CN102553575B - Preparation method of CeO2-MnO2 composite catalyst with efficient photothermal synergistic catalytic purification function for VOCs (Volatile Organic Chemicals) - Google Patents

Preparation method of CeO2-MnO2 composite catalyst with efficient photothermal synergistic catalytic purification function for VOCs (Volatile Organic Chemicals) Download PDF

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CN102553575B
CN102553575B CN201210029241.XA CN201210029241A CN102553575B CN 102553575 B CN102553575 B CN 102553575B CN 201210029241 A CN201210029241 A CN 201210029241A CN 102553575 B CN102553575 B CN 102553575B
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mno
catalyst
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concerted catalysis
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CN102553575A (en
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李远志
侯静涛
任璐
代洋
胡胜鹰
赵修建
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Wuhan University of Technology WUT
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Abstract

The invention relates to a preparation method of a CeO2-MnO2 composite catalyst with an efficient photothermal concerted catalytic purification function for VOCs (Volatile Organic Chemicals), comprising the following steps of: (1) weighting Ce(III) salts and KMnO4 and stirring by utilizing magnetic force to obtain a mixed solution; (2) transferring the mixed solution into a reaction kettle to carry out hydrothermal oxidation reduction reaction; and (3) after the reaction is ended and the reaction kettle is cooled to the room temperature, taking out sediments in an inner polytetrafluoroethylene container, filtering, cleaning and drying. The preparation method has the beneficial effects that: (1) the catalyst provided by the invention has catalytic activity for efficient and low-temperature photothermal concerted catalytic oxidation for the VOCs, the photothermal concerted catalytic activity of the catalyst is far higher than the thermal catalytic activity of the catalyst at the same reaction temperature and the photothermal concerted catalytic activity of the catalyst of pure CeO2 or MnO2, and the catalytic purification effect is improved; (2) raw materials are low in cost and easy to obtain, the reaction condition is mild, the process is simple and industrialization is easy to realize; and (3) the cost is remarkably reduced.

Description

The CeO with efficient photo-thermal concerted catalysis purifying VOCs 2-MnO 2the preparation method of composite catalyst
Technical field
The present invention relates to a kind of CeO 2-MnO 2the preparation method of composite catalyst, this composite catalyst, under light heat synergetic action condition, can purify the volatile organic contaminants such as benzene, toluene and acetone by efficient catalytic.
Background technology
Volatile organic contaminant (VOCs), as: benzene, toluene, formaldehyde, acetone etc., not only have great harm to health, and can cause serious environmental pollution.The improvement technology of VOCs comprises absorption, catalytic oxidation and photocatalysis etc., wherein take adsorption technology that active carbon or molecular sieve be adsorbent, catalytic oxidation technical research report that the carried noble metal of take is catalyst at most.But be subject to the restriction of adsorption capacity, need be to the adsorbent processing of regenerating, and though loaded noble metal catalyst catalytic activity is high, but expensive, these have greatly limited adsorption technology, the extensive use of the catalytic oxidation technology based on noble metal in VOCs administers, and are therefore badly in need of research and development are low-cost, have efficient catalytic purifying VOCs new catalytic material and new technology.CeO 2, manganese dioxide, cerium manganese composite oxides gets more and more people's extensive concerning because having good catalytic oxidation performance.US Patent No. 6458741 adopts dipping decomposition method, precipitation sedimentation and coprecipitation to prepare containing cerium binary or multicomponent composite oxide, and precious metals pt, Pd are carried on these composite oxides, the composite catalyst of gained has good VOCs low-temperature catalytic oxidation activity.Chinese patent CN200510093318.2 adopts infusion process to prepare support type Mn-Ce composite oxide catalytic, and this catalyst has good catalytic oxidation activity to VOCs.The people such as Tang are with (NH 4) 2ce (NO 3) 6, Mn (NO 3) 2.6H 2o, (NH 4) 2ce (NO 3) 6with citric acid be raw material, adopt coprecipitation to prepare MnO x-CeO 2complex catalyst, this catalyst is at 100 ℃, and the conversion ratio of formaldehyde reaches 100%, and has good stability (F. Tang, Y.G. Li, M. Huang, et al. appl. Catal. B2006,62,265).The people such as Delimaris are with Ce (NO 3) 6, Mn (NO 3) 2with urea be raw material, adopt urea-nitrate combustion method to prepare MnO x-CeO 2composite oxides, this catalyst has good catalytic oxidation activity (D. Delimaris, T. Ioannides. to VOCs appl. Catal. B2008,84,303).
CeO 2not only there is good catalytic oxidation performance, as a kind of broadband N-shaped semiconductor, also there is certain photocatalytic activity.The people such as nearest Li Yuanzhi have found mesoporous nano CeO 2there is good oxygen ion conduction coupling photo-thermal concerted catalysis performance, for gas pollutants such as benzene, cyclohexane, acetone, show efficient low-temperature catalytic oxidation activity and stability (Y.Z, Li, * Q. Sun, M. Kong, et al. j. Phys. Chem. C, 2011, 115, 14050).
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of CeO with efficient photo-thermal concerted catalysis purifying VOCs for above-mentioned prior art 2-MnO 2the preparation method of composite catalyst, this preparation method's raw material is cheap and easy to get, technique simple and be easy to industrialization.
The present invention solves the problems of the technologies described above adopted technical scheme, has the CeO of efficient photo-thermal concerted catalysis purifying VOCs 2-MnO 2the preparation method of composite catalyst, is characterized in that including following steps:
1) take 0.04mol ~ 0.01molCe (III) salt and 0.01mol ~ 0.03molKMnO 4, successively joining in the beaker that water is housed, magnetic agitation, obtains Ce (III) salt and KMnO 4mixed solution;
2) mixed solution is gone in the stainless steel cauldron with polytetrafluoroethylliner liner, after good seal, carry out hydrothermal oxidization reduction reaction;
3) after having reacted, question response still is cooled to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains having the CeO of light heat synergetic action 2-MnO 2composite catalyst.
Press such scheme, described Ce (III) salt is cerous nitrate, cerium chloride or cerous sulfate.
Press such scheme, the reaction temperature of described hydrothermal oxidization reduction reaction is 90 ℃～180 ℃, and the reaction time is 12～72 hours.
The present invention utilizes CeO 2good photo-thermal concerted catalysis oxidation susceptibility and MnO 2good heat catalytic oxidation performance, Ce (III) salt of take is reducing agent, KMnO 4for oxidant, adopt hydrothermal oxidization reduction synthesis process, under gentle reaction condition, the design of novelty CeO 2-MnO 2method for preparing composite catalyst, has realized at CeO 2-MnO 2active component CeO in composite catalyst 2and MnO 2between concerted catalysis effect; Find first simultaneously, compare with traditional heat catalytic oxidation, under photo-thermal acting in conjunction, gained CeO 2-MnO 2the catalytic oxidation activity of composite catalyst significantly improves, and its have its source in Lattice Oxygen in composite catalyst and reactivity of organic pollutant molecule are significantly improved under light heat synergetic action.Gained CeO of the present invention 2-MnO 2the photo-thermal concerted catalysis oxidation activity of composite catalyst is far above simple CeO 2or MnO 2photo-thermal concerted catalysis oxidation activity and MnO 2-CeO 2the heat catalytic oxidation of composite oxides is active, gained CeO 2-MnO 2the gas phase volatile organic contaminants such as composite catalyst energy efficient catalytic degraded benzene, toluene, acetone.
The beneficial effect of patent of the present invention is:
1) the prepared CeO of the present invention 2-MnO 2composite catalyst, has the catalytic activity that the concerted catalysis of high efficient cryogenic photo-thermal is oxidized VOCs, and its photo-thermal concerted catalysis activity is active far above the thermocatalytic under same reaction temperature, far above simple CeO 2or MnO 2photo-thermal concerted catalysis active, greatly improved VOC catalytic purification efficiency;
2) CeO that this patent is invented 2-MnO 2method for preparing composite catalyst, raw material is cheap and easy to get, reaction condition is gentle, technique is simple, is easy to industrialization;
3) the prepared CeO of the present invention 2-MnO 2composite catalyst, without carried noble metal, has significantly reduced cost.
Accompanying drawing explanation
In following Fig. 1-Figure 11, curve A is photo-thermal concerted catalysis, and curve B is thermocatalytic:
Fig. 1 is embodiment 1 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:3) is at 120 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram;
Fig. 2 is embodiment 1 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:3) is at 160 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram;
Fig. 3 is embodiment 1CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:3) at 200 ℃, photo-thermal concerted catalysis and thermocatalytic, CeO 2photo-thermal concerted catalysis (curve C) and CeO 2photo-thermal concerted catalysis (curve D) the 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram;
Fig. 4 is embodiment 1 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:3) is at 200 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l acetone of degrading generate CO 2change in concentration comparison diagram;
Fig. 5 is embodiment 1 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:3) is at 200 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l toluene of degrading generate CO 2change in concentration comparison diagram;
Fig. 6 is embodiment 2 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:3) is at 200 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram;
Fig. 7 is embodiment 3 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:3) is at 200 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram;
Fig. 8 is embodiment 4 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 3:1) is at 200 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram;
Fig. 9 is embodiment 5 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:1) is at 200 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram;
Figure 10 is embodiment 6 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 1:3) is at 200 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram;
Figure 11 is embodiment 7 CeO 2-MnO 2catalyst (Ce/Mn mol ratio 2:3) is at 200 ℃, and photo-thermal concerted catalysis and the thermocatalytic 100 μ l benzene of degrading generate CO 2change in concentration comparison diagram.
The specific embodiment
Below in conjunction with embodiment, further set forth substantive distinguishing features of the present invention and significant progressive, but the cited case does not limit protection domain of the present invention.
embodiment 1:
The CeO with efficient photo-thermal concerted catalysis purifying VOCs 2-MnO 2the preparation method of composite catalyst (Ce/Mn mol ratio is 1:3) is as follows:
(1) take 0.01molCe (NO 3) 36H 2o and 0.03molKMnO 4, joining in the beaker that 60ml water is housed, magnetic agitation, obtains Ce (NO 3) 36H 2o and KMnO 4mixed solution;
(2) mixed solution is gone in the stainless steel cauldron of 100 ml with polytetrafluoroethylliner liner, after good seal, at 120 ℃, react 24 hours;
(3) after having reacted, question response still cool to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains CeO 2-MnO 2composite catalyst.
application example 1
The CeO that embodiment 1 is obtained 2-MnO 2the composite catalyst photo-thermal concerted catalysis 100 μ l benzene of degrading, specific experiment step is as follows:
(1) take embodiment 1 gained CeO 2-MnO 2catalyst and distilled water are with 0.5g: 20ml ratio is mixed, and ultrasonic processing 10min, obtains suspension, suspension is transferred in the glass culture dish that diameter is 11mm, and dries under infrared lamp;
(2) culture dish is placed in the gas phase photo-thermal catalytic reactor that a top is provided with silica glass window, silica glass window is placed a high-pressure sodium lamp (250W), reactor is placed on controllable electric hot plate, and be connected with gas chromatograph by automatic sampling device, open high-pressure sodium lamp, regulate electric hot plate, catalytic reaction temperature keeps 120 ℃;
(3) work as CO 2concentration keep stable after, to injecting gas in reactor, the CO that catalytic reaction produces 2concentration detects analysis online with gas chromatograph.
The CO that application example 1 photo-thermal concerted catalysis degraded benzene produces 2change in concentration and time relationship are shown in the curve A in Fig. 1.At 120 ℃, after photo-thermal concerted catalysis 60min, CO 2increment is 3948mg/m 3, CO 2generating rate is 1.5 μ mol/minm 3.
comparison example 1
The CeO that embodiment 1 is obtained 2-MnO 2the composite catalyst thermocatalytic 100 μ l benzene of degrading, specific experiment step and application example 1 are basic identical, and difference is, in catalytic reaction process, to close high-pressure sodium lamp.
The thermocatalytic CO that 100 μ l benzene produce that degrades in comparison example 1 2the relation of change in concentration and time is shown in the curve B in Fig. 1, after thermocatalytic 60min, and CO 2increment is 715mg/m 3, CO 2generating rate be 0.27 μ mol/minm 3.
As shown in Figure 1, CeO at 120 ℃ 2-MnO 2the degrade CO of 100 μ l benzene of catalyst photo-thermal concerted catalysis 2generating rate is thermocatalytic 5.56 times.
application example 2
By the resulting CeO of embodiment 1 2-MnO 2the composite catalyst photo-thermal concerted catalysis 100 μ l benzene of degrading, catalytic reaction temperature is 160 ℃.
The application example 2 photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2the relation of change in concentration and time is shown in the curve A in Fig. 2.After photo-thermal concerted catalysis 60min, CO 2increment is 14346mg/m 3, CO 2generating rate be 5.43 μ mol/ minm 3.
comparison example 2
The CeO that embodiment 1 is obtained 2-MnO 2the composite catalyst thermocatalytic 100 μ l benzene of degrading, catalytic temperature is 160 ℃.
The comparison example 2 thermocatalytics CO that 100 μ l benzene produce that degrades 2the relation of change in concentration and time is shown in the curve B in Fig. 2, after thermocatalytic 60min, and CO 2increment is 5528mg/m 3, CO 2generating rate be 2.1 μ mol/minm 3.
As shown in Figure 2, CeO at 160 ℃ 2-MnO 2the degrade CO of 100 μ l benzene of catalyst photo-thermal concerted catalysis 2generating rate is thermocatalytic 2.60 times.
application example 3:
The CeO that embodiment 1 is obtained 2-MnO 2the composite catalyst photo-thermal concerted catalysis 100 μ l benzene of degrading, catalytic reaction temperature is 200 ℃.
The application example 3 photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2the relation of change in concentration and time is shown in the curve A in Fig. 3, after photo-thermal concerted catalysis 35min, and CO 2increment is 40179mg/m 3, CO 2generating rate be 26.1 μ mol/ minm 3.
comparison example 3(a)
The CeO that embodiment 1 is obtained 2-MnO 2the composite catalyst thermocatalytic 100 μ l benzene of degrading, catalytic reaction temperature is 200 ℃.
The thermocatalytic CO that 100 μ l benzene produce that degrades in comparison example 3 2the relation of change in concentration and time is shown in the curve B in Fig. 3, after thermocatalytic 35min, and CO 2increment is 22094mg/m 3, CO 2generating rate be 14.4 μ mol/minm 3.
comparison example 3(b)
Take 15gCe (NO 3) 36H 2o and 6g urea, join in the 250ml round-bottomed flask that 40ml distilled water is housed ultrasonic processing.Flask is put into micro-wave oven (50Hz, 800W), add thermal response 30min.Reaction end, takes out precipitation, with distilled water filtration, washing, oven dry, then at 400 ℃, calcines 2h, obtains nano Ce O 2powder.
By resulting CeO 2the collaborative thermocatalytic of the catalyst photo-thermal 100 μ l benzene of degrading, catalytic reaction temperature is 200 ℃.CeO 2the photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2the relation of change in concentration and time is shown in the curve C in Fig. 3, after photo-thermal concerted catalysis 35min, and CO 2increment is 16305mg/m 3, CO 2generating rate be 10.59 μ mol/minm 3.
comparison example 3(c)
Take 0.01molMn (NO 3) 2and 0.02molKMnO 4, joining in the beaker that 60ml water is housed, magnetic agitation, obtains Mn (NO 3) 2with KMnO 4mixed solution; Mixed solution is gone in the stainless steel cauldron of 100 ml with polytetrafluoroethylliner liner, after good seal, at 120 ℃, react 24 hours; After having reacted, question response still cool to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains MnO 2powder.
By resulting MnO 2the collaborative thermocatalytic of the catalyst photo-thermal 100 μ l benzene of degrading, catalytic reaction temperature is 200 ℃.MnO 2the photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2change in concentration and time relationship are shown in the curve D in Fig. 3, after photo-thermal concerted catalysis 35min, and CO 2increment is 5147mg/m 3, CO 2generating rate be 3.34 μ mol/minm 3.
As shown in Figure 3, CeO at 200 ℃ 2-MnO 2the catalysis photo-thermal concerted catalysis 100 μ l benzene CO that degrade 2generating rate is thermocatalytic 1.82 times, is CeO 22.46 times of photo-thermal concerted catalysis are MnO 27.81 times of photo-thermal concerted catalysis.
application example 4
By the resulting CeO of embodiment 1 2-MnO 2the composite catalyst photo-thermal concerted catalysis 100 μ l acetone of degrading, catalytic temperature is 200 ℃.
The application example 4 photo-thermal concerted catalysis CO that 100 μ l acetone produce that degrades 2the relation of change in concentration and time is shown in the curve A in Fig. 4.After photo-thermal concerted catalysis 15min, CO 2increment is 24626mg/m 3, CO 2generating rate be 37.3 μ mol/minm 3.
comparison example 4
By the resulting CeO of embodiment 1 2-MnO 2the oxide catalyst thermocatalytic 100 μ l acetone of degrading, catalytic temperature is 200 ℃.
The comparison example 4 thermocatalytics CO that 100 μ l acetone produce that degrades 2the relation of change in concentration and time is shown in the curve B in Fig. 4, after thermocatalytic 15min, and CO 2concentration increment is 5682mg/m 3, CO 2generating rate be 8.6 μ mol/minm 3.
As shown in Figure 4, CeO at 200 ℃ 2-MnO 2the degrade CO of 100 μ l acetone of catalyst photo-thermal concerted catalysis 2generating rate is thermocatalytic 4.33 times.
application example 5
By the resulting CeO of embodiment 1 2-MnO 2the composite catalyst photo-thermal concerted catalysis 100 μ l toluene of degrading, catalytic temperature is 200 ℃.
The application example 5 photo-thermal concerted catalysis CO that 100 μ l toluene produce that degrades 2change in concentration and time relationship are shown in the curve A in Fig. 5.After photo-thermal concerted catalysis 30min, CO 2increment is 13053mg/m 3, CO 2generating rate be 9.89 μ mol/minm 3.
comparison example 5
By the resulting CeO of embodiment 1 2-MnO 2the composite catalyst thermocatalytic 100 μ l toluene of degrading, catalytic temperature is 200 ℃.
The comparison example 5 thermocatalytics CO that 100 μ l toluene produce that degrades 2change in concentration and time relationship are shown in the curve B in Fig. 5, after thermocatalytic 30min, and CO 2increment is 3167mg/m 3, CO 2generating rate be 2.40 μ mol/minm 3.
As shown in Figure 5, CeO at 200 ℃ 2-MnO 2the degrade CO of 100 μ l toluene of catalyst photo-thermal concerted catalysis 2generating rate is 4.12 times that thermocatalytic is used.
embodiment 2
The CeO with efficient photo-thermal concerted catalysis purifying VOCs 2-MnO 2the preparation method of composite catalyst (Ce/Mn mol ratio is 1:3) is as follows:
(1) take 0.01molCe (NO 3) 36H 2o and 0.03molKMnO 4, joining in the beaker that 60ml water is housed, magnetic agitation, obtains Ce (NO 3) 36H 2o and KMnO 4mixed solution;
(2) mixed solution is gone in the stainless steel cauldron of 100 ml with polytetrafluoroethylliner liner, after good seal, at 180 ℃, react 24 hours;
(3) after having reacted, question response still cool to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains CeO 2-MnO 2composite catalyst.
application example 1:
By the resulting CeO of embodiment 2 2-MnO 2composite catalyst is answered the photo-thermal concerted catalysis 100 μ l benzene of degrading, and catalytic temperature is 200 ℃.
The application example 2 photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2the relation of change in concentration and time is shown in the curve A in Fig. 6, after illumination 60min, and CO 2increment is 24737mg/m 3, CO 2generating rate be 9.37 μ mol/minm 3.
comparison example 1
By the resulting CeO of embodiment 2 2-MnO 2the composite catalyst thermocatalytic 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The comparison example 1 thermocatalytic CO that 100 μ l benzene produce that degrades 2the relation of change in concentration and time is shown in the curve B in Fig. 6, CO after illumination 60min 2concentration increment is 4634mg/m 3, CO 2generating rate be 1.76 μ mol/minm 3.
As shown in Figure 6, CeO at 200 ℃ 2-MnO 2the degrade CO of 100 μ l benzene of catalyst photo-thermal concerted catalysis 2generating rate is thermocatalytic 5.32 times.
embodiment 3
The CeO with efficient photo-thermal concerted catalysis purifying VOCs 2-MnO 2the preparation method of composite catalyst (Ce/Mn mol ratio is 1:3) is as follows:
(1) take 0.01molCe (NO 3) 36H 2o and 0.03molKMnO 4, joining in the beaker that 60ml water is housed, magnetic agitation, obtains Ce (NO 3) 36H 2o and KMnO 4mixed solution;
(2) mixed solution is gone in the stainless steel cauldron of 100 ml with polytetrafluoroethylliner liner, after good seal, at 90 ℃, react 15 hours;
(3) after having reacted, question response still cool to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains CeO 2-MnO 2catalyst.
application example 1
By the resulting CeO of embodiment 3 2-MnO 2the catalyst photo-thermal concerted catalysis 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The application example 1 photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2change in concentration and time relationship are shown in the curve A in Fig. 7.After photo-thermal concerted catalysis 20min, CO 2increment is 49514mg/m 3, CO 2generating rate be 56.3 μ mol/minm 3.
comparison example 1
By the resulting CeO of embodiment 3 2-MnO 2the composite catalyst thermocatalytic 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The thermocatalytic CO that 100 μ l benzene produce that degrades in comparison example 1 2the relation of change in concentration and time is shown in the curve B in Fig. 7, after thermocatalytic 15min, and CO 2concentration increment is 36841mg/m 3, CO 2generating rate be 41.9 μ mol/minm 3.
As shown in Figure 7, CeO at 200 ℃ 2-MnO 2the degrade CO of 2 μ l benzene of catalyst photo-thermal concerted catalysis 2generating rate is 1.34 times of thermocatalytic (curve B).
embodiment 4
The CeO with efficient photo-thermal concerted catalysis purifying VOCs 2-MnO 2the preparation method of composite catalyst (Ce/Mn mol ratio is 3:1) is as follows:
(1) take the Ce (NO of 0.03mol 3) 36H 2the KMnO of O and 0.01mol 4, joining in the beaker that 60ml water is housed, magnetic agitation, obtains Ce (NO 3) 36H 2o and KMnO 4mixed solution;
(2) mixed solution is gone in the stainless steel cauldron of 100 ml with polytetrafluoroethylliner liner, after good seal, at 90 ℃, react 15 hours;
(3) after having reacted, question response still cool to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains CeO 2-MnO 2catalyst.
application example 1
By the resulting CeO of the embodiment of the present invention 4 2-MnO 2the catalyst photo-thermal concerted catalysis 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The application example 1 photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2the relation of change in concentration and time is shown in the curve A in Fig. 8.After photo-thermal concerted catalysis 30min, CO 2increment is 46999mg/m 3, CO 2generating rate be 35.6 μ mol/minm 3.
comparison example 1
By the resulting CeO of the embodiment of the present invention 4 2-MnO 2the composite oxide catalysts thermocatalytic 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The comparison example 1 thermocatalytic CO that 100 μ l benzene produce that degrades 2the relation of change in concentration and time is shown in the curve B in Fig. 8.After thermocatalytic 30min, CO 2increment is 33866mg/m 3, CO 2generating rate be 25.7 μ mol/minm 3.
As shown in Figure 8, CeO at 200 ℃ 2-MnO 2the degrade CO of 100 μ l benzene of catalyst photo-thermal concerted catalysis 2generating rate is thermocatalytic 1.39 times.
embodiment 5
There is the active CeO of efficient photo-thermal concerted catalysis 2-MnO 2the preparation method of catalyst (Ce/Mn mol ratio is 1:1) is as follows:
(1) take 0.02molCe (NO 3) 36H 2o and 0.02molKMnO 4, joining in the beaker that 60ml water is housed, magnetic agitation, obtains Ce (NO 3) 36H 2o and KMnO 4mixed solution;
(2) mixed solution is gone in the stainless steel cauldron of 100 ml with polytetrafluoroethylliner liner, after good seal, at 90 ℃, react 15 hours;
(3) after having reacted, question response still cool to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains CeO 2-MnO 2catalyst.
application example 1
By the resulting CeO of the embodiment of the present invention 5 2-MnO 2the composite catalyst photo-thermal concerted catalysis 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The application example 1 photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2change in concentration and time relationship are shown in the curve A in Fig. 9.After photo-thermal concerted catalysis 40min, CO 2increment is 40110mg/m 3, CO 2generating rate be 22.8 μ mol/minm 3.
comparison example 1
By the resulting CeO of embodiment 4 2-MnO 2the composite catalyst thermocatalytic 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The thermocatalytic CO that 100 μ l benzene produce that degrades in comparison example 1 2change in concentration and time relationship are shown in the curve B in Fig. 9, after thermocatalytic 40min, and CO 2concentration increment is 31050mg/m 3, CO 2generating rate be 17.6 μ mol/minm 3.
As shown in Figure 9, CeO at 200 ℃ 2-MnO 2the degrade CO of 100 μ l benzene of catalyst photo-thermal concerted catalysis 2generating rate is thermocatalytic 1.3 times.
embodiment 6
There is the active CeO of efficient photo-thermal concerted catalysis 2-MnO 2the preparation method of catalyst (Ce/Mn mol ratio is 1:3) is as follows:
(1) take 0.01molCeCl 37H 2o and 0.03molKMnO 4, joining in the beaker that 60ml water is housed, magnetic agitation, obtains Ce (NO 3) 36H 2o and KMnO 4mixed solution;
(2) mixed solution is gone in the stainless steel cauldron of 100 ml with polytetrafluoroethylliner liner, after good seal, at 120 ℃, react 24 hours;
(3) after having reacted, question response still cool to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains CeO 2-MnO 2catalyst.
application example 1
By the resulting CeO of the embodiment of the present invention 6 2-MnO 2the composite catalyst photo-thermal concerted catalysis 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The application example 1 photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2change in concentration and time relationship are shown in the curve A in Figure 10.After photo-thermal concerted catalysis 30min, CO 2increment is 13553mg/m 3, CO 2generating rate be 10.27 μ mol/minm 3.
comparison example 1
By the resulting CeO of embodiment 6 2-MnO 2the composite catalyst thermocatalytic 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The thermocatalytic CO that 100 μ l benzene produce that degrades in comparison example 1 2change in concentration and time relationship are shown in the curve B in Figure 10, after thermocatalytic 30min, and CO 2increment is 4667mg/m 3, CO 2generating rate be 3.54 μ mol/minm 3.
As shown in Figure 10, CeO at 200 ℃ 2-MnO 2the degrade CO of 100 μ l benzene of catalyst photo-thermal concerted catalysis 2generating rate is thermocatalytic 2.9 times.
embodiment 7
There is the active CeO of efficient photo-thermal concerted catalysis 2-MnO 2the preparation method of catalyst (Ce/Mn mol ratio is 2:3) is as follows:
(1) take 0.005molCe 2(SO 4) 38H 2o and 0.015molKMnO 4, joining in the beaker that 60ml water is housed, magnetic agitation, obtains Ce 2(SO4) 38H 2o and KMnO 4mixed solution;
(2) mixed solution is gone in the stainless steel cauldron of 100 ml with polytetrafluoroethylliner liner, after good seal, at 120 ℃, react 24 hours;
(3) after having reacted, question response still cool to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains CeO 2-MnO 2catalyst.
application example 1
By the resulting CeO of the embodiment of the present invention 7 2-MnO 2the composite catalyst photo-thermal concerted catalysis 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The application example 1 photo-thermal concerted catalysis CO that 100 μ l benzene produce that degrades 2change in concentration and time relationship are shown in the curve A in Figure 11.After photo-thermal concerted catalysis 40min, CO 2increment is 4582mg/m 3, CO 2generating rate be 2.60 μ mol/minm 3.
comparison example 1
By the resulting CeO of embodiment 7 2-MnO 2the composite catalyst thermocatalytic 100 μ l benzene of degrading, catalytic temperature is 200 ℃.
The thermocatalytic CO that 100 μ l benzene produce that degrades in comparison example 1 2change in concentration and time relationship are shown in the curve B in Figure 11, after thermocatalytic 40min, and CO 2concentration increment is 1284mg/m 3, CO 2generating rate be 0.73 μ mol/minm 3.
As shown in Figure 11, CeO at 200 ℃ 2-MnO 2the degrade CO of 100 μ l benzene of catalyst photo-thermal concerted catalysis 2generating rate is thermocatalytic 3.57 times.

Claims (2)

1. the CeO with efficient photo-thermal concerted catalysis purifying VOCs 2-MnO 2the preparation method of composite catalyst, is characterized in that including following steps:
1) take 0.04mol ~ 0.01molCe (III) salt and 0.01mol ~ 0.03molKMnO 4, successively joining in the beaker that water is housed, magnetic agitation, obtains Ce (III) salt and KMnO 4mixed solution;
2) mixed solution is gone in the stainless steel cauldron with polytetrafluoroethylliner liner, after good seal, carry out hydrothermal oxidization reduction reaction, the reaction temperature of described hydrothermal oxidization reduction reaction is 90 ℃～180 ℃, and the reaction time is 12～72 hours;
3) after having reacted, question response still is cooled to room temperature, takes out the precipitation in polytetrafluoroethylliner liner, filters, washs, dries, and obtains having the CeO of light heat synergetic action 2-MnO 2composite catalyst.
2. by the CeO with efficient photo-thermal concerted catalysis purifying VOCs claimed in claim 1 2-MnO 2the preparation method of composite catalyst, is characterized in that described Ce (III) salt is cerous nitrate, cerium chloride or cerous sulfate.
CN201210029241.XA 2012-02-10 2012-02-10 Preparation method of CeO2-MnO2 composite catalyst with efficient photothermal synergistic catalytic purification function for VOCs (Volatile Organic Chemicals) Expired - Fee Related CN102553575B (en)

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