CN102861609A - Gradient composite molecular sieve membrane catalytic material and preparation method and application thereof - Google Patents
Gradient composite molecular sieve membrane catalytic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a gradient composite molecular sieve membrane catalytic material and a preparation method thereof and application thereof. According to the gradient composite molecular sieve membrane catalytic material, ferrum serving as an active component exists in a molecular sieve structure in modes of framework iron atoms and a non-framework iron surface state or oxidation state. According to the gradient composite molecular sieve membrane catalytic material, a molecular sieve membrane which is continuous, compact and adjustable in thickness is synthesized on the surface of a stainless steel microfiber felt carrier by a secondary growth method, so that the prepared gradient composite molecular sieve membrane catalytic material has a three-dimensional meshed structure, and is high in mechanical strength and ductility, large in porosity and adjustable in range. The catalytic material is applied to the catalytic oxidation treatment of high-concentration phenol-containing waste water, and reaction and separation are integrated, so that the separation process among catalysts, reactants and products is simplified, and the reaction efficiency and selectivity are improved; phenol substances are oxidized and converted into carbon dioxide and water completely, so that the treatment efficiency of the phenol-containing waste water is improved greatly; and active substances are difficult to dissolve out in the treatment process, the secondary pollution of transition metals is avoided, and the catalysts are recycled easily.
Description
Technical field
The invention belongs to the processing technology field of phenol wastewater, relate to a kind of catalytic film reactor and preparation method thereof, be specifically related to a kind of gradient compound molecule sieve membrane catalysis material and preparation method thereof and application.
Background technology
Along with industrial expansion, water pollution problems is more and more serious.Wherein, phenol wastewater is field of Environment Protection outline and hot issue owing to wide material sources, harm are serious always.
Phenol is a kind of widely used industrial chemicals, is widely used in the numerous areas such as paint, fertilizer, rubber, plastics, resin, textile industry, asbestos industry, oil, pharmacy.Phenols in the phenol wastewater mainly is the compound that contains phenolic group, as phenol, cresols, xylenol, neighbour,, paraxylene phenol, alkylphenol and nitrophenol etc.Phenolic compound is highly toxic substance, and bioprotein is solidified, and directly damages various cells, has the potential dangers such as carcinogenic, teratogenesis, mutagenesis.When water body contained the phenol amount greater than 6.5mg/L, fish will mortality.Use the phenol wastewater irrigated farmland, will cause crop production reduction even withered.At present, drainage system is higher for the requirement for restriction of phenolic compound, and the phenols concentration requirement is no more than 1mg/L in three grades of discharge waters.
The processing method of phenol wastewater mainly contains following several: 1) Physical comprises that mainly extraction, absorption method and film separate etc.; 2) advanced oxidation processes mainly comprises chemical oxidization method, photocatalytic oxidation, By Electrocatalytic Oxidation, Catalyzed by Ultrasonic Wave oxidizing process etc.; 3) biological treatment.At present, domestic general employing Physical and advanced oxidation processes come concentration for the treatment of〉high-concentration phenolic wastewater of 1000mg/L, the low concentration phenol wastewater then adopts biological treatment to process.In advanced oxidation processes, chemical oxidization method is because to process wastewater degradation thorough, low secondary pollution, and the advantage such as with low cost is generally favored.Yet, still there are some problems in the method at present: it is oxidant that traditional chemical oxidization method adopts air, ozone, the reaction conditions such as temperature, pressure are required harsh, although and adopt traditional Fenton reagent can under comparatively gentle condition, process waste water because Fe
2+Form with soluble salt is present in the reaction system, still has secondary pollution to a certain degree, and the catalyst recovery difficulty.
Chinese patent CN1498861A discloses a kind of with TiO
2~ ZrO
2Be carrier, adopt the multiple noble metal of infusion process load and rare earth metal, the preparation CWO is processed the catalyst of high phenol wastewater, and the COD clearance can reach 99%.(Chinese patent CN1657158A is with active material TiO for the people such as the Gao Qiuming of Shanghai Silicate Inst., Chinese Academy of Sciences
2Be assembled in micropore nickel phosphate VSB-1, prepare photochemical catalyst, reaction 4h, the phenol degrading rate reaches 64.51%.Chinese patent CN101264968A discloses the nanometer Fe for the treatment of high concentration orthoresol waste water
3O
4The preparation method.These catalyst all are that the form with particle exists, the granulin molecule sieve catalyst is in catalytic reaction, discontinuous, the unstable state of course of reaction, and because the Time Inconsistency that reactant molecule stops in particle surface and duct, side reaction occurs easily, after reaction finishes, there is difficult problem of separating between catalyst and reactant, the product.
Summary of the invention
The object of the invention is the deficiency for the conventional particles molecular sieve catalyst, a kind of gradient molecular-sieve film catalytic material that integrates reaction and separation processes and preparation method thereof is provided, the catalytic oxidation treatment that is used for phenol wastewater improves the reaction efficiency of catalytic oxidation with selective.Gradient molecular-sieve film catalytic material of the present invention is high to the aldehydes matter degradation rate, simplified the separation process between catalyst, reactant and the product, active material is difficult for stripping in catalytic oxidation process, do not cause the transition metal secondary pollution, and catalysis material reclaims easily.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of gradient compound molecule sieve membrane catalysis material is present in the molecular sieve structure by iron surface attitude or the oxidation state form of active component iron species with skeleton position iron atom and non-skeleton position, and the load capacity of active component is 0.5 ~ 3.0wt%.
The present invention also provides the preparation method of described gradient compound molecule sieve membrane catalysis material, comprises the steps:
(1) surface preparation of carrier: after the stainless steel fibre felt soaked 10 ~ 60min respectively with the aqueous sulfuric acid of the sodium hydrate aqueous solution of mass concentration 5 ~ 10% and mass concentration 5 ~ 10wt%, dry, in 600 ~ 700 ℃ of calcining 4 ~ 8h, be soaked in 10 ~ 60min in the poly-hydroxypropyl dimethyl aqueous ammonium chloride solution of mass concentration 0.5%, clean with the rinsing of 0.1mol/L ammonia spirit, natural drying, obtain stainless steel fibre felt carrier;
(2) preparation of crystal seed: TPAOH, deionized water and ethanol are mixed, strong stirring slowly drips tetraethoxysilance on one side on one side, after dropwising at room temperature strong stirring 12 ~ 24h clarify to mixed liquor, above-mentioned mixed liquor is sealed Hydrothermal Synthesis 12 ~ 48h in 100 ~ 130 ℃, centrifugal, obtain crystal seed; The mass ratio of described TPAOH, deionized water, ethanol and tetraethoxysilance is (1 ~ 8): (5 ~ 8): (2 ~ 4): (3 ~ 7);
(3) dip-coating of crystal seed: the crystal seed that step (2) is obtained adds in the ammoniacal liquor and obtains mass concentration 1 ~ 4%, pH is 10 brilliant liquid, the stainless steel fibre felt carrier that step (1) is obtained soaks 0.5 ~ 1h in brilliant liquid, 80 ℃ of dryings, soak again 1 ~ 2.5h, 70 ~ 100 ℃ of dryings obtain adsorbing the carrier of crystal seed; The mass ratio of described crystal seed and carrier is 1:(5 ~ 20);
(4) diauxic growth: sodium metasilicate, NaOH, ferric nitrate, deionized water, sodium metaaluminate and TPAOH are mixed, and the carrier submergence of the absorption crystal seed that step (3) is obtained wherein, in 100 ~ 170 ℃ of heated sealed 24 ~ 96h; The mass ratio of described sodium metasilicate, NaOH, ferric nitrate, deionized water, sodium metaaluminate, TPAOH and carrier is (20 ~ 30): (2 ~ 3): (0.202 ~ 0.808): (0 ~ 0.5): (0 ~ 10): (1 ~ 20);
(5) the template TPAOH is removed in calcining: the ultrasonic washing of the product 20min of step (4), and natural drying, be warming up to 400 ~ 600 ℃ with 5 ℃/min speed, insulation 4h is down to room temperature again, makes gradient compound molecule sieve membrane catalysis material.
The porosity of described stainless steel fibre felt is 70 ~ 90%, and fibre diameter is 0.5 ~ 10 μ m.
The thickness of described gradient compound molecule sieve membrane catalysis material is 1 ~ 10 μ m.
The present invention also provides the application of described gradient compound molecule sieve membrane catalysis material in the phenol wastewater catalytic oxidation.
The step of described catalytic oxidation is as follows: the pH that regulates phenol wastewater is 2 ~ 6, the adding hydrogen peroxide solution mixes and obtains mixed liquor, under normal pressure, 50 ~ 80 ℃, mixed liquor is sealed liquid phase circulation 1 ~ 6h with the speed of 10 ~ 60mL/min by gradient compound molecule sieve membrane catalysis material.
Contain phenol, o-phenol, Resorcino in the described phenol wastewater, in biphenol amino phenols, nitrophenols or the chlorophenol one or more, and phenols total concentration wherein is higher than 1000mg/L.
The mass fraction of described hydrogen peroxide solution is 10 ~ 50%, and its mass fraction in mixed liquor is 1 ~ 24%; The mass fraction of described gradient compound molecule sieve membrane catalysis material in mixed liquor is 0.5 ~ 12%.
The present invention compared with prior art has significant advantage and progress:
(1) gradient compound molecule sieve membrane catalysis material of the present invention is the molecular-sieve film catalytic material that integrates reaction and separation processes, thickness is adjustable, simplify the separation process between catalyst, reactant and the product, can effectively improve the reaction efficiency of catalysis with selective;
(2) gradient compound molecule sieve membrane catalysis material of the present invention is applied to the catalytic oxidation treatment of phenol wastewater, and its degradation rate is high, can be carbon dioxide and water with the phenol exhaustive oxidation;
(3) gradient compound molecule sieve membrane catalysis material of the present invention is applied to the catalytic oxidation treatment reaction condition gentleness of phenol wastewater, and active material is difficult for stripping in catalytic oxidation process, does not cause the transition metal secondary pollution;
(4) preparation method of gradient compound molecule sieve membrane catalysis material of the present invention is simple, and the easy recycling of material after processing, and has reduced the cost of wastewater treatment.
Description of drawings
Fig. 1 is that the ESEM of the gradient compound molecule sieve membrane catalysis material of the embodiment of the invention 1 preparation (is called for short: SEM) figure.
Fig. 2 be gradient compound molecule sieve membrane catalysis material of the present invention X-ray diffraction (be called for short: XRD) figure, wherein, a is stainless steel fibre felt carrier; B is the gradient compound molecule sieve membrane catalysis material of embodiment 1 preparation.
Fig. 3 is the gradient compound molecule sieve membrane catalysis material of the embodiment of the invention 1 preparation time dependent degradation curve of phenol conversion when being used for the catalytic oxidation of phenol wastewater.
The specific embodiment
For better understanding the present invention, the present invention is described in further detail below in conjunction with embodiment, but the scope of protection of present invention is not limited to this.
Embodiment 1
(1) surface preparation of carrier: after 2g stainless steel fibre felt soaked 60min respectively with the aqueous sulfuric acid of the sodium hydrate aqueous solution of 5wt% and 5wt%, dry, in 650 ℃ of calcining 5h, be soaked in 30min in the poly-hydroxypropyl dimethyl aqueous ammonium chloride solution of mass concentration 0.5%, clean with the rinsing of 0.1mol/L ammonia spirit, natural drying, obtain stainless steel fibre felt carrier;
(2) preparation of crystal seed: the 5g TPAOH (is called for short: TPAOH), 6g deionized water and 3g ethanol mixes, strong stirring slowly drips 4g tetraethoxysilance (abbreviation: TEOS) on one side on one side, after dropwising at room temperature strong stirring 24h clarify to mixed liquor, above-mentioned mixed liquor will be changed in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, in 100 ℃ of Hydrothermal Synthesis 24h, centrifugal, obtain crystal seed;
(3) dip-coating of crystal seed: the crystal seed that step (2) is obtained adds in the ammoniacal liquor and obtains mass concentration 2%, and pH is 10 brilliant liquid, and the stainless steel fibre felt carrier that step (1) is obtained soaks 0.5h in brilliant liquid, 80 ℃ of dryings, soak 2.5h, 80 ℃ of dryings obtain adsorbing the carrier of crystal seed again;
(4) diauxic growth: with 28.4gNaSiO
39H
2O, 2.4gNaOH, 0.505g Fe (NO
3)
39H
2O, 90g deionized water and 8.315g TPAOH mix, and change in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, and the vertical submergence of carrier of the absorption crystal seed that step (3) is obtained are wherein, in 170 ℃ of heated sealed 48h;
(5) template TPAOH is removed in calcining: the ultrasonic washing of the product 20min of step (4), and natural drying, be warming up to 550 ℃ with 5 ℃/min speed, insulation 4h is down to room temperature again, makes gradient compound molecule sieve membrane catalysis material.Through aas determination, active material iron-loading rate is 1.26wt% in the catalysis material of preparation.
Embodiment 2
(1) surface preparation of carrier: respectively soak 10min after dry with the aqueous sulfuric acid of the sodium hydrate aqueous solution of 10wt% and 10wt% 1g stainless steel fibre felt, in 700 ℃ of calcining 5h, be soaked in 30min in the poly-hydroxypropyl dimethyl aqueous ammonium chloride solution of mass concentration 0.5%, clean with the rinsing of 0.1mol/L ammonia spirit, natural drying, obtain stainless steel fibre felt carrier;
(2) preparation of crystal seed: 5g TPAOH, 6g deionized water and 3g ethanol are mixed, strong stirring slowly drips 6g TEOS on one side on one side, after dropwising at room temperature strong stirring 24h clarify to mixed liquor, above-mentioned mixed liquor will be changed in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, in 110 ℃ of Hydrothermal Synthesis 48h, centrifugal, obtain crystal seed;
(3) dip-coating of crystal seed: the crystal seed that step (2) is obtained adds in the ammoniacal liquor and obtains mass concentration 1%, and pH is 10 brilliant liquid, and the stainless steel fibre felt carrier that step (1) is obtained soaks 0.5h in brilliant liquid, 80 ℃ of dryings, soak 2.5h, 80 ℃ of dryings obtain adsorbing the carrier of crystal seed again;
(4) diauxic growth: with 28.4g NaSiO
39H
2O, 2.4g NaOH, 0.202g Fe (NO
3)
39H
2O, 90g deionized water and 8.315g TPAOH mix, and change in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, and the vertical submergence of carrier of the absorption crystal seed that step (3) is obtained are wherein, in 170 ℃ of heated sealed 96h;
(5) template TPAOH is removed in calcining: the ultrasonic washing of the product 20min of step (4), and natural drying, be warming up to 550 ℃ with 5 ℃/min speed, insulation 4h is down to room temperature again, makes gradient compound molecule sieve membrane catalysis material.Through aas determination, active material iron-loading rate is 1wt% in the catalysis material of preparation.
Embodiment 3
(1) surface preparation of carrier: after 10g stainless steel fibre felt soaked 30min respectively with the aqueous sulfuric acid of the sodium hydrate aqueous solution of 8wt% and 8wt%, dry, in 600 ℃ of calcining 5h, be soaked in 30min in the poly-hydroxypropyl dimethyl aqueous ammonium chloride solution of mass concentration 0.5%, clean with the rinsing of 0.1mol/L ammonia spirit, natural drying, obtain stainless steel fibre felt carrier;
(2) preparation of crystal seed: 5g TPAOH, 6g deionized water and 3g ethanol are mixed, strong stirring slowly drips 4g TEOS on one side on one side, after dropwising at room temperature strong stirring 24h clarify to mixed liquor, above-mentioned mixed liquor will be changed in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, in 100 ℃ of Hydrothermal Synthesis 12h, centrifugal, obtain crystal seed;
(3) dip-coating of crystal seed: the crystal seed that step (2) is obtained adds in the ammoniacal liquor and obtains mass concentration 3%, and pH is 10 brilliant liquid, and the stainless steel fibre felt carrier that step (1) is obtained soaks 0.5h in brilliant liquid, 80 ℃ of dryings, soak 2.5h, 80 ℃ of dryings obtain adsorbing the carrier of crystal seed again;
(4) diauxic growth: with 28.4gNaSiO
39H
2O, 2.4gNaOH, 0.808g Fe (NO
3)
39H
2O, the 90g deionized water, 0.164g sodium metaaluminate and 8.315g TPAOH mix, and change in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, and the vertical submergence of carrier of the absorption crystal seed that step (3) is obtained are wherein, in 170 ℃ of heated sealed 24h;
(5) template TPAOH is removed in calcining: the ultrasonic washing of the product 20min of step (4), and natural drying, be warming up to 550 ℃ with 5 ℃/min speed, insulation 4h is down to room temperature again, makes gradient compound molecule sieve membrane catalysis material.Through aas determination, active material iron-loading rate is 2.1wt% in the catalysis material of preparation.
Adopt SEM that the microstructure of compound Fe-ZSM-5 molecular screen membrane is characterized, as shown in Figure 1.As shown in Figure 1, behind the diauxic growth, gradient compound molecule sieve membrane catalysis material of the present invention surface has formed one deck continuously and fine and close molecular screen membrane.
Adopt XRD that stainless steel fibre felt carrier and gradient compound molecule sieve membrane catalysis material are characterized, as shown in Figure 2.As shown in Figure 2, stainless steel fibre felt carrier and between 2 θ=7 ~ 9 ° two strong peaks are arranged there is individual triplet between 23 ~ 25 °, possessed typical MFI type molecular sieve characteristic peak; And gradient compound molecule sieve membrane catalysis material also has the characteristic peak of stainless steel fento about 43 ° and 50 °.This shows, the present invention by the diauxic growth method synthetic be the compound MFI type of stainless steel fento molecular screen membrane.
The gradient compound molecule sieve membrane catalysis material of embodiment 1 preparation is used for the catalytic oxidation of phenol wastewater, and process is as follows:
Above-mentioned gradient compound molecule sieve membrane catalysis material is cut into the sequin that diameter is 2cm, get in the stainless pipe reactor that 10 sequins are stacked in 20mm * 20mm, obtain reactant liquor to the middle hydrogen peroxide that adds 12.7g mass fraction 30% of the phenol wastewater (pH=4) of 200mL concentration 2500mg/L, peristaltic pump driving reactant liquor seals liquid phase circulation with the flow velocity of 20mL/min, processes 1 ~ 6h.Timing sampling carries out quantitative analysis in Agilent 1100 type liquid chromatographs (Agilent company, the U.S.).The time dependent degradation curve of phenol conversion as shown in Figure 3.As seen from Figure 3, behind the reaction 30min, the phenol degrading rate can reach 41%, and behind the reaction 4h, the phenol degrading rate reaches 91%, illustrates that gradient compound molecule sieve membrane catalysis material of the present invention is a kind of efficient phenol wastewater catalyst for catalytic oxidation.
Claims (8)
1. a gradient compound molecule sieve membrane catalysis material is characterized in that, is present in the molecular sieve structure by iron surface attitude or the oxidation state form of active component iron species with skeleton position iron atom and non-skeleton position, and the load capacity of active component is 0.5 ~ 3.0wt%.
2. the preparation method of gradient compound molecule sieve membrane catalysis material claimed in claim 1 is characterized in that, comprises the steps:
(1) surface preparation of carrier: after the stainless steel fibre felt soaked 10 ~ 60min respectively with the aqueous sulfuric acid of the sodium hydrate aqueous solution of mass concentration 5 ~ 10% and mass concentration 5 ~ 10%, dry, in 600 ~ 700 ℃ of calcining 4 ~ 8h, be soaked in 10 ~ 60min in the poly-hydroxypropyl dimethyl aqueous ammonium chloride solution of mass concentration 0.1 ~ 1%, clean with the rinsing of 0.05 ~ 0.2mol/L ammonia spirit, natural drying, obtain stainless steel fibre felt carrier;
(2) preparation of crystal seed: TPAOH, deionized water and ethanol are mixed, strong stirring slowly drips tetraethoxysilance on one side on one side, after dropwising at room temperature strong stirring 12 ~ 24h clarify to mixed liquor, above-mentioned mixed liquor is sealed Hydrothermal Synthesis 12 ~ 48h in 100 ~ 130 ℃, centrifugal, obtain crystal seed; The mass ratio of described TPAOH, deionized water, ethanol and tetraethoxysilance is (1 ~ 8): (5 ~ 8): (2 ~ 4): (3 ~ 7);
(3) dip-coating of crystal seed: the crystal seed that step (2) is obtained adds in the ammoniacal liquor and obtains mass concentration 1 ~ 4%, pH is 10 brilliant liquid, the stainless steel fibre felt carrier that step (1) is obtained soaks 0.5 ~ 1h in brilliant liquid, dry, soak again 1 ~ 2.5h, 70 ~ 100 ℃ of dryings obtain adsorbing the carrier of crystal seed; The mass ratio of described crystal seed and carrier is 1:(5 ~ 20);
(4) diauxic growth: sodium metasilicate, NaOH, ferric nitrate, deionized water, sodium metaaluminate and TPAOH are mixed, and the carrier submergence of the absorption crystal seed that step (3) is obtained wherein, in 100 ~ 170 ℃ of heated sealed 24 ~ 96h; The mass ratio of described sodium metasilicate, NaOH, ferric nitrate, deionized water, sodium metaaluminate, TPAOH and carrier is (20 ~ 30): (2 ~ 3): (0.202 ~ 0.808): (0 ~ 0.5): (0 ~ 10): (1 ~ 20);
(5) the template TPAOH is removed in calcining: the ultrasonic washing of product of step (4), and natural drying, be warming up to 400 ~ 600 ℃ with 5 ℃/min speed, insulation 4h is down to room temperature again, makes gradient compound molecule sieve membrane catalysis material.
3. preparation method according to claim 2 is characterized in that, the porosity of described stainless steel fibre felt is 70 ~ 90%, and fibre diameter is 0.5 ~ 10 μ m.
4. preparation method according to claim 3 is characterized in that, the thickness of described gradient compound molecule sieve membrane catalysis material is 1 ~ 10 μ m.
5. the application of gradient compound molecule sieve membrane catalysis material claimed in claim 1 in the phenol wastewater catalytic oxidation.
6. application according to claim 5, it is characterized in that, the step of described catalytic oxidation is as follows: the pH that regulates phenol wastewater is 2 ~ 6, the adding hydrogen peroxide solution mixes and obtains mixed liquor, under normal pressure, 50 ~ 80 ℃, mixed liquor is sealed liquid phase circular treatment 1 ~ 6h with the speed of 10 ~ 60mL/min by gradient compound molecule sieve membrane catalysis material.
7. application according to claim 6 is characterized in that, described Phenolic Compounds From Wastewater Containing Phenols total concentration is higher than 1000mg/L.
8. application according to claim 7 is characterized in that, the mass fraction of described hydrogen peroxide solution is 10 ~ 50%, and its mass fraction in mixed liquor is 1 ~ 24%; The mass fraction of described gradient compound molecule sieve membrane catalysis material in mixed liquor is 0.5 ~ 12%.
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| CN106219723A (en) * | 2016-07-26 | 2016-12-14 | 华南理工大学 | A kind of agitator tank membrane reactor processed for waste water and the method for wastewater treatment of this reactor of employing |
| CN107321349A (en) * | 2017-06-26 | 2017-11-07 | 华南理工大学 | A kind of fento coated carbon nano-tube composite material of carried metal active component and its preparation and application |
| CN109647496A (en) * | 2018-11-09 | 2019-04-19 | 南京工业大学 | A kind of multicomponent catalysis material of Zeolite modifying glass fibre and its preparation method and application |
| CN114351126A (en) * | 2022-01-10 | 2022-04-15 | 万华化学集团股份有限公司 | Preparation method of stainless steel fiber-loaded ZSM-5 molecular sieve, water-based damping coating and preparation method thereof |
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| CN103447064A (en) * | 2013-08-30 | 2013-12-18 | 华南理工大学 | Composite molecular sieve film based on paper-shaped gradient metal microfibers as well as preparation method and application thereof |
| CN106219723A (en) * | 2016-07-26 | 2016-12-14 | 华南理工大学 | A kind of agitator tank membrane reactor processed for waste water and the method for wastewater treatment of this reactor of employing |
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| CN107321349A (en) * | 2017-06-26 | 2017-11-07 | 华南理工大学 | A kind of fento coated carbon nano-tube composite material of carried metal active component and its preparation and application |
| CN109647496A (en) * | 2018-11-09 | 2019-04-19 | 南京工业大学 | A kind of multicomponent catalysis material of Zeolite modifying glass fibre and its preparation method and application |
| CN114351126A (en) * | 2022-01-10 | 2022-04-15 | 万华化学集团股份有限公司 | Preparation method of stainless steel fiber-loaded ZSM-5 molecular sieve, water-based damping coating and preparation method thereof |
| CN114351126B (en) * | 2022-01-10 | 2023-10-17 | 万华化学集团股份有限公司 | Preparation method of ZSM-5 molecular sieve loaded with stainless steel fibers, water-based damping paint and preparation method thereof |
| CN116459864A (en) * | 2023-04-04 | 2023-07-21 | 北京师范大学珠海校区 | Preparation method and application of carrier etching secondary synthesis hollow molecular sieve membrane |
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