CN102653410A - Method for preparing fibriform boehmite - Google Patents
Method for preparing fibriform boehmite Download PDFInfo
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- CN102653410A CN102653410A CN2011100511817A CN201110051181A CN102653410A CN 102653410 A CN102653410 A CN 102653410A CN 2011100511817 A CN2011100511817 A CN 2011100511817A CN 201110051181 A CN201110051181 A CN 201110051181A CN 102653410 A CN102653410 A CN 102653410A
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- boehmite
- sodium metaaluminate
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- preparation
- fibriform
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Abstract
The invention relates to a method for preparing fibriform boehmite, comprising the following steps of: weighing solid sodium metaaluminate and dissolving the solid sodium metaaluminate in de-ionized water to form a sodium metaaluminate solution; dropwise adding the prepared sodium metaaluminate solution to an aluminum sulfate solution along with fierce stirring, wherein the mol ratio of the sodium metaaluminate to the aluminum sulfate is 2.5-10; mixing the final mixture for more than 10 minutes, thus obtaining high-dispersion degree suspension; transferring the obtained suspension to a high-pressure reaction kettle for reaction for 5-72 hours at 160-250 DEG C; after the reaction is completed, naturally reducing the temperature of the high-pressure kettle to the room temperature, centrifugally washing the obtained white precipitate, and drying the precipitate at 60-100 DEG C to obtain pure fibriform boehmite. The boehmite prepared by the method is fibriform, has a fiber diameter of 6-15 nanometers and a pore volume greater than 0.4 ml/g; and the preparation method is simple to operate, rich in source, easy for industrialization, low in cost, good in stability and free of pollution on environment.
Description
Technical field
The present invention relates to a kind of preparation method of fibrous boehmite.Particularly, the present invention relates to Tai-Ace S 150 and sodium metaaluminate is that the feedstock production diameter is the method for 6～15 nanometer fibrous boehmites.
Technical background
Boehmite (boehmite) is also referred to as boehmite, is the hydrate of aluminum oxide.Boehmite has multiple pattern, comprises sheet, fibrous and spherical.Nanometer fibrous boehmite has the advantages that specific surface area is big, pore volume is big, can be used for the carrier of catalyzer and sorbent material.
Bugosh is at USP U.S.Pat.No.2, in 915,475, described a fibrous boehmite method of preparation, obtains through the aluminum chloride of the alkalescence of hydrolysis at high temperature and the aluminum nitrate of alkalescence.The aluminum nitrate of the aluminum chloride of used alkalescence and alkalescence makes with aluminum chloride or aluminum nitrate and metallic aluminium reaction, the raw materials cost height.
Bamboo village one tree waits the people to provide in Chinese patent CN101117231A that the gipsite hydrothermal conversion is specific surface area 20～80m in the presence of mg ion, mn ion
2The preparation method of the fibrous boehmite of/g.The fibrous boehmite of this method preparation is Fibre diameter 16～67 nanometers.
Adopt recent years the tensio-active agent assisted synthesizing method to prepare the one dimension boehmite and obtain broad development.Kuang etc. (J.Mater.Chem.2003,13,660-662) under ctab surface promoting agent condition, synthesize the boehmite nanotube 120 ℃ of following hydro-thermals, the nanotube that obtains is about 30-70nm, internal diameter 3-4nm, external diameter 5-6nm.(Chem.Mater.2002 such as Zhu; 14,2086-2093) reported the growth of boehmite nanofiber, under 100 ℃ of low temperature, PEO tensio-active agent and the thermal treatment of aluminium hydrate mixing water are obtained fibrous boehmite; The fibrous boehmite 3-4nm that obtains is thick, and 30-60nm is long.
But, adopt tensio-active agent householder method synthesizing one-dimensional boehmite to have very big shortcoming, the one, cost is high, and the 2nd, going out tensio-active agent mutually from boehmite is difficulty very, no matter this must cause the existence of impurity in the boehmite product.
Summary of the invention
The purpose of this invention is to provide a kind of is initial feed with sodium metaaluminate and Tai-Ace S 150, does not have under the tensio-active agent existence condition, and the synthetic diameter of hydro-thermal is the method for 6～15 nanometer fibrous boehmites.
The boehmite of the present invention's preparation has high purity, and pattern is fibrous, and Fibre diameter is 6～15 nanometers, and pore volume is not less than 0.4ml/g.
Fibrous boehmite provided by the invention be with sodium metaaluminate and Tai-Ace S 150 as raw material, the suspension-s of the aluminium hydrate that titration obtains obtains in reaction kettle for reaction.
The preparation method of the fibrous boehmite of the present invention is; Adopt volumetry to prepare the intermediate product-aluminium hydrate that forms boehmite earlier; Then intermediate product-aluminium the hydrate that obtains is left standstill hydrothermal treatment consists, cooling at last, washing; Drying obtains boehmite, and the practical implementation step comprises following:
1) takes by weighing 10g～30g sodium metaaluminate solid, be dissolved in the 100ml deionized water, form sodium aluminate solution.
2) take by weighing Patent alum, add deionized water dissolving, be poured in the 250mL volumetric flask, constant volume makes the alum liquor that concentration is 0.1～0.4mol/L.
3) with the sodium aluminate solution that makes under the condition of magnetic agitation, dropwise join in the alum liquor of 0.1～0.4mol/L, wherein sodium metaaluminate and Tai-Ace S 150 al mole ratio are 2.5-10.
4) final mixture is stirred more than the 10min, to obtain dispersity suspension-s preferably.
5) suspension-s that obtains is transferred in the autoclave, handles 5h～72h down at 160 ℃～250 ℃.
6) reaction naturally cools to room temperature with autoclave temp after accomplishing, and the white depositions that obtains is used centrifuge washing, obtains boehmite 60～100 ℃ of following dryings.
The prepared boehmite of present method is fibrous, Fibre diameter 6～15 nanometers, and pore volume is greater than 0.4ml/g, and this preparation method is simple to operate, and raw material is easy to get, and is prone to industriallization; Cost is low, good stability and free from environmental pollution.
Embodiment
The specific surface area of product boehmite and pore volume are used determination of nitrogen adsorption among the embodiment, and the evaluation product also calculates percent crystallinity and measures with xrd method, and the size of fibrous width and length obtains through transmission electron microscope observing.
Embodiment 1
Present embodiment is explained the preparation of boehmite provided by the invention
(German Sigma-aldrich company produces, Al accurately to take by weighing the 29.5g sodium metaaluminate
2O
3Content is 50-56 weight %, Na
2O content is 40-45%), be dissolved in the 100ml deionized water, be mixed with sodium aluminate solution A.Take by weighing 66.64g Patent alum (Shantou Xilong Chemical Factory Co., Ltd produces, analytical pure), add deionized water dissolving, be poured in the 250mL volumetric flask, constant volume makes the alum liquor that concentration is 0.4mol/L.The alum liquor 180mL that is mixed with is changed in the 500mL there-necked flask; Under room temperature and agitation condition; The sodium aluminate solution A that makes is added drop-wise in the there-necked flask with the speed of 2 ml/min; After sodium aluminate solution A dropwised, white suspension stirred 2.5h fast under room temperature, obtain uniform white suspension.
The uniform white suspension that obtains is encapsulated in the autoclave of 100mL; Oven temperature is adjusted to 165 ℃, the reaction kettle that installs is put in the baking oven, leave standstill and placed 5 hours; Naturally cool to room temperature; Products therefrom with deionized water centrifuge washing 3 times after, in 60 ℃ of dryings 24 hours, obtain boehmite.
The boehmite that obtains is done corresponding sign, characterize through XRD, the JCPDSCard No.21-1307 diffraction peak card comparison with standard shows that the product that is obtained is a boehmite, and does not contain the existence of any impurity that the product that makes has high purity.The shape characteristic of product obtains through transmission electron microscope observing, and the boehmite product that obtains is fibrous and blocky mixture.With the specific surface area and the pore volume of determination of nitrogen adsorption product boehmite, specific surface area is 218.0m
2g
-1, Fibre diameter 6.1 nanometers, pore volume is 0.5136ml/g.
Embodiment 2
Present embodiment is explained the preparation of boehmite provided by the invention
(German Sigma-aldrich company produces, Al accurately to take by weighing the 14.75g sodium metaaluminate
2O
3Content is 50-56 weight %, Na
2O content is 40-45%), be dissolved in the 100ml deionized water, be mixed with sodium aluminate solution B.Take by weighing 33.32g Patent alum (Shantou Xilong Chemical Factory Co., Ltd produces, analytical pure), add deionized water dissolving, be poured in the 250mL volumetric flask, constant volume makes the alum liquor that concentration is 0.2mol/L.The alum liquor 180mL that is mixed with is changed in the 500mL there-necked flask; Under room temperature and agitation condition; The sodium aluminate solution B that makes is added drop-wise in the there-necked flask with the speed of 2 ml/min; After sodium aluminate solution B dropwised, white suspension stirred 0.5h fast under room temperature, obtain uniform white suspension.
The uniform white suspension that obtains is encapsulated in the autoclave of 100mL; Oven temperature is adjusted to 180 ℃, the reaction kettle that installs is put in the baking oven, leave standstill and placed 24 hours; Naturally cool to room temperature; Products therefrom with deionized water centrifuge washing 3 times after, in 60 ℃ of dryings 24 hours, obtain boehmite.
The boehmite that obtains is done corresponding sign; Characterize through XRD, the JCPDSCard No.21-1307 diffraction peak card comparison with standard shows that the product that is obtained is a boehmite; And do not contain the existence of any impurity, the product that makes has high purity and high percent crystallinity.The shape characteristic of product obtains through transmission electron microscope observing, and the boehmite product that obtains is fibrous, the about 50-150nm of length.With the specific surface area and the pore volume of determination of nitrogen adsorption product boehmite, specific surface area is 159.5m
2g
-1, Fibre diameter 8.3 nanometers, pore volume is 0.4540ml//g.
Embodiment 3
Present embodiment is explained the preparation of boehmite provided by the invention
(German Sigma-aldrich company produces, Al accurately to take by weighing the 29.5g sodium metaaluminate
2O
3Content is 50-56 weight %, Na
2O content is 40-45%), be dissolved in the 100ml deionized water, be mixed with sodium aluminate solution C.Take by weighing 66.64g Patent alum (Shantou Xilong Chemical Factory Co., Ltd produces, analytical pure), add deionized water dissolving, be poured in the 250mL volumetric flask, constant volume makes the alum liquor that concentration is 0.4mol/L.The alum liquor 180mL that is mixed with is changed in the 500mL there-necked flask; Under room temperature and agitation condition; The sodium aluminate solution C that makes is added drop-wise in the there-necked flask with the speed of 3 ml/min; After sodium aluminate solution C dropwised, white suspension stirred 2 hours under room temperature fast, obtained uniform white suspension.
The uniform white suspension that obtains is encapsulated in the autoclave of 100mL; Oven temperature is adjusted to 180 ℃, the reaction kettle that installs is put in the baking oven, leave standstill and placed 24 hours; Naturally cool to room temperature; Products therefrom with deionized water centrifuge washing 3 times after, in 60 ℃ of dryings 24 hours, obtain boehmite.
The boehmite that obtains is done corresponding sign; Characterize through XRD, the JCPDSCard No.21-1307 diffraction peak card comparison with standard shows that the product that is obtained is a boehmite; And do not contain the existence of any impurity, the product that makes has high purity and high percent crystallinity.The shape characteristic of product obtains through transmission electron microscope observing, and the boehmite product that obtains is fibrous, the about 100-200nm of length.With the specific surface area and the pore volume of determination of nitrogen adsorption product boehmite, specific surface area is 193.1m
2g
-1, Fibre diameter 6.9 nanometers, pore volume is 0.4795ml/g.
Embodiment 4
Present embodiment is explained the preparation of boehmite provided by the invention
(German Sigma-aldrich company produces, Al accurately to take by weighing the 14.75g sodium metaaluminate
2O
3Content is 50-56 weight %, Na
2O content is 40-45%), be dissolved in the 100ml deionized water, be mixed with sodium aluminate solution A.Take by weighing 33.32g Patent alum (Shantou Xilong Chemical Factory Co., Ltd produces, analytical pure), add deionized water dissolving, be poured in the 250mL volumetric flask, constant volume makes the alum liquor that concentration is 0.2mol/L.The alum liquor 180mL that is mixed with is changed in the 500mL there-necked flask; Under room temperature and agitation condition; The sodium aluminate solution A that makes is added drop-wise in the there-necked flask with the speed of 2 ml/min; After sodium aluminate solution A dropwised, white suspension stirred 2 hours under room temperature fast, obtained uniform white suspension.
The uniform white suspension that obtains is encapsulated in the autoclave of 100mL; Oven temperature is adjusted to 220 ℃, the reaction kettle that installs is put in the baking oven, leave standstill and placed 12 hours; Naturally cool to room temperature; Products therefrom with deionized water centrifuge washing 3 times after, in 60 ℃ of dryings 24 hours, obtain product.
The product that obtains is done corresponding sign; Characterize through XRD, the JCPDS CardNo.21-1307 diffraction peak card comparison with standard shows that the product that is obtained is a boehmite; And do not contain the existence of any impurity, the product that makes has high purity and high percent crystallinity.The shape characteristic of product obtains through transmission electron microscope observing, and the boehmite product that obtains is fibrous, the about 50-100nm of length.With the specific surface area and the pore volume of determination of nitrogen adsorption product boehmite, specific surface area is 102.1m
2g
-1, Fibre diameter 13 nanometers, pore volume is 0.4023ml/g.
Claims (4)
1. the preparation method of a fibrous boehmite is characterized in that:
Preparing method's step is following:
1) takes by weighing 10～30g sodium metaaluminate solid, be dissolved in the 100ml deionized water, form sodium aluminate solution;
2) under vigorous stirring, the sodium aluminate solution that makes dropwise is added in the alum liquor of 0.1～0.4mol/L;
3) final mixture is stirred more than the 10min, to obtain dispersity suspension-s preferably, wherein sodium metaaluminate and Tai-Ace S 150 al mole ratio are 2.5-10;
4) suspension-s that obtains is transferred in the autoclave, at 160 ℃～250 ℃ reactions down, 5h～72h;
5) reaction naturally cools to room temperature with autoclave temp after accomplishing, and the white depositions that obtains is used centrifuge washing, obtains pure fibrous boehmite 60～100 ℃ of following dryings.
2. according to the preparation method of the described fibrous boehmite of claim 1, it is characterized in that: the pH value of the suspension-s that step 3 obtains is controlled at 7～9.
3. according to the preparation method of the described fibrous boehmite of claim 1, it is characterized in that: the temperature of reaction in the step 4 is controlled at 160 ℃～220 ℃.
4. according to the preparation method of the described fibrous boehmite of claim 1, it is characterized in that: the reaction times in the step 4 should be controlled at 5～48h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910654A (en) * | 2012-11-08 | 2013-02-06 | 北京化工大学 | Preparation method of fibrous boehmite with large specific surface area and large pore area |
| CN103131411A (en) * | 2013-02-22 | 2013-06-05 | 北京化工大学 | Rare-earth-cerium-doped nano-grade fibrous aluminum oxide luminescent material and preparation method thereof |
| CN104209129A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Catalyst for reducing content of NOX in FCC flue gas and application thereof |
| CN104692429A (en) * | 2015-02-16 | 2015-06-10 | 北京化工大学 | Controllable preparation method of large-specific-area large-pore-volume boehmite |
| CN105036163A (en) * | 2015-08-14 | 2015-11-11 | 黄志强 | Preparation method of nanometer fiber type thin diaspore |
| CN105858783A (en) * | 2016-04-18 | 2016-08-17 | 北京化工大学 | Application of nanometer flaky aluminum oxide to removal of fluorine ions from water |
| CN105905974A (en) * | 2016-06-27 | 2016-08-31 | 北京化工大学 | Application of phosphorus-modified nano flaky aluminium oxide in removal of cadmium ions in water |
| CN107720792A (en) * | 2016-08-12 | 2018-02-23 | 中国石油天然气股份有限公司 | The preparation method of fibrous boehmite |
| CN110015673A (en) * | 2018-01-10 | 2019-07-16 | 北京化工大学 | Boehmite and preparation method thereof |
| CN115611299A (en) * | 2021-07-15 | 2023-01-17 | 北京化工大学 | Nano fibrous boehmite and preparation method thereof |
| CN115611299B (en) * | 2021-07-15 | 2024-04-23 | 北京化工大学 | Nanofiber-shaped boehmite and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910654B (en) * | 2012-11-08 | 2014-07-30 | 北京化工大学 | Preparation method of fibrous boehmite with large specific surface area and large pore area |
| CN102910654A (en) * | 2012-11-08 | 2013-02-06 | 北京化工大学 | Preparation method of fibrous boehmite with large specific surface area and large pore area |
| CN103131411A (en) * | 2013-02-22 | 2013-06-05 | 北京化工大学 | Rare-earth-cerium-doped nano-grade fibrous aluminum oxide luminescent material and preparation method thereof |
| CN103131411B (en) * | 2013-02-22 | 2015-02-18 | 北京化工大学 | Rare-earth-cerium-doped nano-grade fibrous aluminum oxide luminescent material and preparation method thereof |
| CN104209129B (en) * | 2013-06-05 | 2016-08-10 | 中国石油天然气股份有限公司 | One is used for reducing NO in FCC flue gasxthe catalyst of content and application |
| CN104209129A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Catalyst for reducing content of NOX in FCC flue gas and application thereof |
| CN104692429A (en) * | 2015-02-16 | 2015-06-10 | 北京化工大学 | Controllable preparation method of large-specific-area large-pore-volume boehmite |
| CN105036163A (en) * | 2015-08-14 | 2015-11-11 | 黄志强 | Preparation method of nanometer fiber type thin diaspore |
| CN105858783A (en) * | 2016-04-18 | 2016-08-17 | 北京化工大学 | Application of nanometer flaky aluminum oxide to removal of fluorine ions from water |
| CN105905974A (en) * | 2016-06-27 | 2016-08-31 | 北京化工大学 | Application of phosphorus-modified nano flaky aluminium oxide in removal of cadmium ions in water |
| CN107720792A (en) * | 2016-08-12 | 2018-02-23 | 中国石油天然气股份有限公司 | The preparation method of fibrous boehmite |
| CN110015673A (en) * | 2018-01-10 | 2019-07-16 | 北京化工大学 | Boehmite and preparation method thereof |
| CN115611299A (en) * | 2021-07-15 | 2023-01-17 | 北京化工大学 | Nano fibrous boehmite and preparation method thereof |
| CN115611299B (en) * | 2021-07-15 | 2024-04-23 | 北京化工大学 | Nanofiber-shaped boehmite and preparation method thereof |
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Application publication date: 20120905 |