CN105289583A - Preparation method of carbon nanosphere supported manganese oxide based catalyst - Google Patents
Preparation method of carbon nanosphere supported manganese oxide based catalyst Download PDFInfo
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- CN105289583A CN105289583A CN201510721869.XA CN201510721869A CN105289583A CN 105289583 A CN105289583 A CN 105289583A CN 201510721869 A CN201510721869 A CN 201510721869A CN 105289583 A CN105289583 A CN 105289583A
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- nano carbon
- manganese oxide
- carbon balls
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- based catalyst
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Abstract
The invention relates to a preparation method of a carbon nanosphere supported manganese oxide based catalyst. The active component manganese oxide of the catalyst is supported on carbon nanospheres by adopting an oxidation reduction method, the manganese oxide and the carrier of the catalyst have stronger mutual effect after drying, and the NO catalytic oxidation activity under normal temperature and pressure is improved. The preparation method is simple and low in cost, can be applied to efficient purification treatment of NO pollutants in parking lots, underground shopping malls and urban highway tunnels and has important social significance and practical application value.
Description
Technical field
The present invention relates to manganese oxide catalyst and preparation that a kind of Nano carbon balls supports, what be applied to normal temperature low concentration of NO in tunnel, parking lot, market place builet below the ground and urban road tunnel removes purification, and can keep high conversion and high activity for a long time.
Background technology
Nitrogen oxide (NOx) forms one of nitric acid type acid rain and photochemical fog, the Air Pollutants that damages the ozone layer, has very strong toxicity.Tunnel, the hemi-closure spaces such as parking lot are restricted due to gravity-flow ventilation, and the tail gas of vehicular emission cannot be discharged in time, and nitrogen oxide (NOx) is accumulated, and air pollution is serious.Wherein, nitric oxide (NO) accounts for the 90%-95% of NOx total amount, and NO effectively removes purification and seems particularly important.The Treatment process of NO comprises catalytic reduction method, catalytic decomposition, plasma method, liquid absorption method, absorption method, microbial method etc., and its activity is all relatively low.The selection of NO room-temperature catalytic oxidation catalyst carrier is very important, can improve the atom utilization of catalyst on the one hand, can reduce the cost of catalyst on the other hand; A kind of cheapness, efficiently carrier is found to improve the activity of catalyst so need badly.
Nano carbon balls surface has abundant oxygen-containing functional group, and the manganese oxide of load improves atom utilization, enhances the interaction of manganese oxide and carrier, improves its activity; The cost utilizing Nano carbon balls to make carried catalyst is on the other hand reduced significantly.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides the preparation method that a kind of Nano carbon balls supports manganese oxide based catalyst, for NO room-temperature catalytic oxidation.
Nano carbon balls supports a preparation method for manganese oxide based catalyst, it is characterized in that, utilize sulfuric acid to support manganese oxide to CNT and carry out surface modification, its preparation process comprises:
(1) Nano carbon balls is dispersed in deionized water for ultrasonic 20min, then adds appropriate polyvinylpyrrolidone ultrasonic 20min again, obtain the first dispersion liquid of Nano carbon balls and polyvinylpyrrolidone; Certain density potassium permanganate solution and sulfuric acid solution dropwise to be instilled in above-mentioned dispersion liquid and vigorous stirring; After stirring at normal temperature mixes, put into teflon-lined hydrothermal crystallizing still, crystallization temperature is 160 DEG C, and reaction 40min-1h obtains precipitation;
(2) with the washing of a large amount of deionized water, filter out gained precipitation, put into 50-80 DEG C of baking oven and within 12 hours, carry out drying i.e. obtained Nano carbon balls and support manganese oxide based catalyst.
The mass ratio 1:6 of surfactant and Nano carbon balls described in step (1); The mass ratio 7:0.3 of potassium permanganate and Nano carbon balls.
In first dispersion liquid described in step (1), the mass percent of Nano carbon balls is 0.6%; The mass percent of surfactant is 0.1%; The concentration of described potassium permanganate solution is 0.1 ~ 0.6mol/L; Described surfactant PVP, the one of polyvinyl alcohol.
The present inventor finds that Nano carbon balls supports manganese oxide based catalyst after deliberation, improves the life-span of room-temperature catalytic oxidation NO and reduces the cost of catalyst.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates that Nano carbon balls obtained in the invention process supports manganese oxide catalyst.
Fig. 2 be comparative example one is shown, the Nano carbon balls of embodiment one supports the figure that manganese oxide low concentration of NO normal temperature removes the performance test results, test condition is: reaction gas NO concentration ~ 10ppm, O
2concentration 21%, carrier gas N
2, temperature ~ 30 DEG C, air speed 120000mLh
-1g
-1.
Detailed description of the invention
Following instance is by reference to the accompanying drawings for illustrating in greater detail the present invention, but the present invention is not limited to this.
Manganese oxide based catalysis material is supported to Nano carbon balls of the present invention and carries out the test that normal temperature removes low concentration of NO.Method of testing can be: pass into containing oxygen NO waste gas in the reactor, and described comprises NO, N containing oxygen NO waste gas
2and O
2, to contain the O in oxygen NO waste gas
2for oxidant, by NO catalytic oxidative desulfurization under room temperature (30 DEG C ± 5 DEG C) condition.Wherein, described containing O in oxygen NO waste gas
2content is the content of ~ 21%, NO is ~ 10ppm, and all the other are N
2.High-speed is 120000mLh
-1g
-1.The consumption of the manganese oxide based catalysis material of Nano carbon balls load is 0.25g.
comparative example 1:
By 7g potassium permanganate (KMnO
4) be dissolved in 150ml deionized water, get the 5ml concentrated sulfuric acid (95wt%) and dropwise instill also constantly stirring in liquor potassic permanganate, teflon-lined hydrothermal crystallizing still is transferred to after dropwising, crystallization temperature is 160 DEG C of reaction 40min, vacuum filtration, massive laundering, dry in 60 DEG C of baking ovens, obtained unsupported manganese oxide based catalyst, is designated as: MS.
embodiment 1:
0.3g Nano carbon balls and 0.05g polyvinylpyrrolidone are dispersed in 100ml deionized water, and ultrasonic 20min; Get 8g potassium permanganate (KMnO
4) be dissolved in 160ml deionized water.Potassium permanganate sulfuric acid solution is dropwise joined in Nano carbon balls dispersion liquid and also constantly stir, teflon-lined hydrothermal crystallizing still is transferred to after dropwising, crystallization temperature is 160 DEG C of reaction 40min, vacuum filtration, massive laundering, dry in 60 DEG C of baking ovens, obtained Nano carbon balls supports manganese oxide based catalyst, is designated as: MSC.
Table 1: the activity of MSC-160 under different preparation condition:
embodiment 2:
0.3g Nano carbon balls and 0.05g polyvinylpyrrolidone are dispersed in 100ml deionized water, and ultrasonic 20min; Get 8g potassium permanganate (KMnO
4) be dissolved in 160ml deionized water.Potassium permanganate sulfuric acid solution is dropwise joined in Nano carbon balls dispersion liquid and also constantly stir, teflon-lined hydrothermal crystallizing still is transferred to after dropwising, crystallization temperature is 140 DEG C of reaction 40min, vacuum filtration, massive laundering, dry in 60 DEG C of baking ovens, obtained Nano carbon balls supports manganese oxide based catalyst, is designated as: MSC-140.
Table 2: the activity of MSC-140 under different preparation condition:
embodiment 3:
0.3g Nano carbon balls and 0.05g polyvinylpyrrolidone are dispersed in 100ml deionized water, and ultrasonic 20min; Get 8g potassium permanganate (KMnO
4) be dissolved in 160ml deionized water.Potassium permanganate sulfuric acid solution is dropwise joined in Nano carbon balls dispersion liquid and also constantly stir, teflon-lined hydrothermal crystallizing still is transferred to after dropwising, crystallization temperature is 180 DEG C of reaction 40min, vacuum filtration, massive laundering, dry in 60 DEG C of baking ovens, obtained Nano carbon balls supports manganese oxide based catalyst, is designated as: MSC-180.
Table 3: the activity of MSC-180 under different preparation condition:
Claims (3)
1. Nano carbon balls supports a preparation method for manganese oxide based catalyst, it is characterized in that, utilize sulfuric acid to support manganese oxide to CNT and carry out surface modification, its preparation process comprises:
(1) Nano carbon balls is dispersed in deionized water for ultrasonic 20min, then adds appropriate polyvinylpyrrolidone ultrasonic 20min again, obtain the first dispersion liquid of Nano carbon balls and polyvinylpyrrolidone; Certain density potassium permanganate solution and sulfuric acid solution dropwise to be instilled in above-mentioned dispersion liquid and vigorous stirring; After stirring at normal temperature mixes, put into teflon-lined hydrothermal crystallizing still, crystallization temperature is 160 DEG C, and reaction 40min-1h obtains precipitation;
(2) with the washing of a large amount of deionized water, filter out gained precipitation, put into 50-80 DEG C of baking oven and within 12 hours, carry out drying i.e. obtained Nano carbon balls and support manganese oxide based catalyst.
2. a kind of Nano carbon balls supports the preparation method of manganese oxide based catalyst according to claim 1, it is characterized in that, the mass ratio 1:6 of surfactant and Nano carbon balls described in step (1); The mass ratio 7:0.3 of potassium permanganate and Nano carbon balls.
3. a kind of Nano carbon balls supports the preparation method of manganese oxide based catalyst according to claim 1, it is characterized in that, in the first dispersion liquid described in step (1), the mass percent of Nano carbon balls is 0.6%; The mass percent of surfactant is 0.1%; The concentration of described potassium permanganate solution is 0.1 ~ 0.6mol/L; Described surfactant PVP, the one of polyvinyl alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111157A (en) * | 2016-07-04 | 2016-11-16 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of catalyst for propane catalytic combustion elimination and preparation and application |
| CN106179340A (en) * | 2016-07-04 | 2016-12-07 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of prepare the loaded catalyst of nitrogen oxides and preparation and application for ammonia low-temperature catalytic oxidation |
| CN113755883A (en) * | 2021-07-22 | 2021-12-07 | 齐齐哈尔大学 | Preparation method and performance of biomass boron-doped carbon sphere induced manganese oxide composite catalyst electrode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008133750A9 (en) * | 2006-12-20 | 2009-04-23 | Headwaters Tech Innovation Llc | Method for manufacturing carbon nanostructures having minimal surface functional groups |
| CN102568855A (en) * | 2012-03-12 | 2012-07-11 | 重庆大学 | Carbon material-loading manganese dioxide nanowire array composite and method for producing same |
| CN103394354A (en) * | 2013-08-22 | 2013-11-20 | 神华集团有限责任公司 | Catalyst loaded on carbon sphere and preparation method of catalyst |
| CN104409225A (en) * | 2014-11-28 | 2015-03-11 | 西北师范大学 | Preparation method of manganese dioxide/ carbon microspheres composite material and application of composite material serving as supercapacitor electrode material |
| US20150068917A1 (en) * | 2012-02-28 | 2015-03-12 | Fritz Haber Institut Der Max Planck Gesellschaft | Electrolytic water splitting using a carbon-supported mnox-composite |
| CN104971716A (en) * | 2015-07-10 | 2015-10-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Multi-walled carbon nano-tube supported manganese oxide-based catalyst preparation method |
-
2015
- 2015-10-30 CN CN201510721869.XA patent/CN105289583A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008133750A9 (en) * | 2006-12-20 | 2009-04-23 | Headwaters Tech Innovation Llc | Method for manufacturing carbon nanostructures having minimal surface functional groups |
| US20150068917A1 (en) * | 2012-02-28 | 2015-03-12 | Fritz Haber Institut Der Max Planck Gesellschaft | Electrolytic water splitting using a carbon-supported mnox-composite |
| CN102568855A (en) * | 2012-03-12 | 2012-07-11 | 重庆大学 | Carbon material-loading manganese dioxide nanowire array composite and method for producing same |
| CN103394354A (en) * | 2013-08-22 | 2013-11-20 | 神华集团有限责任公司 | Catalyst loaded on carbon sphere and preparation method of catalyst |
| CN104409225A (en) * | 2014-11-28 | 2015-03-11 | 西北师范大学 | Preparation method of manganese dioxide/ carbon microspheres composite material and application of composite material serving as supercapacitor electrode material |
| CN104971716A (en) * | 2015-07-10 | 2015-10-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Multi-walled carbon nano-tube supported manganese oxide-based catalyst preparation method |
Non-Patent Citations (3)
| Title |
|---|
| RUITING DONG 等: ""Shape-controlled synthesis of Mn2O3 hollow structures and their catalytic properties"", 《CRYSTENGCOMM》 * |
| YUXIAN WANG 等: ""Synthesis of magnetic core/shell carbon nanosphere supported manganese catalysts for oxidation of organics in water by peroxymonosulfate"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| *** 等: ""纳米碳球负载钯纳米粒子催化合成1, 10-邻菲咯啉-5, 6-二胺"", 《应用化学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111157A (en) * | 2016-07-04 | 2016-11-16 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of catalyst for propane catalytic combustion elimination and preparation and application |
| CN106179340A (en) * | 2016-07-04 | 2016-12-07 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of prepare the loaded catalyst of nitrogen oxides and preparation and application for ammonia low-temperature catalytic oxidation |
| CN106179340B (en) * | 2016-07-04 | 2018-10-16 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of loaded catalyst and preparation and application preparing nitrogen oxides for ammonia low-temperature catalytic oxidation |
| CN113755883A (en) * | 2021-07-22 | 2021-12-07 | 齐齐哈尔大学 | Preparation method and performance of biomass boron-doped carbon sphere induced manganese oxide composite catalyst electrode |
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