CN104162445B - A kind of method of carrying silver-colored OMS-2 catalyst of preparing - Google Patents
A kind of method of carrying silver-colored OMS-2 catalyst of preparing Download PDFInfo
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- CN104162445B CN104162445B CN201410238373.2A CN201410238373A CN104162445B CN 104162445 B CN104162445 B CN 104162445B CN 201410238373 A CN201410238373 A CN 201410238373A CN 104162445 B CN104162445 B CN 104162445B
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Abstract
The invention discloses a kind of method of the Ag-OMS-2 of preparation catalyst material. Taking propionic aldehyde, silver ammino solution and liquor potassic permanganate as raw material, in same system, taking potassium permanganate as oxidant, propionic aldehyde is that reducing agent generation redox reaction generates OMS-2; Taking silver ammino solution as oxidant, propionic aldehyde is reducing agent, by Ag+Be reduced to Ag0, and be doped in newly-generated OMS-2, thereby obtain carrying silver-colored manganese oxide octahedron molecular screen XAg-OMS-2 catalyst material, wherein, X represents silver-colored manganese mol ratio. Preparation process of the present invention is simple. Taking XAg-OMS-2 as catalyst, taking ortho-xylene as target contaminant, the catalytic combustion properties of evaluating material, XAg-OMS-2 can be converted into CO by 400ppm ortho-xylene completely at 180 ~ 220 DEG C2And H2O. Catalytic combustion temperature is low, and treatment effeciency is high, there is no secondary pollution.
Description
Technical field
The present invention relates to a kind of method of Kaolinite Preparation of Catalyst material, be specifically related to carry silver-colored OMS-2 catalyst a kind of preparationMethod, belong to chemical industry catalysis technical field.
Background technology
The especially row of benzo pollutants of volatile organic matter (volatileorganiccompounds is called for short VOCs)Put and have a strong impact on the healthy of environment and people. In numerous VOCs control technologys, it is current that catalytic combustion technology is considered toThere is most a kind of VOCs control technology of development prospect. And exploitation efficient cryogenic catalyst is the key link of catalytic combustion. Benzene,The benzene homologues such as toluene and dimethylbenzene as important chemical raw material and good organic solvent at medicine, chemical industry and building decoration materialIn the suitability for industrialized production such as material, be widely used, this class VOCs is serious harm environment and human health after discharge entered environment. ?Control in all multi-methods of pollutant emission, catalytic combustion can, under the effect of catalyst, be converted into dioxy by VOCsChange carbon and water. Therefore, it is a kind of technology most with development prospect. And the development of effective catalyst realizes catalytic combustionCrucial.
MnO2There is variable valence state, the abundant feature such as pore structure and good heat endurance, in environmental catalysis fieldMore and more receive publicity. Manganese dioxide has a, beta, gamma, the multiple crystal formation such as δ. Manganese oxide octahedron molecular screen (OMS-2) belongs toa-MnO2One of. OMS-2 has tunnel-shaped structure, and its molecular formula can be write as KMn8O16, OMS-2 is a large amount of spacious owing to havingManganese ion (the Mn of the interlayer of opening and pore passage structure, mixed valence2+、Mn3+And Mn4+), gentle surface acid alkalescence andDesign features such as surface hydrophobic and the catalytic combustion of benzo pollutants class is shown to excellent effect. But than noble metalCatalyst, the low temperature active of OMS-2 need to improve. The manganese oxide octahedron molecular screen of Ag doping can improve reactivity.The synthetic method of Ag-OMS-2 mainly contains solid-solid reaction method, infusion process and hydro-thermal method etc. The people such as Chang (Chang, F.M.;Jansen,M.Angew.Chem.,Int.Ed.1984,23,906-907.Chang,F.M.;Jansen,M.ReV.Chim.Mineral.1986,23,48-54) at first with AgMnO4With AgO be raw material, adopt solid-solid reaction method,At 970 DEG C, react and within 7 days, prepared Ag-OMS-2 material; The people such as Hu (Hu Rongrong, Cheng Yi, Xie Lanying etc., catalysis journal,2007, vol.28,5,463-468) by manganese sulfate and silver nitrate and nitric acid, splash in liquor potassic permanganate, vigorous stirring is also returnedStream 48h makes Ag/OMS-2 catalyst, for CO catalytic oxidation; The people such as Chen (JunliChen, XingfuTang,JunlongLiu, EnshengZhanChem.Mater.2007,19,4292-4299) utilize AgMnO4And Mn(NO3)2Between redox reaction, at 120-200 DEG C, adopt hydrothermal synthesis method reaction 12h, obtained Ag-OMS-2 materialAnd for the catalytic oxidation of ethanol; Gac (WojciechGacAppliedCatalysisB:Environmental75(2007) 107 – 117) first make OMS-2 with hydrothermal synthesis method, use subsequently AgNO3Solution adopts initial infusion process to obtain Ag-OMS-2 material; Chinese patent (CN102918404A) report, in OMS-2 suspension, splashes into silver ammino solution and H2O2, be prepared intoArrive Ag0-OMS-2。
In above document, Ag-OMS-2 be prepared with need to first prepare after OMS-2, then by Ag or Ag+Doping wherein; OrPerson need to first obtain AgMnO4Deng intermediate, adopt the method for HTHP to obtain Ag-OMS-2. Preparation process is relatively numerous and diverse, rawProduct cost is high.
Summary of the invention
The object of this invention is to provide a kind of method of carrying silver-colored OMS-2 catalyst of preparing, its technique is simple, has reduced one-tenthThis.
Design of the present invention is such, and the present invention is taking propionic aldehyde, silver ammino solution and liquor potassic permanganate as raw material, sameIn system, taking potassium permanganate as oxidant, propionic aldehyde is that reducing agent generation redox reaction generates OMS-2; Taking silver ammino solution asOxidant, propionic aldehyde is reducing agent, by Ag+Be reduced to Ag0, and be doped in newly-generated OMS-2, obtain carrying silver-colored manganese oxide eightFace body molecular sieve-4 A g-OMS-2 material.
Concrete, method of the present invention comprises the following steps:
(1) take the KMnO of 0.02mol4Be dissolved in 50ml distilled water, under stirring, in 30 DEG C of water-baths, splash into 0.02 ~0.032mol propionic aldehyde;
(2) preparation silver ammino solution
The AgNO that first preparation quality mark is 0.05%3Solution, then to prepare mass fraction be 25% NH3.H2O solution, thenBy the NH preparing3.H2O solution is added drop-wise to AgNO3In solution, dropping limit, limit is shaken to solution and is just become clarification by muddiness, makesMass fraction is 0.05% silver ammino solution;
(3) silver ammino solution configuring is dropwise added in step (1) gained system, dropwise, in 30 DEG C of water-bathsContinue to stir 20 ~ 24h, filter, be washed to neutrality, wash 3 times with ethanol;
(4) alcohol washing step (3) being obtained is in 100 ~ 110 DEG C of dry 12 ~ 20h, and 400 DEG C of roasting 4 ~ 6h, obtain carrying silverManganese oxide octahedron molecular screen (OMS-2) class catalyst material, be denoted as XAg-OMS-2, wherein, X represents silver-colored manganese mol ratio.
In preparation method of the present invention, silver-colored manganese mol ratio can be got 0:1,0.01:1,0.02:1,0.05:1.
The present invention is in same system, and taking potassium permanganate as oxidant, propionic aldehyde is that reducing agent generation redox reaction is rawBecome OMS-2; Taking silver ammino solution as oxidant, propionic aldehyde is reducing agent, by Ag+Be reduced to Ag0, and be doped in newly-generated OMS-2In, a step obtains XAg-OMS-2 catalyst material.
The present invention gives the application of XAg-OMS-2. Taking ortho-xylene as target contaminant, the catalysis combustion of evaluating materialBurn performance. Be exactly specifically that catalyst XAg-OMS-2 eliminates the application in VOCs gas at low-temperature catalytic burning. Taking ortho-xylene asThe VOCs gas catalytic combustion of representative is eliminated reaction and is carried out in fixed bed quartz tube reactor. Taking XAg-OMS-2 as catalyst,Pass into and be mixed with ortho-xylene and simulated air (N2/O2=4/1) mist, wherein the concentration of ortho-xylene is 400ppm, gasStream air speed is 7200h-1. Conversion ratio and the CO of the gas chromatographic detection ortho-xylene of two FID are housed2Productive rate.
The beneficial effect that the present invention obtains is as follows: one-step method of the present invention prepares XAg-OMS-2 catalyst material, preparationProcess is simple. Experiment showed, that XAg-OMS-2 can be converted into CO by 400ppm ortho-xylene completely at 180 ~ 220 DEG C2And H2O, urgesChange ignition temperature low, treatment effeciency is high, there is no secondary pollution.
Brief description of the drawings
Fig. 1 is embodiment 1,2, the catalytic activity test data figure of the XAg-OMS-2 catalyst of 3,4 preparations.
Fig. 2 is embodiment 1,2, the XRD figure of the XAg-OMS-2 catalyst of 3,4 preparations.
Fig. 3, Fig. 4 are embodiment 1,2, the scanning electron microscope (SEM) photograph of the XAg-OMS-2 catalyst of 3,4 preparations.
Fig. 5 is the energy dispersion type x-ray spectrometer of the 0Ag-OMS-2 catalyst prepared of embodiment 1
(EDX) collection of illustrative plates.
Fig. 6 is the energy dispersion type X ray spectrum of the 0.02Ag-OMS-2 catalyst prepared of embodiment 2
Instrument (EDX) collection of illustrative plates.
Detailed description of the invention
Following examples are used for illustrating the present invention.
Embodiment 1
(1) take the KMnO of 0.02mol4Be dissolved in 50ml distilled water, under stirring, in 30 DEG C of water-baths, splash into 0.02mol thirdAldehyde;
(2) dropwise, in 30 DEG C of water-baths, continue to stir 24h, filter, be washed to neutrality, wash 3 times with ethanol;
(3) alcohol washing step (2) being obtained is in 110 DEG C of dry 20h, and 400 DEG C of roasting 6h, obtain octahedra point of manganese oxideSon sieve (OMS-2) class catalyst 0Ag-OMS-2 material (silver-colored manganese mol ratio is 0:1).
(4) catalyst activity evaluation
Ortho-xylene concentration is 400ppm, and air-flow air speed is 7200h-1. The two FID of gas-chromatography detect the conversion of ortho-xyleneRate and CO2Productive rate. Taking prepared material as the complete catalytic combustion elimination ortho-xylene of catalyst (ortho-xylene 100% transforms)Temperature be 190 DEG C, 176 DEG C time, the conversion ratio of ortho-xylene reaches 50%, when temperature is in the scope of 170 DEG C～190 DEG C, neighbourDimethylbenzene conversion ratio straight line raises until reach 100%, and in the catalytic combustion elimination reaction of ortho-xylene, ortho-xylene is completeChange into CO2And H2O。
Embodiment 2
(1) take the KMnO of 0.02mol4Be dissolved in 50ml distilled water, under stirring, in 30 DEG C of water-baths, splash into 0.0224molPropionic aldehyde;
(2) preparation silver ammino solution
First by the AgNO of 0.0002mol3Be prepared into mass fraction and be 0.05% AgNO3Solution, then prepare mass fraction and be25% NH3.H2O solution, then by the NH preparing3.H2O solution is added drop-wise to above-mentioned AgNO3In solution, shake extremely on dropping limit, limitSolution just becomes clarification by muddiness, makes mass fraction and be 0.05% silver ammino solution;
(3) silver ammino solution preparing is dropwise added in step (1) gained system, dropwise, in 30 DEG C of water-bathsContinue to stir 24h, filter, be washed to neutrality, wash 3 times with ethanol;
(4) alcohol washing step (3) being obtained is in 110 DEG C of dry 20h, and 400 DEG C of roasting 6h, obtain carrying silver-colored manganese oxide eightFace body molecular sieve (OMS-2) class catalyst 0.01Ag-OMS-2 material (silver-colored manganese mol ratio is 0.01:1).
(5) catalyst activity evaluation (evaluation procedure of catalyst is with embodiment 1), taking prepared material as catalyst completeThe temperature of catalytic combustion elimination ortho-xylene (ortho-xylene 100% transforms) is 190 DEG C, the conversion ratio of ortho-xylene 173 DEG C timeReach 50%, when temperature is in the scope of 175 DEG C～190 DEG C, ortho-xylene conversion ratio straight line raises until reach 100%,In the catalytic combustion elimination reaction of ortho-xylene, ortho-xylene changes into CO completely2And H2O。
Embodiment 3
(1) take the KMnO of 0.02mol4Be dissolved in 50ml distilled water, under stirring, in 30 DEG C of water-baths, splash into 0.0247molPropionic aldehyde;
(2) preparation silver ammino solution
First by the AgNO of 0.0004mol3Be prepared into mass fraction and be 0.05% AgNO3Solution, then prepare mass fraction and be25% NH3.H2O solution, then by the NH preparing3.H2O solution is added drop-wise to above-mentioned AgNO3In solution, shake extremely on dropping limit, limitSolution just becomes clarification by muddiness, makes mass fraction and be 0.05% silver ammino solution;
(3) silver ammino solution preparing is dropwise added in step (1) gained system, dropwise, in 30 DEG C of water-bathsContinue to stir 24h, filter, be washed to neutrality, wash 3 times with ethanol;
(4) alcohol washing step (3) being obtained is in 110 DEG C of dry 20h, and 400 DEG C of roasting 6h, obtain carrying silver-colored manganese oxide eightFace body molecular sieve (OMS-2) class catalyst 0.02Ag-OMS-2 material (silver-colored manganese mol ratio is 0.02:1).
(5) catalyst activity evaluation (evaluation procedure of catalyst is with embodiment 1), taking prepared material as catalyst completeThe temperature of catalytic combustion elimination ortho-xylene (ortho-xylene 100% transforms) is 180 DEG C, the conversion ratio of ortho-xylene 158 DEG C timeReach 50%, when temperature is in the scope of 150 DEG C～180 DEG C, ortho-xylene conversion ratio straight line raises until reach 100%,In the catalytic combustion elimination reaction of ortho-xylene, ortho-xylene changes into CO completely2And H2O。
Embodiment 4
(1) take the KMnO of 0.02mol4Be dissolved in 50ml distilled water, under stirring, in 30 DEG C of water-baths, splash into 0.032molPropionic aldehyde;
(2) preparation silver ammino solution
First by the AgNO of 0.001mol3Be prepared into mass fraction and be 0.05% AgNO3Solution, then prepare mass fraction and be25% NH3.H2O solution, then by the NH preparing3.H2O solution is added drop-wise to above-mentioned AgNO3In solution, shake extremely on dropping limit, limitSolution just becomes clarification by muddiness, makes mass fraction and be 0.05% silver ammino solution;
(3) silver ammino solution preparing is dropwise added in step (1) gained system, titration is complete, in 30 DEG C of water-bathsContinue to stir 24h, filter, be washed to neutrality, wash 3 times with ethanol;
(4) alcohol washing step (3) being obtained is in 110 DEG C of dry 20h, and 400 DEG C of roasting 6h, obtain carrying silver-colored manganese oxide eightFace body molecular sieve (OMS-2) class catalyst 0.05Ag-OMS-2 material (silver-colored manganese mol ratio is 0.05:1).
(5) catalyst activity evaluation (evaluation procedure of catalyst is with embodiment 1), taking prepared material as catalyst completeThe temperature of catalytic combustion elimination ortho-xylene (ortho-xylene 100% transforms) is 220 DEG C, the conversion ratio of ortho-xylene 210 DEG C timeReach 50%, when temperature is in the scope of 190 DEG C～220 DEG C, ortho-xylene conversion ratio straight line raises until reach 100%,In the catalytic combustion elimination reaction of ortho-xylene, ortho-xylene changes into CO completely2And H2O。
Claims (1)
1. prepare a method of carrying silver-colored OMS-2 catalyst, it is characterized in that comprising the following steps:
(1) take the KMnO of 0.02mol4Be dissolved in 50ml distilled water, under stirring, in 30 DEG C of water-baths, splash into 0.02 ~ 0.032molPropionic aldehyde;
(2) preparation silver ammino solution
The AgNO that first preparation quality mark is 0.05%3Solution, then prepare 25% NH3.H2O solution, then will prepareNH3.H2O solution is added drop-wise to AgNO3In solution, dropping limit, limit is shaken to solution and is just become clarification by muddiness, makes mass fraction and is0.05% silver ammino solution;
(3) silver ammino solution preparing is dropwise added in step (1) gained system, dropwise, in 30 DEG C of water-baths, continueStir 20 ~ 24h, filter, be washed to neutrality, wash 3 times with ethanol;
(4) alcohol washing step (3) being obtained, in 100 ~ 110 DEG C of dry 12 ~ 20h, then at 400 DEG C of roasting 4 ~ 6h, obtains carryingSilver manganese oxide octahedron molecular screen OMS-2 catalyst A g-OMS-2 material, its silver-colored manganese mol ratio be 0.01:1,0.02:1,0.05:1 one of them.
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| CN104888801A (en) * | 2015-05-21 | 2015-09-09 | 河北师范大学 | Method for preparing cuprous oxide-doped OMS-2 catalyst |
| CN110354894B (en) * | 2019-07-22 | 2022-03-04 | 三峡大学 | CuOXPreparation method of/OMS-2 catalyst and application of catalyst in synthesizing phenoxathiin derivative |
| CN110697870A (en) * | 2019-10-18 | 2020-01-17 | 武汉纺织大学 | Ag-OMS-2 composite material and preparation method and application thereof |
| CN111266129B (en) * | 2020-02-01 | 2021-04-23 | 浙江大学 | Solid-phase OMS-2 molecular sieve catalyst for room-temperature formaldehyde purification and preparation method thereof |
| CN115253665B (en) * | 2022-07-04 | 2023-05-30 | 江苏理工学院 | Method for degrading VOCs and NOx by K modified OMS-2 in cooperation with low-temperature plasma catalysis |
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