CN1935355A - Manganese bioxide/carbon nano tube composite adsorbent and its preparing method - Google Patents
Manganese bioxide/carbon nano tube composite adsorbent and its preparing method Download PDFInfo
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- CN1935355A CN1935355A CN 200610068772 CN200610068772A CN1935355A CN 1935355 A CN1935355 A CN 1935355A CN 200610068772 CN200610068772 CN 200610068772 CN 200610068772 A CN200610068772 A CN 200610068772A CN 1935355 A CN1935355 A CN 1935355A
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Abstract
The present invention provides a manganese dioxide/carbon nano tube composite adsorbing agent. Said adsorbing agent includes manganese dioxide and carbon nano tube, the manganese dioxide can be adsorbed on the carbon nano tube, the manganese dioxide content is 10%-40% of total mass. Besides, said invention also provides its preparation method and its concrete steps.
Description
Technical field
The present invention relates to a kind of adsorbent and preparation method thereof, belong to the water treatment absorbent field.
Background technology
CNT has obtained extensive studies as the newcomer of carbon family in performance and application facet, as enhancing base, field emission body, hydrogen storage material, microelectronic element and the catalyst carrier as composite.
In recent years, CNT and also obtained deep research as adsorbent in water treatment field as the related compound material of carrier.But the research to CNT and related compound material thereof focuses mostly in the removal to heavy metal ion, and can not be satisfactory to organic absorption.Hydrated manganese dioxide has big specific area and abundant surface hydroxyl, thereby many pollutants especially organic matter are all shown good absorption property.
Summary of the invention
The present invention is directed to the deficiency of existing CNT, provide a kind of and can effectively adsorb inorganic matter and organic new adsorbent----manganese bioxide/carbon nano tube composite adsorbent organic adsorption capacity, and this preparation of adsorbent method.
Manganese bioxide/carbon nano tube composite adsorbent of the present invention comprises manganese dioxide and CNT, and manganese dioxide is adsorbed on the CNT, and wherein manganese dioxide accounts for the 10%-40% of gross mass.
The preparation method of above-mentioned manganese bioxide/carbon nano tube composite adsorbent may further comprise the steps:
(1) preliminary treatment of CNT; CNT successively put into soak 6～24h in red fuming nitric acid (RFNA) and the hydrofluoric acid respectively, behind the washing and filtering, again CNT is immersed volume ratio and be in the mixed solution of 5: 3 nitric acid and sulfuric acid and boil 0.5～2h, then CNT is filtered with nucleopore membranes, the aperture of nucleopore membranes is 2～4 μ m, and cyclic washing reaches till 7 up to carbon nano-tube aqueous solutions pH value;
(2) MnO
2Load; The above-mentioned pretreated CNT of learning from else's experience is added in the water and stirs, 0.25 liter of wherein per 1 gram CNT water; Add (CH
3COO)
2Mn adds the KMnO of every liter of 0.13mol subsequently
4Solution, wherein every gram (CH
3COO)
2Mn adds 25----40 and rises KMnO
4Solution; Continue in the whole process to stir, the color of solution becomes till the brownish black, shows that then MnO2 generates; Gained suspension is heated 15min-60min under the temperature of 350K-410K, then filtration, drying; Control (CH
3COO)
2Mn and KMnO
4The addition of solution is made the manganese bioxide/carbon nano tube composite adsorbent of different manganese dioxide content.
On the basis of adsorbent heavy metal ion in the removal water of still remaining valid that the present invention is made, improved the organic ability of removing by a relatively large margin.CNT and manganese dioxide all have bigger specific area and abundant hydroxyl, and heavy metal ion is had strong adsorption capacity.During adsorb organic compound, on the original adsorption effect of CNT, the double effects of manganese dioxide performance oxidation and absorption can strengthen organic removal ability.
The specific embodiment
Embodiment 1
The preparation method of manganese bioxide/carbon nano tube composite adsorbent is:
(1) preliminary treatment of CNT.With CNT successively put into and soak 6h in red fuming nitric acid (RFNA) and the hydrofluoric acid respectively with the catalyst granules and the catalyst carrier of dissolving in the pipe, behind the washing and filtering, again CNT is immersed and boil 1h in the mixed solution (volume ratio of nitric acid and sulfuric acid is 5: 3) of nitric acid and sulfuric acid to remove the amorphous carbon particle, then CNT is filtered with nucleopore membranes (aperture 2～4 μ m), cyclic washing reaches till 7 up to carbon nano-tube aqueous solutions pH value.
(2) MnO
2Load.Get the pretreated CNT of 4g and be added in the 1L water, high strength stirs.Add 1.4g (CH
3COO)
2Mn adds 50mLKMnO subsequently
4(0.13mol/L) solution continues in the whole process to stir, and solution colour becomes till the brownish black, then shows MnO
2Generate.Gained suspension is heated 60min under 353K, make MnO after filtration, the drying then
2/ carbon nano tube composite adsorbent, wherein load capacity be manganese dioxide account for gross mass 20%.
Embodiment 2:
The preparation method of manganese bioxide/carbon nano tube composite adsorbent is:
(1) preliminary treatment of CNT.CNT successively put into soak 12h in red fuming nitric acid (RFNA) and the hydrofluoric acid respectively with catalyst granules in the dissolved carbon nanotube and catalyst carrier, behind the washing and filtering, the mixed solution (volume ratio 5: 3) of again CNT being put into nitric acid and sulfuric acid boils 0.5h to remove the amorphous carbon particle, then CNT is filtered with nucleopore membranes (aperture 2～4 μ m), cyclic washing reaches till 7 up to carbon nano-tube aqueous solutions pH value.
(2) MnO
2Load.Get the pretreated CNT of 4g and be added in the 1L water, high strength stirs.Add 0.7g (CH
3COO)
2Mn adds 25mL KMnO subsequently
4(0.13mol/L) solution continues in the whole process to stir, and solution colour becomes till the brownish black, then shows MnO
2Generate.Gained suspension 383K is heated 15min down, filter drying then.Making load capacity is that manganese dioxide accounts for 10% manganese bioxide/carbon nano tube composite adsorbent.
Embodiment 3
The preparation method of manganese bioxide/carbon nano tube composite adsorbent is:
(1) preliminary treatment of CNT.CNT successively put into soak 24h in red fuming nitric acid (RFNA) and the hydrofluoric acid respectively with the catalyst granules and the catalyst carrier of dissolving in the pipe, behind the washing and filtering, the mixed solution (volume ratio 5: 3) of again CNT being put into nitric acid and sulfuric acid boils 2h to remove the amorphous carbon particle, then CNT is filtered with nucleopore membranes (aperture 2～4 μ m), cyclic washing reaches till 7 up to carbon nano-tube aqueous solutions pH value.
(2) MnO
2Load.Get the pretreated CNT of 4g and be added in the 1L water, high strength stirs.Add 2.8g (CH
3COO)
2Mn adds 75mL KMnO subsequently
4(0.13mol/L) solution continues in the whole process to stir, and solution colour becomes till the brownish black, shows that then MnO2 generates.Gained suspension is heated 15min under 403K, filter drying then.Making load capacity is that manganese dioxide accounts for 40% manganese bioxide/carbon nano tube composite adsorbent.
Claims (2)
1. a manganese bioxide/carbon nano tube composite adsorbent comprises manganese dioxide and CNT, it is characterized in that: manganese dioxide is adsorbed on the CNT, and wherein manganese dioxide accounts for the 10%-40% of gross mass.
2. the preparation method of the described manganese bioxide/carbon nano tube composite adsorbent of claim 1 is characterized in that: may further comprise the steps:
(1) preliminary treatment of CNT; CNT successively put into soak 6～24h in red fuming nitric acid (RFNA) and the hydrofluoric acid respectively, behind the washing and filtering, again CNT is immersed volume ratio and be in the mixed solution of 5: 3 nitric acid and sulfuric acid and boil 0.5～2h, then CNT is filtered with nucleopore membranes, the aperture of nucleopore membranes is 2～4 μ m, and cyclic washing reaches till 7 up to carbon nano-tube aqueous solutions pH value;
(2) MnO
2Load; The above-mentioned pretreated CNT of learning from else's experience is added in the water and stirs, 0.25 liter of wherein per 1 gram CNT water; Add (CH
3COO)
2Mn adds the KMnO of every liter of 0.13mol subsequently
4Solution, wherein every gram (CH
3COO)
2Mn adds 25----40 and rises KMnO
4Solution; Continue in the whole process to stir, the color of solution becomes till the brownish black, then shows MnO
2Generate; Gained suspension is heated 15min-60min under the temperature of 350K-410K, then filtration, drying; Control (CH
3COO)
2Mn and KMnO
4The addition of solution is made the manganese bioxide/carbon nano tube composite adsorbent of different manganese dioxide content.
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| CN 200610068772 CN1935355A (en) | 2006-09-07 | 2006-09-07 | Manganese bioxide/carbon nano tube composite adsorbent and its preparing method |
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| CN 200610068772 CN1935355A (en) | 2006-09-07 | 2006-09-07 | Manganese bioxide/carbon nano tube composite adsorbent and its preparing method |
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| CN101923960A (en) * | 2010-08-18 | 2010-12-22 | 东华大学 | Preparation method of composite electrode material using flap-like manganese dioxide nanocrystal to coat carbon nanotubes |
| CN101513612B (en) * | 2009-03-23 | 2012-01-11 | 浙江大学 | Catalyst for removing nitrogen oxide and organic pollutant discharged in burning and method for preparing same |
| 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 |
| CN103086438A (en) * | 2013-02-28 | 2013-05-08 | 陕西师范大学 | Preparation method of regular layer manganese oxide nanowire bundle parallel to substrate |
| CN104392849A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Manganese dioxide/ con composite material preparing method |
| CN104741081A (en) * | 2015-03-25 | 2015-07-01 | 杭州笨鸟环保科技有限公司 | Preparation method of filtering core material for air purifier for eliminating formaldehyde in long-acting manner |
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| CN105854802A (en) * | 2016-05-17 | 2016-08-17 | 遵义师范学院 | Cadmium-containing sewage treatment nano-composite material and preparing method thereof |
| WO2017096638A1 (en) * | 2015-12-07 | 2017-06-15 | 中国科学院生态环境研究中心 | Manganese dioxide nanofiber @ multidimensional mesoporous metal-organic framework adsorbent and preparation therefor |
| CN106925236A (en) * | 2017-03-28 | 2017-07-07 | 武汉轻工大学 | A kind of gelatin manganese dioxide composites preparation method and applications of Adsorption of Heavy Metals |
| CN107093527A (en) * | 2017-04-14 | 2017-08-25 | 燕山大学 | A kind of method for improving carbide-derived carbon super capacitor performance |
| CN109759015A (en) * | 2019-02-26 | 2019-05-17 | 广东工业大学 | A kind of calcium manganese modified magnetic carbon nano tube compound material, preparation method and applications |
| CN110665512A (en) * | 2019-09-27 | 2020-01-10 | 浙江大学 | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof |
| CN111606309A (en) * | 2020-06-30 | 2020-09-01 | 江苏理工学院 | Composite separation membrane for extracting tellurium and preparation method thereof |
| CN113634248A (en) * | 2020-05-11 | 2021-11-12 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
| CN113908690A (en) * | 2021-11-11 | 2022-01-11 | 沂水鸿羽环境科技中心 | Coating capable of purifying organic pollutants in air and having efficient sterilization performance |
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2006
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101513612B (en) * | 2009-03-23 | 2012-01-11 | 浙江大学 | Catalyst for removing nitrogen oxide and organic pollutant discharged in burning and method for preparing same |
| CN101923960B (en) * | 2010-08-18 | 2012-05-23 | 东华大学 | Preparation method of composite electrode material using flap-like manganese dioxide nanocrystal to coat carbon nanotubes |
| CN101923960A (en) * | 2010-08-18 | 2010-12-22 | 东华大学 | Preparation method of composite electrode material using flap-like manganese dioxide nanocrystal to coat carbon nanotubes |
| 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 |
| CN103086438A (en) * | 2013-02-28 | 2013-05-08 | 陕西师范大学 | Preparation method of regular layer manganese oxide nanowire bundle parallel to substrate |
| CN104392849B (en) * | 2014-11-20 | 2017-03-08 | 中南大学 | A kind of preparation method of manganese dioxide/carbon composite |
| CN104392849A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Manganese dioxide/ con composite material preparing method |
| CN104741081A (en) * | 2015-03-25 | 2015-07-01 | 杭州笨鸟环保科技有限公司 | Preparation method of filtering core material for air purifier for eliminating formaldehyde in long-acting manner |
| WO2017096638A1 (en) * | 2015-12-07 | 2017-06-15 | 中国科学院生态环境研究中心 | Manganese dioxide nanofiber @ multidimensional mesoporous metal-organic framework adsorbent and preparation therefor |
| CN105709720A (en) * | 2016-01-22 | 2016-06-29 | 湖北思搏盈环保科技有限公司 | Low-temperature SCR denitration catalyst using halloysite as carrier |
| CN105854802A (en) * | 2016-05-17 | 2016-08-17 | 遵义师范学院 | Cadmium-containing sewage treatment nano-composite material and preparing method thereof |
| CN106925236A (en) * | 2017-03-28 | 2017-07-07 | 武汉轻工大学 | A kind of gelatin manganese dioxide composites preparation method and applications of Adsorption of Heavy Metals |
| CN106925236B (en) * | 2017-03-28 | 2019-05-14 | 武汉轻工大学 | A kind of gelatin-manganese dioxide composites preparation method and applications for adsorbing heavy metal |
| CN107093527A (en) * | 2017-04-14 | 2017-08-25 | 燕山大学 | A kind of method for improving carbide-derived carbon super capacitor performance |
| CN109759015A (en) * | 2019-02-26 | 2019-05-17 | 广东工业大学 | A kind of calcium manganese modified magnetic carbon nano tube compound material, preparation method and applications |
| CN110665512A (en) * | 2019-09-27 | 2020-01-10 | 浙江大学 | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof |
| CN113634248A (en) * | 2020-05-11 | 2021-11-12 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
| CN113634248B (en) * | 2020-05-11 | 2022-12-30 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
| CN111606309A (en) * | 2020-06-30 | 2020-09-01 | 江苏理工学院 | Composite separation membrane for extracting tellurium and preparation method thereof |
| CN113908690A (en) * | 2021-11-11 | 2022-01-11 | 沂水鸿羽环境科技中心 | Coating capable of purifying organic pollutants in air and having efficient sterilization performance |
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