge reactor, the inner medium and the outer medium are quartz, the outer diameter of the quartz outer tube is 25mm, the thickness is 2.5mm, the outer diameter of the quartz inner tube is 14mm, the thickness is 2mm, the surface of the quartz outer tube is tightly wound with a metal mesh as a ground electrode, the quartz inner tube is tightly filled with metal powder as an anode, the discharge length of the reactor is 100mm, and the discharge gap is 3mm; the power supply adopts a modulated pulse power supply; simulation of industrial waste gas from N 2 、O 2 Methyl mercaptan composition, wherein O 2 20% of methyl mercaptan 100ppm, and the flow rate is 1L/min; gas chromatography is adopted to measure foul gas, CO and CO at the inlet and outlet of the reactor 2 Concentration. When the energy density is 400J/L, the removal rate of methyl mercaptan molecules can reach 96%.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (10)
1. The preparation method of the mullite composite catalyst suitable for the low-temperature plasma is characterized by comprising the following steps of:
the yttrium nitrate, the manganese acetate and the citric acid with certain molar ratio are dissolved in deionized water together to form metal salt, and then stirred and evaporated to dryness at proper temperature, and the YMn is obtained after calcination 2 O 5 /MnO x A composite catalyst.
2. The method for preparing the mullite composite catalyst suitable for low-temperature plasma according to claim 1, wherein the molar ratio of yttrium nitrate to manganese acetate is 2:1-1:10.
3. The method for preparing the mullite composite catalyst for low-temperature plasma according to claim 1, wherein the amount of the citric acid is 1.5-3 times of the molar total amount of the metal salt.
4. The method for preparing a mullite composite catalyst for low temperature plasma as claimed in claim 1, wherein the concentration of the metal salt solution is 10-200M.
5. The method for preparing a mullite composite catalyst for low temperature plasma as claimed in claim 4, wherein the concentration of the metal salt solution is 40-100M.
6. The method for preparing a mullite composite catalyst for low temperature plasma according to claim 1, wherein the temperature of stirring is 80-150 ℃.
7. The method for preparing a mullite composite catalyst suitable for low temperature plasma according to claim 1, wherein the calcination atmosphere is an air atmosphere, the calcination temperature is 400-1000 ℃ and the calcination time is 4-12 h.
8. The method for preparing a mullite composite catalyst for low temperature plasma as claimed in claim 7, wherein the calcination temperature is 600-800 ℃ and the calcination time is 6-9 hours.
9. A composite catalyst prepared by the method for preparing a mullite composite catalyst suitable for low temperature plasma according to any one of claims 1 to 8, characterized in that the YMn 2 O 5 And MnO x The two components are generated in situ by a one-step method, and have strong interface interaction, so that electron transmission can be accelerated in the reaction process.
10. The use of the mullite composite catalyst for low-temperature plasma in the synergistic catalytic oxidative degradation of typical malodorous gases of the low-temperature plasma according to claim 9.
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