CN100457637C - Method for preparing nano manganese dioxide - Google Patents
Method for preparing nano manganese dioxide Download PDFInfo
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- CN100457637C CN100457637C CNB021577374A CN02157737A CN100457637C CN 100457637 C CN100457637 C CN 100457637C CN B021577374 A CNB021577374 A CN B021577374A CN 02157737 A CN02157737 A CN 02157737A CN 100457637 C CN100457637 C CN 100457637C
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Abstract
The preparation method of nano manganese dioxide is characterized by that it uses potassium permanganate, uses alkylol polyethenoxy ether as reducing agent, surface dispersing agent and grain size stabilizing agent, and makes then produce oxidation and reduction reaction to prepare nano manganese dioxide.
Description
Technical field
The present invention addresses a kind of preparation method of nano-manganese dioxide, belongs to technical field of chemical compound preparation.
Background technology
Manganse Dioxide is a kind of important material in the fields such as the energy and electronics, is widely used in the cathode material of battery and electrical condenser; In electronic industry, be used to make magneticsubstance in addition; In chemical industry, be used for the manufacturing of glass, pottery and dyestuff and be used as oxygenant.Because extensive exploitation, the application of natural manganese dioxide, resource is exhausted day by day, the high energy consumption of electrolytic manganese dioxide and seriously polluted, and the Manganse Dioxide performance requriements improved constantly the research that has impelled the Manganse Dioxide study on the modification and prepared Manganse Dioxide by chemical method.Chemical method generally includes at present: thermal decomposition method, and liquid phase oxidation, reduction method, the manganous hydroxide oxidation style, and the preparation of dopping manganese dioxide etc.The size of nano-manganese dioxide is 1～100nm, owing to have high surface, so nano-manganese dioxide has various particular performances in each field.For the preparation of nano-manganese dioxide, traditional sol-gel method etc. is arranged, sol-gel method is difficult to the fixedly size of crystal grain because the stability difference of preparation colloidal solution is unfavorable for controlling the grain growing of Manganse Dioxide.
Summary of the invention
The purpose of this invention is to provide a kind of chemical process and make nano-manganese dioxide, enable to produce stable crystal formation and grain size.
Preparation method of the present invention is different from traditional chemical process, it is characterized in that with potassium permanganate being raw material, make full use of the property of alkyl alcohol Soxylat A 25-7, with the alkyl alcohol Soxylat A 25-7 as reductive agent, surface dispersant, size are stablized the utmost point and solvent, make nano-manganese dioxide by the oxidation-reduction reaction.Its reaction formula is as follows:
That wherein the alkyl alcohol Soxylat A 25-7 adopts is n=1-10, and R is the alkyl of 4-22 carbon.
Its preparation method is as described below:
With potassium permanganate in molar ratio: 1: 1～3 put into the alkyl alcohol Soxylat A 25-7 in batches, and control reaction temperature is below 60 ℃, and stirring reaction is 3～4 hours then, add dehydrated alcohol, continue to stir 30 minutes, leach solids, carry out refluxing wash-out in 2～3 hours with dehydrated alcohol again; Filter once more, leaching solids is rough Manganse Dioxide, places 75～85 ℃ of oven dry then, and under 400 ℃ condition, crystallization 4 hours promptly gets the powder of the nano-manganese dioxide of black with the Manganse Dioxide after the oven dry.
The consumption of alkyl alcohol Soxylat A 25-7 is 1.5～3 times of potassium permanganate mole number, and 1 part is used for reducing, and all the other are used for serving as solvent and surface dispersant; Its twice add-on of described dehydrated alcohol equate, all with reactant volume ratio 1: 1.
Little and the good stability of the particle diameter of the prepared Manganse Dioxide of the inventive method owing to adopted the alkyl alcohol Soxylat A 25-7, utilizes its property, and it is still reductive agent, surface dispersant and solvent not, or particle diameter stablizer and tensio-active agent.
In the inventive method, its byproduct of reaction alkyl polyoxyethylene ether carboxylic acid is a kind of broad-spectrum tensio-active agent, through reclaiming, handles and can collect this width of cloth product.Can also recycling for the dehydrated alcohol in the manufacturing processed, the non-environmental-pollution problem produces.
In addition, the present invention utilizes the alkyl alcohol Soxylat A 25-7 as reductive agent and potassium permanganate reaction, different and the general alcohol of the special construction of this compound, speed of response is accelerated greatly, and can invest the surface of the Manganse Dioxide of generation, fabulous dispersion the Manganse Dioxide that produces of reaction, reduce agglomeration.Adopt the dehydrated alcohol can be, size that simultaneously can stabilized chlorine manganese crystal grain with the tensio-active agent wash-out of Manganse Dioxide surface adsorption.In preparation process, because the crystal formation instability that produces, so also must be under 400 ℃ of certain temperatures, crystallization 4 hours.
The easy convenience of preparation method's technology of the present invention, and reaction is fast, fully.
Embodiment
Now embodiments of the invention are described in the back:
Embodiment one: earlier with alkyl alcohol Soxylat A 25-7 (n=7, R=10～12) 750g (1.5mol) puts into reaction flask, add potassium permanganate 158g (1mol) in the stirring in batches, react a large amount of heat releases,,, continue to stir 3 hours after all adding below 60 ℃ with suitable feed rate controlled temperature, add 1: 1 dehydrated alcohol of volume ratio then, continue to stir 30 minutes.Carry out suction filtration then, obtain the chocolate filter cake, filter cake slightly after the seasoning, was refluxed 4 hours with dehydrated alcohol, suction filtration once more, obtaining filter residue is the rough Manganse Dioxide of gained.Be placed on 75～85 ℃ of bakings 4 hours then.With the crystallization 4 hours under 400 ℃ condition of the Manganse Dioxide after the oven dry, obtain the powder 71.8g of the Manganse Dioxide of black, its particle diameter is at 6～60nm.Yield is 82%.
The alkyl alcohol Soxylat A 25-7 that adopt in this place is a chemicals, and is on sale on market, needn't prepare voluntarily again.
Embodiment two: earlier alkyl alcohol Soxylat A 25-7 (n=3, R=10～12) 109g (0.12mol) is put into reaction flask, adds potassium permanganate 10g (0.06mol) in the stirring in batches, react a large amount of heat releases, with suitable feed rate controlled temperature below 60 ℃.After all adding, continue to stir 2 hours.Add 1: 1 dehydrated alcohol of volume ratio then, continue to stir 30 minutes.Suction filtration obtains the chocolate filter cake then.After filter cake carried out seasoning, refluxed 2 hours with dehydrated alcohol again, suction filtration once more, obtaining filter residue is the rough Manganse Dioxide of gained.Be placed on 75～85 ℃ of bakings 4 hours then.Under 400 ℃ condition, crystallization 4 hours can obtain the powder 4.73g of the Manganse Dioxide of black with the Manganse Dioxide after the oven dry, and its particle diameter is at 8～65nm, and yield is 86%.
Embodiment three: earlier with the alkyl alcohol Soxylat A 25-7 (n=1, R=12) 40g (0.16mol) puts into reaction flask, adds potassium permanganate 10g (0.06mol) in the stirring in batches, reacts a large amount of heat releases, with suitable feed rate controlled temperature below 60 ℃.After all adding, continue to stir 2 hours.Add 1: 1 dehydrated alcohol of volume ratio then, continue to stir 30 minutes.Carry out suction filtration then, obtain the chocolate filter cake.Filter cake slightly after the seasoning, was refluxed 2 hours with dehydrated alcohol again, suction filtration once more, obtaining filter residue is the rough Manganse Dioxide of gained.Be placed on 75～85 ℃ of bakings 4 hours then.Under 400 ℃ condition, crystallization 4 hours promptly obtains the powder 4.4g of the Manganse Dioxide of black with the Manganse Dioxide after the oven dry, and its particle diameter is at 8～60nm, and yield is 80%.
Claims (2)
1. the preparation method of a nano-manganese dioxide, the concrete steps that it is characterized in that this method are: with potassium permanganate in molar ratio: 1: 1～3 put into the alkyl alcohol Soxylat A 25-7 in batches, control reaction temperature is below 60 ℃, stirring reaction is 3～4 hours then, add dehydrated alcohol, continue to stir 30 minutes, leach solids, carry out refluxing wash-out in 2～3 hours with dehydrated alcohol again; Filter once more, leaching solids is rough Manganse Dioxide, places 75～85 ℃ of oven dry then, and under 400 ℃ condition, crystallization 4 hours promptly gets the powder of the nano-manganese dioxide of black with the Manganse Dioxide after the oven dry; The molecular formula of the alkyl alcohol Soxylat A 25-7 that is adopted is:
N=1-10 wherein, R is the alkyl of 4-22 carbon.
2. the preparation method of a kind of nano-manganese dioxide as claimed in claim 1, the consumption that it is characterized in that described alkyl alcohol Soxylat A 25-7 is 1.5～3 times of potassium permanganate mole number, its twice add-on of described dehydrated alcohol equate, all with reactant volume ratio 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021577374A CN100457637C (en) | 2002-12-24 | 2002-12-24 | Method for preparing nano manganese dioxide |
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| CNB021577374A CN100457637C (en) | 2002-12-24 | 2002-12-24 | Method for preparing nano manganese dioxide |
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| CN1438181A CN1438181A (en) | 2003-08-27 |
| CN100457637C true CN100457637C (en) | 2009-02-04 |
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| CNB021577374A Expired - Fee Related CN100457637C (en) | 2002-12-24 | 2002-12-24 | Method for preparing nano manganese dioxide |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308245C (en) * | 2005-03-30 | 2007-04-04 | 山东师范大学 | Method for synthesizing nano material of manganese dioxide in dandelion and stick shape |
| CN100393626C (en) * | 2005-11-07 | 2008-06-11 | 山东师范大学 | Method for synthesizing nano-structure of bunchy manganese dioxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377832A (en) * | 2002-01-18 | 2002-11-06 | 清华大学 | Process for synthesizing different crystal form one-dimensional single crystal mangnesium dioxide nano wire |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377832A (en) * | 2002-01-18 | 2002-11-06 | 清华大学 | Process for synthesizing different crystal form one-dimensional single crystal mangnesium dioxide nano wire |
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Granted publication date: 20090204 Termination date: 20111224 |