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CN104437666A - Al-SBA-15 support and Ag/Al-SBA-15 catalyst and preparation method of support and catalyst and application of catalyst in environmental pollution control - Google Patents

Al-SBA-15 support and Ag/Al-SBA-15 catalyst and preparation method of support and catalyst and application of catalyst in environmental pollution control Download PDF

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CN104437666A
CN104437666A CN201410804862.XA CN201410804862A CN104437666A CN 104437666 A CN104437666 A CN 104437666A CN 201410804862 A CN201410804862 A CN 201410804862A CN 104437666 A CN104437666 A CN 104437666A
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catalyst
sba
hours
preparation
mesoporous supports
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张晓东
董寒
赵迪
左元慧
崔立峰
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention discloses an Al-doped SBA-15 mesoporous support and a preparation method of the Al-doped SBA-15 mesoporous support. The Al-doped SBA-15 mesoporous support is that the molar ratio of Si to Al is (250-50): 1; the aperture of the mesoporous support is 6.0 to 8.5nm, the specific surface area is 350 to 600m<2>/g, and the total pore volume is 0.50 to 1.50cm<3>g<-1>. The invention also discloses a nano-silver catalyst loaded on the Al-SBA-15 support and a preparation method of the nano-silver catalyst. The nano-silver catalyst loaded on the Al-SBA-15 support is that Ag in the support accounts for 2 to 20wt% of the weight of the catalyst; and the aperture of the catalyst is 6.8 to 8.5nm, the specific surface area is 300 to 500m<2>/g, and the total pore volume is 0.50 to 1.50cm<3>g<-1>. The invention further discloses an application of the catalyst for removing CO in hydrogen-rich gas, as well as the application of oxidizing CO in the hydrogen-rich gas and removing volatile organic pollutants and nitric oxide in sulfur dioxide containing gas.

Description

The application in control environmental pollution of a kind of Al-SBA-15 carrier, Ag/Al-SBA-15 catalyst, their preparation method and catalyst
Technical field
The invention belongs to inorganic nano catalysis material field, be specifically related to the preparation method of the preparation method of a kind of mesoporous silicon oxide carrier A l-SBA-15 and this carrier, the Ag/Al-SBA-15 catalyst be made up of this carrier and active component and this catalyst, and the application of catalyst in control environmental pollution.
Background technology
Polymer electrode membrane fuel electrode (Polymer Electrolyte Membrane FuelCell, PEMFC) for traditional internal combustion engine, have the feature of higher energy conversion efficiency and no pollution discharge, therefore PEMFC is paying close attention to widely for the application on motor receives.At present, the hydrogen source of fuel cell obtains primarily of the steam reforming of the hydrocarbon such as methyl alcohol, natural gas, the technology such as partial oxidation and thermal reforming.Because the operating temperature of PEMFC is lower, platinum (Pt) electrode is easy to micro CO (CO) (about 1%) be reformed in gas and pollutes.Therefore CO in hydrogen source is eliminated very important to the application of PEMFC.Remove for selective catalytic oxidation for the CO in hydrogen rich gas, key is the oxidation to CO, improve CO on a catalyst with O 2the performance (i.e. activity) of reaction and compete the ability (namely selective) of oxygen with hydrogen, also requires that reaction temperature can not be too high simultaneously.
Up to now, people adopt the noble metal catalyst such as platinum (Pt), rhodium (Rh), gold (Au) to carry out CO catalytic oxidation.Chemically technique and reduce costs consideration, reduces reaction temperature, seeking cheap metal and part, to replace noble metal will be the main target studying CO selective oxidation from now on.As everyone knows, relatively inexpensive silver is a kind of ethylene epoxidation catalyst preferably.Report silver (Ag) load at mesoporous silicon oxide (SiO 2) on, it has good catalytic reaction activity (Zhang, X.D. to CO oxidation; Qu, Z.P.; Yu, F.L.; Wang, Y.J.Catal.2013,297,264-271.), but when this catalyst uses in hydrogen rich gas atmosphere, the conversion ratio of CO is lower, limits its commercial Application.
Summary of the invention
One aspect of the present invention provides a kind of for the carrier of supported catalyst and the preparation method of this carrier.
The carrier of catalyst of the present invention is a kind of SBA-15 mesoporous supports being doped with Al, is expressed as Al-SBA-15.The mol ratio of Si and the Al in carrier is 250 ~ 50:1, and aperture is 6.0 ~ 8.5nm, and specific area is 350 ~ 600m 2/ g, total pore volume is 0.50 ~ 1.50cm 3g -1.In some embodiments, the mol ratio of Si and Al is 200 ~ 50:1, and aperture is 6.5 ~ 8.0nm, and specific area is 400 ~ 500m 2/ g, total pore volume is 0.60 ~ 1.20cm 3g -1.
Above-mentioned carrier can adopt in-situ synthetic method, prepares according to the following steps:
(1) template triblock copolymer P123 (PEO-PPOX-PEO triblock copolymer, PEO-PPO-PEO) is joined acid solution, at 30-50 DEG C, vigorous stirring makes it dissolve completely;
(2) in the above-mentioned acid solution dissolving P123, add silicon source, stir 2 ~ 6 hours, then add aluminium source, continue stirring 24 ~ 48 hours, obtain microemulsion;
(3) microemulsion of above gained is placed in closed container crystallization 24 ~ 48 hours at 80 ~ 120 DEG C;
(4) regulate pH to 3 ~ 9 with alkali, again microemulsion be placed in closed container crystallization 24 ~ 48 hours at 80 ~ 120 DEG C afterwards, washing, filter, at 60 ~ 120 DEG C dry 6 ~ 24 hours;
(5) solids will obtained above, calcines 6 ~ 12 hours, obtains carrier A l-SBA-15 in air atmosphere at 500-600 DEG C.
In the above-mentioned methods, acid solution can be such as any inorganic acid or organic acid, such as solution of hydrochloric acid, sulfuric acid, nitric acid etc. with acidity, is preferably hydrochloric acid solution.
Above-mentioned silicon source can be such as compound of silicate class, the lower alkoxy ester of the lower alkyl esters of such as positive silicic acid or the positive silicic acid of positive silicic acid.The lower alkyl esters of positive silicic acid can be such as methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester etc., is preferably methyl silicate and ethyl orthosilicate.The lower alkoxy ester of positive silicic acid can be such as positive silicic acid methoxyethoxy ester, positive silicic acid ethoxy ester, positive silicic acid third oxygen ester etc., is preferably positive silicic acid methoxyethoxy ester and positive silicic acid ethoxy ester.
Above-mentioned aluminium source can be such as inorganic acid aluminium or organic acid aluminium, such as aluminum sulfate, aluminum nitrate, aluminium isopropoxide etc.
Above-mentioned for regulating the alkali of the pH value of above-mentioned microemulsion can be such as the material that ammoniacal liquor, NaOH etc. have alkalescence.
Prepare in the embodiment of carrier A l-SBA-15 a kind of, the mol ratio of silicon source, P123, hydrochloric acid is 1:0.017:5.8, and the aluminium source added and the mol ratio in silicon source can in the scopes of 0.005 ~ 0.02:1.
Inventor finds, by regulating the pH value of microemulsion, it is made to change in the scope of 3 ~ 9, the Si/Al mol ratio in the catalyst carrier Al-SBA-15 obtained can be made to be 200 ~ 50:1, catalyst carrier has homogeneous meso-hole structure, and aperture is 6.0 ~ 8.5nm, and has high specific area and large pore volume, wherein, specific area is 350 ~ 600m 2/ g, total pore volume is 0.50 ~ 1.50cm 3g -1.
The present invention provides on the other hand a kind of preparation method being carried on nano-silver catalyst on Al-SBA-15 carrier and this catalyst.
In the nano-silver catalyst be carried on Al-SBA-15 carrier of the present invention, active component A g weight content is in the catalyst 2 ~ 20wt%, and the aperture of catalyst is 6.0 ~ 8.5nm, and specific area is 300 ~ 500m 2/ g, total pore volume is 0.50 ~ 1.50cm 3g -1, in some embodiments, Ag weight content is in the catalyst 2 ~ 16wt%, and the aperture of catalyst is 6.5 ~ 8.0nm, and specific area is 350 ~ 450m 2/ g, total pore volume is 0.60 ~ 1.10cm 3g -1.
Loaded nano silver catalyst of the present invention adopts infusion process to be prepared under the condition of lucifuge.Preparation process is as follows: by Al-SBA-15 carrier solubilizes obtained above in water, under agitation add silver nitrate, stir 0.5 ~ 1 hour, leaves standstill 6 ~ 24 hours, and at 80 ~ 120 DEG C, drying 6 ~ 24 hours, prepares Ag/Al-SBA-15 catalyst.In gained loaded nano silver catalyst, active component A g weight content is in the catalyst 2 ~ 20wt%, and the aperture of catalyst is 6.0 ~ 8.5nm, and specific area is 300 ~ 500m 2/ g, total pore volume is 0.50 ~ 1.50cm 3g -1.
Another aspect of the invention provide loaded nano silver catalyst eliminate in hydrogen rich gas atmosphere CO, CO oxidation in oxygen-enriched atmosphere, volatile organic contaminant oxidation, containing the application in sulfur dioxide atmosphere NO_x elimination etc.
The technology and equipment of Kaolinite Preparation of Catalyst carrier of the present invention and catalyst is simple, with low cost, reproducible, prepared Al-SBA-15 carrier has homogeneous meso-hole structure and high-ratio surface sum pore volume, prepared Ag/Al-SBA-15 catalyst has the activity of the carbon monoxide in higher selective oxidation hydrogen at a lower temperature, and good stability can also be kept, can effectively resist carbon dioxide and water mitigation.In addition, this catalyst can also be used as catalysis CO oxidation in oxygen-enriched atmosphere, volatile organic contaminant, containing in the reactions such as sulfur dioxide atmosphere NO_x elimination, have wide prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is little angle x-ray diffraction pattern (XRD) of Al-SBA-15 carrier (a) and Ag/Al-SBA-15 catalyst (b).Abscissa is the angle of diffraction (2 θ) of twice, and ordinate is the intensity (cps) of diffraction maximum.
Fig. 2 is wide angle x-ray diffraction pattern (XRD) of Ag/Al-SBA-15 catalyst.Abscissa is the angle of diffraction (2 θ) of twice, and ordinate is the intensity (cps) of diffraction maximum.
Fig. 3 is the N of Al-SBA-15 carrier (a) and Ag/Al-SBA-15 catalyst (b) 2adsorption-desorption figure.Abscissa is relative pressure (P/P 0), ordinate absorbs volume (cm 3/ g -1).
Fig. 4 is the graph of pore diameter distribution of Al-SBA-15 carrier (a) and Ag/Al-SBA-15 catalyst (b).Abscissa is aperture (nm), and ordinate is pore volume (cm 3g -1nm -1).
Fig. 5 is that Ag/Al-SBA-15 Catalyst for CO low-temperature oxidation activity is with reaction time change curve.Abscissa is reaction time (min), and ordinate is CO conversion ratio (%).
Fig. 6 is that Ag/Al-SBA-15 Catalyst for CO is selective with reaction time change curve.Abscissa is reaction time (min), and ordinate is CO selective (%).
Detailed description of the invention
During CO oxidation activity in the hydrogen rich gas atmosphere of catalyst is evaluated, the composition of unstripped gas by volume percentages is: 1%CO, 0.5-20%O 2, 0-10%CO 2, 0-5%H 2o, 98.5-64%H 2, gaseous mixture flow velocity is 30-100ml/min, obtains the conversion ratio of CO, thus evaluate the activity of catalyst by the content of CO before and after detection reaction.
In the CO oxidation of catalyst in oxygen-enriched atmosphere, volatile organic contaminant oxidation, activity rating containing sulfur dioxide atmosphere NO_x elimination, not hydrogen in the composition of unstripped gas, but containing a certain amount of specific pollutants, as formaldehyde, toluene, nitric oxide and sulfur dioxide.Obtained the conversion ratio of pollutant by the content of the pollutant in detection reaction product, thus the activity of catalyst is evaluated.
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing, but content of the present invention is not limited thereto.
embodiment 1
The preparation of Al-SBA-15 carrier: 4g template triblock copolymer P123 joins in the 2Mol/L hydrochloric acid solution prepared in advance, wherein hydrochloric acid solution 125ml, then 40 DEG C of stirrings in water-bath, P123 dissolves completely, to forming clear solution.Add 8.5g ethyl orthosilicate and stir 4h, 0.068g aluminum sulfate is added again in solution, after stirring 24h, the microemulsion obtained is transferred in autoclave, put into 100 DEG C of baking ovens and leave standstill crystallization 48h, to be cooled to room temperature, pH value of solution is regulated to be 7.5 with ammoniacal liquor, again mixed liquor is transferred in autoclave, put into 100 DEG C of baking ovens and leave standstill crystallization 48h, to be cooled to room temperature filtration, washing, 100 DEG C of dry 12h in vacuum drying chamber, 540 DEG C of calcining 10h in Muffle furnace, can obtain Al-SBA-15 carrier in air atmosphere.
The preparation of Ag/Al-SBA-15 catalyst: take 1gAl-SBA-15 carrier solubilizes in 5ml water, under agitation add 0.126g silver nitrate, continue to stir 1h, leave standstill 12h, 100 DEG C of dry 12h, prepare 8wt%Ag/Al-SBA-15 catalyst in an oven.
XRD, N of above-mentioned carrier and catalyst 2adsorption-desorption and pore-size distribution as Fig. 1,2,3, shown in 4.
The activity rating of catalyst carries out in fixed bed continuous-flow differential reactor, and reactor is the glass U-tube of internal diameter 4mm, and loaded catalyst is 200mg, and unstripped gas forms: 1%CO (volume ratio), 1%O 2, 98%H 2, gas flow rate is 30ml/min, and the CO in reaction 20min afterproduct gas is through being furnished with the GC-7890II gas chromatograph on-line analysis of thermal conductivity cell detector.Reactivity is represented by the conversion ratio of CO.Its catalytic activity and selectively the results are shown in Figure 5,6.CO conversion increases along with the rising of reaction temperature, and 60 DEG C time, CO conversion ratio reaches a maximum is 51.5%, then reduces along with the rising of temperature (Fig. 5).The reduction of high temperature CO conversion causes because oxygen and hydrogen react.The selective of selectivity oxidizing carbon monoxide is monotone decreasing trend (Fig. 6) with the rising of reaction temperature.Illustrate that Ag/Al-SBA-15 catalyst is conducive to the selectivity oxidizing carbon monoxide of low temperature.
embodiment 2
According to the Al-SBA-15 preparation method of the present invention of embodiment 1, add 6.2g methyl silicate to replace ethyl orthosilicate.The evaluation method of catalyst is with embodiment 1.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst CO conversion ratio 60 DEG C time using this method to prepare remains on more than 50%.
embodiment 3
According to the Al-SBA-15 preparation method of the present invention of embodiment 1, add 0.0104g aluminium isopropoxide to replace aluminum sulfate, silver nitrate addition becomes 0.0315g.The evaluation method of catalyst is with embodiment 1.Active testing shows, the 2wt%Ag/Al-SBA-15 catalyst CO conversion ratio 60 DEG C time using this method to prepare remains on more than 50%.
embodiment 4
According to the Al-SBA-15 preparation method of the present invention of embodiment 1, add NaOH to replace ammoniacal liquor, regulate pH value of solution to become 9, silver nitrate addition becomes 0.2520g.The evaluation method of catalyst is with embodiment 1.Active testing shows, the 16wt%Ag/Al-SBA-15 catalyst CO conversion ratio 60 DEG C time using this method to prepare remains on more than 50%.
embodiment 5
According to the Al-SBA-15 preparation method of the present invention of embodiment 1, 4g P123 joins in 2Mol/L hydrochloric acid solution, water-bath temperature becomes 30 DEG C, add 8.5g ethyl orthosilicate mixing time and become 6h, add 0.0191g aluminum nitrate to replace aluminum sulfate, continue mixing time and become 48h, the microemulsion obtained is transferred in autoclave, oven temperature becomes 80 DEG C, standing crystallization time becomes 36h, to be cooled to room temperature, pH value of solution is regulated to become 5 with ammoniacal liquor, again the microemulsion obtained is transferred in autoclave afterwards, oven temperature becomes 80 DEG C, standing crystallization time becomes 36h, to be cooledly to filter to room temperature, washing, vacuum drying chamber temperature becomes 60 DEG C, time becomes 24h, Muffle furnace calcining heat becomes 500 DEG C, time becomes 12h.The evaluation method of catalyst is with embodiment 1.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst CO conversion ratio 60 DEG C time using this method to prepare remains on more than 50%.
embodiment 6
According to the Al-SBA-15 preparation method of the present invention of embodiment 1, 4g P123 joins in 2Mol/L hydrochloric acid solution, water-bath temperature becomes 50 DEG C, add 8.5g ethyl orthosilicate mixing time and become 2h, aluminum sulfate addition becomes 0.272g, continue mixing time and become 36h, the microemulsion obtained is transferred in autoclave, oven temperature becomes 120 DEG C, standing crystallization time becomes 24h, to be cooled to room temperature, pH value of solution is regulated to become 3 with ammoniacal liquor, again the microemulsion obtained is transferred in autoclave afterwards, oven temperature becomes 120 DEG C, standing crystallization time becomes 24h, to be cooledly to filter to room temperature, washing, vacuum drying chamber temperature becomes 120 DEG C, time becomes 6h, Muffle furnace calcining heat becomes 600 DEG C, time becomes 6h.The evaluation method of catalyst is with embodiment 1.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst CO conversion ratio 60 DEG C time using this method to prepare remains on more than 50%.
embodiment 7
According to the Ag/Al-SBA-15 method for preparing catalyst of the present invention of embodiment 1, under agitation add silver nitrate, continue to stir 0.5h, leave standstill 24h, 120 DEG C of dry 6h.The evaluation method of catalyst is with embodiment 1.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst CO conversion ratio 60 DEG C time using this method to prepare remains on more than 50%.
embodiment 8
According to the Ag/Al-SBA-15 method for preparing catalyst of the present invention of embodiment 1, unstripped gas composition becomes: 1%CO (volume ratio), 0.5%O 2, 98.5%H 2, gas flow rate is 100ml/min.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst CO conversion ratio 60 DEG C time using this method to prepare remains on more than 50%.
embodiment 9
According to the Ag/Al-SBA-15 method for preparing catalyst of the present invention of embodiment 1, unstripped gas composition becomes: 1%CO (volume ratio), 20%O 2, 10%CO 2, 5%H 2o, 64%H 2, gas flow rate is 30ml/min.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst CO conversion ratio 60 DEG C time using this method to prepare remains on more than 40%, and this catalyst has the performance of good resistant to carbon dioxide and water.
embodiment 10
According to the Ag/Al-SBA-15 method for preparing catalyst of the present invention of embodiment 1, be applied to the CO oxidation under oxygen-enriched atmosphere, unstripped gas composition becomes: 1%CO (volume ratio), 20%O 2, 79%He, gas flow rate is 30ml/min.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst using this method to prepare is converted into CO completely at 30 DEG C of complete catalysis CO 2.
embodiment 11
According to the Ag/Al-SBA-15 method for preparing catalyst of the present invention of embodiment 1, be applied to volatile organic contaminant oxidation of formaldehyde, unstripped gas composition becomes: 500ppm formaldehyde, 20%O 2, He balances, and gas flow rate is 30ml/min.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst formaldehyde 60 DEG C time using this method to prepare is eliminated completely.
embodiment 12
According to the Ag/Al-SBA-15 method for preparing catalyst of the present invention of embodiment 1, be applied to volatile organic contaminant toluene oxidation, unstripped gas composition becomes: 500ppm toluene, 20%O 2, He balances, and gas flow rate is 30ml/min.Active testing shows, the 8wt%Ag/Al-SBA-15 catalyst toluene 150 DEG C time using this method to prepare is eliminated completely.
embodiment 13
According to the Ag/Al-SBA-15 method for preparing catalyst of the present invention of embodiment 1, be applied to the NO_x elimination containing sulfur dioxide atmosphere, unstripped gas composition becomes: 1000ppm NO, 1000ppm C 3h 6, 250ppm SO 2, 10%O 2, 10%H 2o, He balance, and gas flow rate is 100ml/min.Active testing shows, uses 8wt%Ag/Al-SBA-15 catalyst N 200 DEG C time prepared by this method 2yield can reach more than 60%.
Table 1 Al-SBA-15 carrier and Ag/Al-SBA-15 catalyst performance index
The catalytic performance of table 2 Ag/Al-SBA-15

Claims (10)

1. be doped with a SBA-15 mesoporous supports of Al, be expressed as Al-SBA-15, wherein, the mol ratio of Si and Al is 250 ~ 50:1, and the aperture of mesoporous supports is 6.0 ~ 8.5nm, and specific area is 350 ~ 600m 2/ g, total pore volume is 0.50 ~ 1.50cm 3g -1.
2. the mesoporous supports of claim 1, wherein the mol ratio of Si and Al is 200 ~ 50:1, and aperture is 6.5 ~ 8.0nm, and specific area is 400 ~ 500m 2/ g, total pore volume is 0.60 ~ 1.20cm 3g -1.
3. be doped with a preparation method for the SBA-15 mesoporous supports of Al, comprise the following steps:
(1) template triblock copolymer P123 (PEO-PPOX-PEO triblock copolymer, PEO-PPO-PEO) is joined acid solution, at 30-50 DEG C, vigorous stirring makes it dissolve completely;
(2) in the above-mentioned acid solution dissolving P123, add silicon source, stir 2 ~ 6 hours, then add aluminium source, continue stirring 24 ~ 48 hours, obtain microemulsion;
(3) microemulsion of above gained is placed in closed container crystallization 24 ~ 48 hours at 80 ~ 120 DEG C;
(4) regulate pH to 3 ~ 9 with alkali, again microemulsion be placed in closed container crystallization 24 ~ 48 hours at 80 ~ 120 DEG C afterwards, washing, filter, at 60 ~ 120 DEG C dry 6 ~ 24 hours;
(5) solids will obtained above, calcines 6 ~ 12 hours, obtains carrier in air atmosphere at 500-600 DEG C.
4. the preparation method being doped with the SBA-15 mesoporous supports of Al of claim 3, wherein the mol ratio in aluminium source and silicon source is 0.005 ~ 0.02:1.
5. the preparation method of the mesoporous supports of claim 3, wherein acid solution is hydrochloric acid solution, and silicon source is methyl silicate or ethyl orthosilicate, is ammoniacal liquor for regulating the alkali of the pH value of microemulsion.
6. be carried on the nano-silver catalyst be doped with on the SBA-15 mesoporous supports of Al, wherein Ag weight content is in the catalyst 2 ~ 20wt%, and the aperture of catalyst is 6.0 ~ 8.5nm, and specific area is 300 ~ 500m 2/ g, total pore volume is 0.50 ~ 1.50cm 3g -1.
7. the catalyst of claim 6, wherein Ag weight content is in the catalyst 2 ~ 16wt%, and the aperture of catalyst is 6.5 ~ 8.0nm, and specific area is 350 ~ 450m 2/ g, total pore volume is 0.60 ~ 1.10cm 3g -1.
8. one kind is carried on the preparation method of the nano-silver catalyst be doped with on the SBA-15 mesoporous supports of Al, infusion process is wherein adopted to be prepared under the condition of lucifuge, preparation process comprises the following steps: by the mesoporous supports any one of claim 1-2 or be dissolved in water according to mesoporous supports prepared by the method any one of claim 3-5, under agitation add silver nitrate, stir 0.5 ~ 1 hour, leave standstill 6 ~ 24 hours, at 80 ~ 120 DEG C, drying 6 ~ 24 hours, prepares catalyst.
9. the application of CO eliminated by the catalyst any one of claim 6-7 in hydrogen rich gas atmosphere.
10. the CO oxidation of the catalyst any one of claim 6-7 in oxygen-enriched atmosphere, volatile organic contaminant, containing the application in the NO_x elimination of sulfur dioxide atmosphere.
CN201410804862.XA 2014-12-18 2014-12-18 Al-SBA-15 support and Ag/Al-SBA-15 catalyst and preparation method of support and catalyst and application of catalyst in environmental pollution control Pending CN104437666A (en)

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CN113019432A (en) * 2019-12-25 2021-06-25 中国石油化工股份有限公司 Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN109482223A (en) * 2017-09-13 2019-03-19 神华集团有限责任公司 The method of fly ash base denitrating catalyst and preparation method thereof and denitration
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CN109437223A (en) * 2018-11-06 2019-03-08 中国神华能源股份有限公司 It is a kind of to utilize Al-SBA-15 molecular sieve made from white clay and preparation method thereof
CN113019432A (en) * 2019-12-25 2021-06-25 中国石油化工股份有限公司 Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof
CN113019432B (en) * 2019-12-25 2023-09-01 中国石油化工股份有限公司 Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof

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Application publication date: 20150325