CN102602951B - Method for preparing kaoline nanotube - Google Patents
Method for preparing kaoline nanotube Download PDFInfo
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- CN102602951B CN102602951B CN 201210077376 CN201210077376A CN102602951B CN 102602951 B CN102602951 B CN 102602951B CN 201210077376 CN201210077376 CN 201210077376 CN 201210077376 A CN201210077376 A CN 201210077376A CN 102602951 B CN102602951 B CN 102602951B
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Abstract
The invention discloses a method for preparing a kaoline nanotube, which belongs to the technology of nanotubes. The method comprises the steps of: mixing kaoline and an intercalator, performing ultrasound treatment for 30min at a certain temperature, and then reacting in the condition of heating in water bath; then mixing the mixture with methanol and agitating at room temperature to perform a surface grafting reaction; finally, mixing the mixture with a methanol solution of a quaternary ammonium salt surfactant and reacting for a period of time under agitation at room temperature; and calcining to obtain the kaoline nanotube. The method for preparing the kaoline nanotube provided by the invention is performed at room temperature and is low in energy consumption, cheap and easily accessible in raw material, and simple, easily accessible in processing step, high in yield; and the kaoline nanotube prepared by the method is uniformly distributed in tube diameter and good in stability.
Description
Technical field
The present invention relates to a kind of preparation method of kaolin nanotube, belong to kaolin application performance development field.
Background technology
Distribute from the kaolin resource of China, the halloysite reserves of tubular structure are lower, the kaolinite of sheet structure is then more relatively, the raw material of producing high-grade ceramic is the kaolin that contains the tubular crystal structure mostly, utilize new technology that the kaolin of common sheet structure is prepared into the kaolin nanotube, the abundant common kaolin of reserves will be expected to become the substitute raw material of production high-quality pottery.From structure-forming process, be curled into the kaolin nanotube by the kaolin layer, feature by contrasting into the pipe pre-structure and the feature of Cheng Guanhou, the easier constitutional features of pipe that shows is to the Effect on Performance situation, in addition, the kaolin plane of crystal has the hydroxyl layer, has the very large space of modifying, so the kaolin nanotube is expected to be used widely in the new function/contour technological applications of structure-integrated material field.
At present the technology of preparing of kaolin nanotube adopts the technology of intercalation-peel off to carry out repeatable operation mostly, reported a kind of kaolin nanotube and preparation method thereof as Chinese patent CN102167346 A, this method is in operation more than 100 ℃, the reagent that uses has frowziness or toxicants such as methyl iodide, trolamine, needs large-scale instrument and equipments such as ball mill.Therefore, this method not only technology is loaded down with trivial details relatively, the energy consumption height, and economic benefit is not high enough, and the length-to-diameter ratio of product nanotube is also less.
Summary of the invention
The object of the present invention is to provide a kind of kaolin nanotube preparation method, this method has the advantages that flow process is simple, with low cost, efficient is high.
For achieving the above object, the present invention takes following technical proposals: a kind of kaolin nanotube preparation method is characterized in that comprising following process:
1) selecting the above kaolin of 100 orders for use is raw material, kaolin is added in intercalator dimethyl sulfoxide (DMSO) or the N-methylformamide, be mixed with every milliliter of intercalator and contain the kaolinic slurries of 0.5 ~ 1g, in 50 ~ 60 ℃ of following ultrasonic 30min of temperature, reacted under water bath condition 20 ~ 30 hours subsequently, drying gets powder after the reaction;
2) powder that step 1) is obtained adds powder in the methyl alcohol and mixes by wherein the kaolin quality and the mass ratio 1: 10 ~ 30 of methyl alcohol, and at room temperature stirring reaction is 48 ~ 72 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal;
3) contain 0.16 ~ 0.2g surface methoxyl group grafted kaolin according to every milliliter of concentration of slurry, with step 2) the methoxyl group grafted kaolin that obtains joins in the methanol solution that concentration is 1 ~ 1.5mol/L quaternary surfactant, described quaternary surfactant is a palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide or Trimethyllaurylammonium bromide, at room temperature stirred 10 ~ 30 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying again, with 3 ~ 5 ℃/min of temperature rise rate, be warming up to 400 ~ 500 ℃ of constant temperature 4 ~ 6h calcinings, obtain the kaolin nanotube.
The invention has the advantages that: all inexpensive being easy to get of raw material that present method adopts, preparation technology is simple, energy consumption is lower, the kaolin nanotube diameter that makes is 13 ~ 25nm, caliber distribution homogeneous, and productive rate is higher, stability better, satisfy the requirement in the new function/contour technological applications of structure-integrated material field fully, kaolinic deep processing and utilization is produced far-reaching influence, have bigger economic worth.
Description of drawings
Fig. 1 is the prepared kaolin nanotube TEM photo of example of the present invention 6.
Embodiment
Example 1
Selecting the 100 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator dimethyl sulfoxide (DMSO), is mixed with every milliliter of intercalator and contains the kaolinic slurries of 0.5g.In 50 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 20 hours subsequently.Drying gets powder 11.6g after the reaction, drying is got powder add in the 100ml methyl alcohol, and at room temperature stirring reaction is 48 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Getting 5g methoxyl group grafted kaolin adding concentration is among the methanol solution 31ml of 1mol/L palmityl trimethyl ammonium chloride, at room temperature stirred 10 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 3 ℃/min of temperature rise rate, is warming up to 400 ℃ of constant temperature 6h calcinings again, obtain the kaolin nanotube, average caliber 18nm, mean length is 1000-1100nm, productive rate is about the 50%(mass percent).
Example 2
Selecting the 150 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator dimethyl sulfoxide (DMSO), is mixed with every milliliter of intercalator and contains the kaolinic slurries of 1g.In 60 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 25 hours subsequently.Drying gets powder 11.8g after the reaction, drying is got powder add in the 200ml methyl alcohol, and at room temperature stirring reaction is 56 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Getting 5g methoxyl group grafted kaolin adding concentration is among the methanol solution 28ml of 1.25mol/L palmityl trimethyl ammonium chloride, at room temperature stirred 20 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 4 ℃/min of temperature rise rate, is warming up to 500 ℃ of constant temperature 5h calcinings again, obtain the kaolin nanotube, average caliber 20nm, mean length is 800-900nm, productive rate is about the 60%(mass percent).
Example 3
Selecting the 200 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator dimethyl sulfoxide (DMSO), is mixed with every milliliter of intercalator and contains the kaolinic slurries of 0.5g.In 50 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 30 hours subsequently.Drying gets powder 11.5g after the reaction, drying is got powder add in the 300ml methyl alcohol, and at room temperature stirring reaction is 72 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Getting 5g methoxyl group grafted kaolin adding concentration is among the methanol solution 25ml of 1.5mol/L palmityl trimethyl ammonium chloride, at room temperature stirred 30 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 5 ℃/min of temperature rise rate, is warming up to 500 ℃ of constant temperature 4h calcinings again, obtain the kaolin nanotube, average caliber 18nm, mean length is 900-1100nm, productive rate is about the 70%(mass percent).
Example 4
Selecting the 100 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator N-methylformamide, is mixed with every milliliter of intercalator and contains the kaolinic slurries of 0.5g.In 60 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 20 hours subsequently.Drying gets powder 11.6g after the reaction, drying is got powder add in the 100ml methyl alcohol, and at room temperature stirring reaction is 48 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Getting 5g methoxyl group grafted kaolin adding concentration is among the methanol solution 31ml of 1mol/L palmityl trimethyl ammonium chloride, at room temperature stirred 10 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 3 ℃/min of temperature rise rate, is warming up to 400 ℃ of constant temperature 4h calcinings again, obtain the kaolin nanotube, average caliber 18nm, mean length is 1000-1200nm, productive rate is the 70%(mass percent).
Example 5
Selecting the 150 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator N-methylformamide, is mixed with every milliliter of intercalator and contains the kaolinic slurries of 1g.In 50 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 25 hours subsequently.Drying gets powder 11.7g after the reaction, drying is got powder add in the 200ml methyl alcohol, and at room temperature stirring reaction is 56 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Getting 5g methoxyl group grafted kaolin adding concentration is among the methanol solution 28ml of 1.25mol/L palmityl trimethyl ammonium chloride, at room temperature stirred 20 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 4 ℃/min of temperature rise rate, is warming up to 500 ℃ of constant temperature 5h calcinings again, obtain the kaolin nanotube, average caliber 20nm, mean length is 900-1100nm, productive rate is the 75%(mass percent).
Example 6
Selecting the 200 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator N-methylformamide, is mixed with every milliliter of intercalator and contains the kaolinic slurries of 0.5g.In 60 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 30 hours subsequently.Drying gets powder 11.2g after the reaction, drying is got powder add in the 300ml methyl alcohol, and at room temperature stirring reaction is 72 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Getting 5g methoxyl group grafted kaolin adding concentration is among the methanol solution 25ml of 1.5mol/L palmityl trimethyl ammonium chloride, at room temperature stirred 30 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 5 ℃/min of temperature rise rate, is warming up to 500 ℃ of constant temperature 4h calcinings again, obtain the kaolin nanotube, average caliber 18nm, mean length is 800-1100nm, productive rate is the 80%(mass percent).
Example 7
Selecting the 150 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator dimethyl sulfoxide (DMSO), is mixed with every milliliter of intercalator and contains the kaolinic slurries of 0.5g.In 50 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 25 hours subsequently.Drying gets powder 11.5g after the reaction, drying is got powder add in the 200ml methyl alcohol, and at room temperature stirring reaction is 48 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Getting 5g methoxyl group grafted kaolin adding concentration is among the methanol solution 28ml of 1mol/L cetyl trimethylammonium bromide, at room temperature stirred 25 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 3 ℃/min of temperature rise rate, is warming up to 500 ℃ of constant temperature 5h calcinings again, obtain the kaolin nanotube, average caliber 18nm, mean length is 900-1100nm, productive rate is the 60%(mass percent).
Example 8
Selecting the 150 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator dimethyl sulfoxide (DMSO), is mixed with every milliliter of intercalator and contains the kaolinic slurries of 0.5g.In 50 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 25 hours subsequently.Drying gets powder 11.4g after the reaction, drying is got powder add in the 200ml methyl alcohol, and at room temperature stirring reaction is 48 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Getting 5g methoxyl group grafted kaolin adding concentration is among the methanol solution 31ml of 1mol/L Trimethyllaurylammonium bromide, at room temperature stirred 25 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 3 ℃/min of temperature rise rate, is warming up to 500 ℃ of constant temperature 5h calcinings again, obtain the kaolin nanotube, average caliber 18nm, mean length is 900-1000nm, productive rate is the 70%(mass percent).
Example 9
Selecting the 150 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator N-methylformamide, is mixed with every milliliter of intercalator and contains the kaolinic slurries of 1g.In 60 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 25 hours subsequently.Drying gets powder 11.9g after the reaction, drying is got powder add in the 200ml methyl alcohol, and at room temperature stirring reaction is 56 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Get among the methanol solution 28ml of 5g methoxyl group grafted kaolin adding concentration 1.25mol/L cetyl trimethylammonium bromide, at room temperature stirred 20 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying with 3 ℃/min of temperature rise rate, is warming up to 500 ℃ of constant temperature 5h calcinings again, obtain the kaolin nanotube, average caliber 20nm, mean length is 1000-1100nm, productive rate is the 75%(mass percent).
Example 10
Selecting the 150 purpose Suzhou kaolin 10g that handle well through washing for use is raw material, and kaolin is added in the intercalator N-methylformamide, is mixed with every milliliter of intercalator and contains the kaolinic slurries of 1g.In 50 ℃ of following ultrasonic 30min of temperature, under water bath condition, reacted 25 hours subsequently.Drying gets powder 11.5g after the reaction, drying is got powder add in the 200ml methyl alcohol, and at room temperature stirring reaction is 56 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal.Get 5g methoxyl group grafted kaolin, add among the methanol solution 31ml of 30ml concentration 1.25mol/L cetyl trimethylammonium bromide, at room temperature stirred 20 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying again, with 3 ℃/min of temperature rise rate, be warming up to 500 ℃ of constant temperature 5h calcinings, obtain the kaolin nanotube, average caliber 20nm, mean length is 800-1100nm, and productive rate is the 70%(mass percent).
Claims (1)
1. kaolin nanotube preparation method is characterized in that comprising following process:
1) selecting the above kaolin of 100 orders for use is raw material, kaolin is added in intercalator dimethyl sulfoxide (DMSO) or the N-methylformamide, be mixed with every milliliter of intercalator and contain the kaolinic slurries of 0.5 ~ 1g, in 50 ~ 60 ℃ of following ultrasonic 30min of temperature, reacted under water bath condition 20 ~ 30 hours subsequently, drying gets powder after the reaction;
2) powder that step 1) is obtained is by wherein the kaolin quality and the mass ratio 1: 10 ~ 30 of methyl alcohol, powder added in the methyl alcohol mix, and at room temperature stirring reaction is 48 ~ 72 hours, obtains surperficial methoxyl group grafted kaolin through centrifugal;
3) contain 0.16 ~ 0.2g surface methoxyl group grafted kaolin according to every milliliter of concentration of slurry, with step 2) the methoxyl group grafted kaolin that obtains joins in the methanol solution that concentration is 1 ~ 1.5mol/L quaternary surfactant, described quaternary surfactant is a palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide or Trimethyllaurylammonium bromide, at room temperature stirred 10 ~ 30 hours, afterwards with ethanol wash add the water non-foam to the washings till, drying again, with 3 ~ 5 ℃/min of temperature rise rate, be warming up to 400 ~ 500 ℃ of constant temperature 4 ~ 6h calcinings, obtain the kaolin nanotube.
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| CN 201210077376 CN102602951B (en) | 2012-03-22 | 2012-03-22 | Method for preparing kaoline nanotube |
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| CN 201210077376 CN102602951B (en) | 2012-03-22 | 2012-03-22 | Method for preparing kaoline nanotube |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103922358B (en) * | 2014-05-04 | 2016-03-16 | 张玉德 | The preparation method of kaolinite nanotube |
| CN104386702A (en) * | 2014-11-05 | 2015-03-04 | 吴俊荣 | Preparation method of kaolin nanotube |
| CN104475025A (en) * | 2014-11-06 | 2015-04-01 | 天津大学 | Preparation method of kaolin nanotube used for desulfurizer |
| CN105185450A (en) * | 2015-09-22 | 2015-12-23 | 晋源电气集团股份有限公司 | Oil platform cable |
| CN106276938A (en) * | 2016-07-21 | 2017-01-04 | 中南大学 | A kind of kaolinite methanol intercalated compound and preparation method thereof |
| CN106517224B (en) * | 2016-11-28 | 2018-09-18 | 河南理工大学 | A kind of preparation method of kaolinite nanometer sheet |
| CN108049285A (en) * | 2017-12-01 | 2018-05-18 | 金华市纯体育器材有限公司 | A kind of vapor-permeable type ties line plastic cement race track and its laying method certainly |
| CN109704352B (en) * | 2018-12-16 | 2022-04-15 | 桂林理工大学 | Preparation method of stable pickering emulsion based on kaolinite with lock catch type structure |
| CN110156035A (en) * | 2019-07-03 | 2019-08-23 | 南京大学 | A kind of kaolin nanotube preparation method |
| CN110203944A (en) * | 2019-07-03 | 2019-09-06 | 南京大学 | It is a kind of efficiently to prepare kaolin nanotube method |
| CN114261969A (en) * | 2021-12-25 | 2022-04-01 | 太原科技大学 | Preparation method of coal-series kaolin with high oil absorption |
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| CN1204206C (en) * | 2001-09-13 | 2005-06-01 | 湖北葛店开发区地大纳米材料制造有限公司 | Mechanical and chemical stripping process for preparing superfine kaolin |
| CN1218871C (en) * | 2003-11-17 | 2005-09-14 | 陕西科技大学 | Kaolinite intercalation method |
| CN101058425A (en) * | 2006-04-21 | 2007-10-24 | 同济大学 | Method for preparing nano-grade sheet kaolinite |
| CN100584896C (en) * | 2007-08-24 | 2010-01-27 | 中国地质大学（武汉） | A kind of production technology of paper coating kaoline |
| CN101723392A (en) * | 2008-10-25 | 2010-06-09 | 杜一挺 | Method for preparing nanometer silver/clay intercalated compound |
| CN102167346B (en) * | 2011-01-30 | 2012-08-22 | 福州大学 | Kaolin nanotube and preparation method thereof |
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