CN109772444A - A kind of MCM-41 Supported CuO-CeO2The preparation method and application of nanocrystalline catalyst - Google Patents
A kind of MCM-41 Supported CuO-CeO2The preparation method and application of nanocrystalline catalyst Download PDFInfo
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Abstract
The invention discloses a kind of MCM-41 Supported CuO-CeO2The preparation method and application of nanocrystalline catalyst, preparation method include: the preparation of (1) carrier MCM-41；(2)CuO-CeO2The preparation of/MCM-41 catalyst, prepared catalyst is for the catalysis burning of low concentration chlorobenzene.The active component size of catalyst prepared by the present invention is small, the characteristics of being uniformly dispersed, and the activity for being catalyzed burning chlorobenzene is high, and durability is good, is the catalyst of degradation VOC haveing excellent performance with applications well prospect a kind of.
Description
Technical field
The present invention relates to catalyst technical fields, more particularly to a kind of MCM-41 Supported CuO-CeO2Nanocrystalline catalyst
Preparation and its low concentration chlorobenzene catalysis burning application.
Background technique
MCM-41 molecular sieve has the hole of hexagon ordered arrangement, and large specific surface area, size is uniform, thermal stability
Height, aperture can continuously adjust in a certain range, be suitable as carrier.In existing literature, about MCM-41 carried noble metal
Catalyst it has been reported that but noble metal catalyst may be inactivated due to fluorine poisoning and the generation of polychloride by-product, and
And Precious Metals Resources are seldom, the cost for accordingly acting as preparing catalyst is very high.In existing research, do not find transition gold
Category oxide nanocrystalline is carried on the report in terms of MCM-41 is applied to chlorobenzene catalytic degradation, and existing transition metal-catalyzed
Activity of the agent for chlorobenzene catalysis burning is lower, therefore needs a kind of catalyst of high activity.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, a kind of MCM-41 Supported CuO-CeO is provided2Nanometer
The preparation method and application of brilliant catalyst, the active component size of the catalyst of preparation is small, scattered feature, can be used for height
Effect catalysis burning low concentration chlorobenzene.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of MCM-41 Supported CuO-CeO2The preparation method of nanocrystalline catalyst, includes the following steps:
(1) preparation of carrier MCM-41: by 40wt%TEAOH solution and SiO2It is mixed to get with the ratio of mass ratio 10:1
Mixed liquor A adds SiO after being stirred gained mixed liquor A and 25wt%CTAC solution, deionized water2Gel is obtained,
Middle mixed liquor A, CTAC solution, deionized water and SiO2Mass ratio be 12.21:20.3:5.94:5.91, then gel is set
In Teflon bottles, the heating crystallization 120h at 100 DEG C, crystallization terminate after through cooling, be filtered, washed after obtained solid product
Dry 12h is placed in 80 DEG C of baking oven, finally by the solid product after drying in air atmosphere, 550 DEG C of temperature lower calcination 5h
To remove template CTAC, carrier MCM-41 is obtained；
(2)CuO-CeO2The preparation of/MCM-41 catalyst: obtained MCM-41 is dispersed in ultrapure water, is then dripped
Enter Cu (NO3)2·3H2O solution and Ce (NO3)3·6H2O solution, and 1h is sufficiently stirred at 25 DEG C, wherein MCM-41, ultrapure
Water, Cu (NO3)2·3H2O solution and Ce (NO3)3·6H2The amount ratio of O solution is 1g:100mL:1.7mL:0.288mL, then is dripped
Add ammonium hydroxide to adjust pH to 9.0, continues to be centrifuged after stirring 12h, washs to obtain solid product, by solid product in 60 DEG C of air atmospheres
Middle dry 12h is enclosed, 500 DEG C of calcining 2h in Muffle furnace is then placed in again, obtains CuO-CeO2/ MCM-41 catalyst, wherein Cu and
The molar ratio that Ce accounts for 10%, the Cu and Ce of catalyst gross mass altogether is 6:1.
In the step (2), Cu (NO3)2·3H2The concentration of O solution is 1mol/L, Ce (NO3)3·6H2The concentration of O solution
For 1mol/L, the concentration of ammonium hydroxide is 1mol/L.
The catalyst is for the catalysis burning of low concentration chlorobenzene.
Since carrier MCM-41 has biggish specific surface area and gap structure abundant, pass through in volatile organic matter
When, porous effect can be played, adsorb a large amount of organic matter, and MCM-41 active component can be made on its surface as carrier or
Hole inner height dispersion, to improve the activity of catalysis burning low concentration chlorobenzene.
The beneficial effects of the present invention are: preparing CuO-CeO by carrier of MCM-412Nanocrystalline catalyst, active component
Particle size is small, is uniformly dispersed, and the activity of catalysis burning chlorobenzene is high, and durability is good, is a kind of property with applications well prospect
The catalyst of degradation VOC that can be excellent.
Detailed description of the invention
Fig. 1 is CuO-CeO2The high-resolution-ration transmission electric-lens figure of/MCM-41 catalyst；
Fig. 2 is carrier MCM-41 and CuO-CeO2The nitrogen adsorption desorption comparison diagram of/MCM-41 catalyst；
Fig. 3 is CuO-CeO2The activity figure of/MCM-41 catalyst for the catalysis burning of low concentration chlorobenzene；
Fig. 4 is CuO-CeO2The durability test figure of/MCM-41 catalyst.
Specific embodiment
Present invention will be further described below with reference to the accompanying drawings and specific embodiments:
The preparation of catalyst
(1) preparation of carrier MCM-41: by 40wt%TEAOH solution and SiO2It is mixed to get with the ratio of mass ratio 10:1
Mixed liquor A adds SiO after being stirred gained mixed liquor A and 25wt%CTAC solution, deionized water2Gel is obtained,
Middle mixed liquor A, CTAC solution, deionized water and SiO2Mass ratio be 12.21:20.3:5.94:5.91, then gel is set
In Teflon bottles, the heating crystallization 120h at 100 DEG C, crystallization terminate after through cooling, be filtered, washed after obtained solid product
Dry 12h is placed in 80 DEG C of baking oven, finally by the solid product after drying in air atmosphere, 550 DEG C of temperature lower calcination 5h
To remove template CTAC, carrier MCM-41 is obtained；
(2)CuO-CeO2The preparation of/MCM-41 catalyst: obtained MCM-41 is dispersed in ultrapure water, is then dripped
Enter the Cu (NO of 1mol/L3)2·3H2Ce (the NO of O solution and 1mol/L3)3·6H2O solution, and 1h is sufficiently stirred at 25 DEG C,
Wherein MCM-41, ultrapure water, Cu (NO3)2·3H2O solution and Ce (NO3)3·6H2The amount ratio of O solution is 1g:100mL:
1.7mL:0.288mL, then the ammonium hydroxide adjusting pH to 9.0 of 1mol/L is added dropwise, continue to be centrifuged after stirring 12h, wash to obtain solid
Solid product is dried in 60 DEG C of air atmospheres 12h, is then placed in 500 DEG C of calcining 2h in Muffle furnace again, obtains CuO- by product
CeO2/ MCM-41 catalyst, it is 6:1 that wherein Cu and Ce accounts for the molar ratio of 10%, the Cu and Ce of catalyst gross mass altogether.
The catalyst is for the catalysis burning of low concentration chlorobenzene.
Interpretation of result:
Fig. 1 is CuO-CeO2The high-resolution-ration transmission electric-lens figure of/MCM-41 catalyst.The pattern of sample utilizes JEOL-2010
Type transmission electron microscope characterization, operating voltage 200kV.As shown in Figure 1, CuO-CeO2The active component CuO of/MCM-41 catalyst and
CeO2Particle diameter in 3~5nm, and active component is evenly dispersed in the surface MCM-41.
Fig. 2 is carrier MCM-41 and CuO-CeO2The nitrogen adsorption desorption comparison diagram of/MCM-41 catalyst.Nitrogen adsorption desorption is real
It tests in Tristar II 3020 (Micromeritics Company, USA) automatic adsorption device and is analyzed, experiment condition is such as
Under: under liquid nitrogen temperature (77K), utilize N2Determination of adsorption method SBET, surveyed using Barrett-Joyner-Halenda (BJH) method
Determine Vp.As shown in Figure 2, obtained CuO-CeO2For/MCM-41 catalyst there are meso-hole structure, specific surface area is very big.
Table 1 is carrier MCM-41 and CuO-CeO2Specific surface area, the total pore volume statistics of/MCM-41 catalyst.From table 1
As can be seen that the S of carrier MCM-41BETAnd VpRespectively in 805.9m2/ g and 0.795cm3/ g, Supported CuO-CeO2After nanocrystalline,
CuO-CeO2The S of/MCM-41 catalystBETAnd VpRespectively reduce 478.5m2/ g and 0.367cm3/ g, the load of this declaratives
CuO-CeO2In the nanocrystalline duct for entering MCM-41, so that cell channels are blocked.
Table 1 carrier MCM-41 and CuO-CeO2Specific surface area, the total pore volume statistics of/MCM-41 catalyst
aBET specific surface area.
bTotal pore volume estimated at P/P0=0.99.
Fig. 3 is CuO-CeO2The activity figure of/MCM-41 catalyst for low concentration chlorobenzene catalytic degradation.Active appraisal experiment
It is carried out on WFS-3010 (Tianjin is first weighed) reaction unit, air speed 20000h-1, chlorobenzene concentration is 1000ppm.Using online
Gas-chromatography (Shimadzu, GC-14C, apan) enters the organic of chromatography using flame ionization ditector (FID) detection
Object concentration.Chromatography operating condition is as follows: 120 DEG C of temperature of vaporization chamber, 80 DEG C of column temperature.It is recorded using N2000 on-line chromatograph work station
Analyze data.From the figure 3, it may be seen that CuO-CeO2/ MCM-41 catalyst makes the conversion ratio of chlorobenzene reach 99.2% at 260 DEG C.
Fig. 4 is CuO-CeO2The durability test figure of/MCM-41 catalyst.The test condition of durability experiment is commented with activity
Valence experiment is identical.As shown in Figure 4, benzene and H is being not added2When O, CuO-CeO2/ MCM-41 successive reaction 100h, chlorobenzene at 260 DEG C
Conversion ratio be only reduced to 93% from 96%, illustrate that prepared catalyst has very good stability；When introduce benzene into
When row durability test, the conversion ratio decline of the preceding 5h of successive reaction at 260 DEG C, chlorobenzene are very fast, and after successive reaction 5h,
The conversion ratio of chlorobenzene maintains 66%, as introducing H2When O carries out durability test, the preceding 5h of successive reaction, chlorobenzene at 260 DEG C
Conversion ratio decline it is very fast, and after successive reaction 5h, the conversion ratio of chlorobenzene maintains 78%, and the above results show CuO-
CeO2/ MCM-41 catalyst can be effective against benzene and H2The influence of O.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of MCM-41 Supported CuO-CeO2The preparation method of nanocrystalline catalyst, characterized by the following steps:
(1) preparation of carrier MCM-41: by 40wt%TEAOH solution and SiO2Mixing is mixed to get with the ratio of mass ratio 10:1
Liquid A adds SiO after being stirred gained mixed liquor A and 25wt%CTAC solution, deionized water2Gel is obtained, wherein mixing
Close liquid A, CTAC solution, deionized water and SiO2Mass ratio be 12.21:20.3:5.94:5.91, then gel is placed in
In Teflon bottles, the heating crystallization 120h at 100 DEG C, crystallization terminate after through cooling, be filtered, washed after obtained solid product set
The dry 12h in 80 DEG C of baking oven, finally by the solid product after drying in air atmosphere, 550 DEG C of temperature lower calcination 5h with
Template CTAC is removed, carrier MCM-41 is obtained；
(2)CuO-CeO2The preparation of/MCM-41 catalyst: obtained MCM-41 is dispersed in ultrapure water, Cu is then instilled
(NO3)2·3H2O solution and Ce (NO3)3·6H2O solution, and 1h is sufficiently stirred at 25 DEG C, wherein MCM-41, ultrapure water, Cu
(NO3)2·3H2O solution and Ce (NO3)3·6H2The amount ratio of O solution is 1g:100mL:1.7mL:0.288mL, then ammonium hydroxide is added dropwise
PH to 9.0 is adjusted, continues to be centrifuged after stirring 12h, wash to obtain solid product, solid product is done in 60 DEG C of air atmospheres
Then dry 12h is placed in 500 DEG C of calcining 2h in Muffle furnace again, obtains CuO-CeO2/ MCM-41 catalyst, wherein Cu and Ce are accounted for altogether
The molar ratio of 10%, the Cu and Ce of catalyst gross mass are 6:1.
2. a kind of MCM-41 Supported CuO-CeO as described in claim 12The preparation method of nanocrystalline catalyst, it is characterised in that:
In the step (2), Cu (NO3)2·3H2The concentration of O solution is 1mol/L, Ce (NO3)3·6H2The concentration of O solution is 1mol/
L, the concentration of ammonium hydroxide are 1mol/L.
3. a kind of MCM-41 Supported CuO-CeO according to claim 12The preparation method preparation of nanocrystalline catalyst is urged
The application of agent, it is characterised in that: the catalyst is for the catalysis burning of low concentration chlorobenzene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234055A (en) * | 2020-01-19 | 2020-06-05 | 上海化工研究院有限公司 | Supported titanium catalyst and preparation method and application thereof |
| CN112023976A (en) * | 2020-08-31 | 2020-12-04 | 中国科学院地球环境研究所 | Bimetallic modified MCM-41 molecular sieve catalyst, preparation method and application |
| CN115364864A (en) * | 2021-05-20 | 2022-11-22 | 中国科学院大连化学物理研究所 | Application of Cu-Ce composite metal oxide in degradation of chlorinated aromatic organic pollutants |
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| CN101185796A (en) * | 2007-12-11 | 2008-05-28 | 华东理工大学 | Chlorination aromatic hydrocarbon waste gases catalytic purification method |
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| CN101185796A (en) * | 2007-12-11 | 2008-05-28 | 华东理工大学 | Chlorination aromatic hydrocarbon waste gases catalytic purification method |
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| QINQIN HUANG等: "Catalytic behavior and durability of CeO2 or/and CuO modified USY zeolite catalysts for decomposition of chlorinated volatile organic compounds", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234055A (en) * | 2020-01-19 | 2020-06-05 | 上海化工研究院有限公司 | Supported titanium catalyst and preparation method and application thereof |
| CN111234055B (en) * | 2020-01-19 | 2022-11-08 | 上海化工研究院有限公司 | Supported titanium catalyst, and preparation method and application thereof |
| CN112023976A (en) * | 2020-08-31 | 2020-12-04 | 中国科学院地球环境研究所 | Bimetallic modified MCM-41 molecular sieve catalyst, preparation method and application |
| CN115364864A (en) * | 2021-05-20 | 2022-11-22 | 中国科学院大连化学物理研究所 | Application of Cu-Ce composite metal oxide in degradation of chlorinated aromatic organic pollutants |
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Application publication date: 20190521 |