CN101643217A - Method for preparing ordered mesoporous material by utilizing bentonite - Google Patents
Method for preparing ordered mesoporous material by utilizing bentonite Download PDFInfo
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- CN101643217A CN101643217A CN200910044290A CN200910044290A CN101643217A CN 101643217 A CN101643217 A CN 101643217A CN 200910044290 A CN200910044290 A CN 200910044290A CN 200910044290 A CN200910044290 A CN 200910044290A CN 101643217 A CN101643217 A CN 101643217A
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- mesoporous material
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Abstract
The invention relates to a method for preparing ordered mesoporous material by utilizing bentonite. Bentonite material and alkali with the weight ratio of 1: 0.5-2 are mixed and roasted for activation, a sample after roasting is stirred and leached in deionized water at common temperature, leaching solution is the synthesized material, the leaching solution is dripped in surfactant solution, the pH value of the solution is adjusted to 7-13, the solution is put in a reaction kettle for crystallization at 100-180 DEG C, filtered, washed, dried and roasted at 500-600 DEG C to obtain white power,i.e. the ordered mesoporous material. The method has simple preparation process, cheap and easily available raw material, low concentration of organic material and difficult initiation of environmentpollution. The specific surface area of the prepared ordered mesoporous material has a maximum of over 1000m<2>*g<-1>, the pore volume can reach over 1.00cm<3>*g<-1>, and the distribution of pore diameters is centralized.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, particularly a kind of method of utilizing wilkinite to prepare ordered mesoporous material.
Background technology
The M41S ordered mesoporous material has been synthesized in the human organosilicon sources such as Beck of Mobil company in 1992, because but its aperture size with orderly pore passage structure, big specific surface area modulation becomes one of focus of catalytic material area research rapidly, can bring into play its good adsorption separation function (Journal of American ChemicalSociety in fields such as catalysis, medicine, petroleum industries, 1992,114,10834-10843).Along with the progress of synthetic technology, from the silicon species to the template, from the synthetic method to the synthesis condition, all constantly bring forth new ideas.
With the self-assembly tensio-active agent is that template prepares the extensive interest that mesoporous silicon material has attracted the investigator in recent years, but wherein great majority are devoted to organosilicon, prepare mesoporous material as tetraethoxy and methyl silicate as the silicon source, simple with this class alkoxide as feedstock production ordered mesoporous material technology, but cost an arm and a leg, limited its widespread use.Then can reduce preparation cost greatly with inorganic silicon source such as water glass, silicon sol as raw material, make ordered mesoporous material be widely used.With natural mineral such as wilkinite as raw material, utilize its silane agent and special construction,, can obtain ordered mesoporous material by structure activation transformation directly with alkaline purification, this method can be widened the Application Areas of clay mineral when reducing preparation cost, and promotes its added value.At present also few about the report of this respect.
The wilkinite main component is a montmorillonite, be silicate with 2: 1 type laminate structures, abundant in occurring in nature storage, be widely used in fields such as catalysis and absorption, if the smectite structure unit is incorporated in the hole wall of mesopore molecular sieve then can improves the stability of ordered mesoporous material.
In recent years, wilkinite is not studied mesopore molecular sieve synthetic that the person is applied to high stability, as Zhou etc. at ambient temperature, with natural clay, ethyl orthosilicate, aluminum isopropylate is raw material, and cetyl trimethylammonium bromide is the mesopore molecular sieve that contains B acid position that template has synthesized high stability; But with the organoaluminum is raw material, not only cost height and toxicity big (ChineseChemistry Letters, 2005,16:261-264); The natural montmorillonite of usefulness such as Liu Jianfen, silica gel are raw material, cetyl trimethylammonium bromide is a template, original position has been synthesized the Al-MCM-41 of high stability on montmorillonite, but this method need add must pure reagent silicon source, the surfactant concentration that reacts required is higher, and during consumption energy consumption, the not high (Journal of Inorganic Materials of the specific surface area of the Al-MCM-41 of gained, 2003,18:867-871); It is the mesopore molecular sieve that raw material has synthesized high stability with wilkinite, water glass and aluminum chloride that Tang Ya waits adopting microwave method quietly, but the usage quantity of water glass and aluminum chloride is bigger, bentonite consumption few (nanotechnology and precision engineering, 2008,6:185-189).
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with the wilkinite, the method for the aluminium silicon ordered mesoporous material that preparation high-specific surface area, pore size distribution are concentrated.The method that the present invention proposes directly activates wilkinite with alkali, need not to add acid treatment, and need not add any pure silicon or fine aluminium chemical reagent.
Detailed protocol of the present invention is:
With the wilkinite calcination activation, activation method is that wilkinite is mixed the back roasting with the NaOH solid, adds water logging again and goes out.
Wilkinite is mixed according to 1: 0.5～2 with the NaOH solid, the high-temperature roasting activation, naturally cooling, then with wilkinite: the ratio of deionized water=1g: 10mL～30mL adds deionized water, making wherein, soluble silicate fully dissolves, leave standstill 12h～36h then, it is standby as silicon and aluminum source to get the leaching supernatant liquid.Silicon and aluminum source is joined in the surfactant soln, and tensio-active agent is C
nH
2n+1(CH
3)
3N
+X
-The series quaternary ammonium salt, wherein n is 14,16 or 18, X is Cl or Br.Regulate pH value to 7～13, stir 30min, change autoclave over to, crystallization obtains presoma, with presoma suction filtration, washing, and drying, tensio-active agent is removed in high-temperature roasting, promptly makes ordered mesoporous material.
The present invention compares with existing Technology and has the following advantages:
(1) the present invention is to be that raw material prepares aluminium silicon ordered mesoporous material through chemical process with the wilkinite, directly obtain with alkaline purification, need not to add earlier acid treatment, need not additionally to add silicon, aluminium source, the raw material availability height, can reduce production costs greatly, widen bentonitic range of application simultaneously, produce high value-added product.
(2) technology of the present invention is simple, and raw material is easy to get, cheap, and condition is comparatively loose, less energy intensive;
(3) prepared ordered mesoporous material has the pore size distribution of high-specific surface area, duct homogeneous, and permeability can be good.
Description of drawings
Fig. 1: the little angle XRD figure of different Si/Al mol ratio Al-MCM-41.
Wherein: (a) Si/Al=13.72, (b) Si/Al=32.66
The HRTEM figure of Fig. 2: prepared Al-MCM-41 (Si/Al=32.66).
Embodiment
Embodiment 1
Mix crossing the bentonite material 15g of 200 mesh sieves and NaOH solid mass ratio with 1: 1.25,600 ℃ of roasting 2h, the deionized water that adds 300mL behind the naturally cooling, leave standstill 16h, leaching supernatant liquid with 80mL dropwise adds in the solution of cetyl trimethylammonium bromide afterwards, continue to stir, regulate the pH value to 11 of mixed solution with hydrochloric acid, behind the 30min mixed solution changed over to 110 ℃ of crystallization 24h obtain presoma in the reactor, presoma is through suction filtration, washing, dry 4h, 540 ℃ of roasting 6h, naturally cool to room temperature, promptly obtain ordered mesoporous material Al-MCM-41, its silica alumina ratio is 13.72.The specific surface area of prepared Al-MCM-41 can be up to 840m
2G
-1, pore volume can reach 1.04cm
3G
-1
Mix crossing the bentonite material 15g of 200 mesh sieves and NaOH solid mass ratio with 1: 1,600 ℃ of roasting 2h, the deionized water that adds 300mL behind the naturally cooling, leave standstill 12h, leaching supernatant liquid with 80mL dropwise adds in the solution of tetradecyl trimethyl ammonium chloride afterwards, continue to stir, regulate the pH value to 9 of mixed solution with hydrochloric acid, behind the 30min mixed solution changed over to 160 ℃ of crystallization 24h obtain presoma in the reactor, presoma is through suction filtration, washing, dry 4h, 540 ℃ of roasting 6h, naturally cool to room temperature, promptly obtain ordered mesoporous material Al-MCM-41, its silica alumina ratio is 32.66.The specific surface area of prepared Al-MCM-41 can be up to 1000m
2G
-1More than, pore volume can reach 1.00cm
3G
-1More than.
Embodiment 3
Mix crossing the bentonite material 15g of 200 mesh sieves and NaOH solid mass ratio with 1: 1.5,600 ℃ of roasting 2h, the deionized water that adds 300mL behind the naturally cooling, leave standstill 20h, leaching supernatant liquid with 80mL dropwise adds in the solution of octadecyl trimethylammonium bromide afterwards, continue to stir, regulate the pH value to 9 of mixed solution with hydrochloric acid, behind the 30min mixed solution changed over to 130 ℃ of crystallization 24h obtain presoma in the reactor, presoma is through suction filtration, washing, dry 4h, 540 ℃ of roasting 6h, naturally cool to room temperature, promptly obtain ordered mesoporous material Al-MCM-41, its silica alumina ratio is 22.69.The specific surface area of prepared Al-MCM-41 can be up to 721m
2G
-1, pore volume can reach 0.88cm
3G
-1
Claims (2)
1. a method of utilizing wilkinite to prepare ordered mesoporous material is characterized in that: wilkinite is mixed calcination activation, wilkinite in the calcination activation process: alkali=1: 0.5～1: 2 with the NaOH solid; Maturing temperature is 500～600 ℃, adds deionized water behind the naturally cooling, makes wherein that soluble silicate fully dissolves, and wilkinite: the ratio=1g of deionized water: 10mL～30mL, time of repose are 12h～36h; Get and leach supernatant liquid as silicon and aluminum source; Silicon and aluminum source is joined in the surfactant soln, stirring and regulating the pH value is 7～13, change autoclave again over to, crystallization obtains presoma, and crystallization time is 12～72h, and the crystallization temperature scope is 100～180 ℃, with presoma suction filtration, washing, drying, tensio-active agent is removed in high-temperature roasting, makes ordered mesoporous material.
2. wilkinite according to claim 1 prepares the method for ordered mesoporous material, it is characterized in that: described tensio-active agent is C
nH
2n+1(CH
3)
3N
+X
-The series quaternary ammonium salt, wherein n is 14,16 or 18, X is Cl or Br.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100442909A CN101643217B (en) | 2009-09-07 | 2009-09-07 | Method for preparing ordered mesoporous material by utilizing bentonite |
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|---|---|---|---|
| CN2009100442909A CN101643217B (en) | 2009-09-07 | 2009-09-07 | Method for preparing ordered mesoporous material by utilizing bentonite |
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|---|---|
| CN101643217A true CN101643217A (en) | 2010-02-10 |
| CN101643217B CN101643217B (en) | 2012-02-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761241A (en) * | 2018-12-27 | 2019-05-17 | 济南大学 | A method of utilizing alkaline matter activated clays pore-creating |
| CN112707405A (en) * | 2021-01-08 | 2021-04-27 | 北京建筑材料科学研究总院有限公司 | Modified phyllosilicate, preparation method and application thereof |
| CN113769550A (en) * | 2021-09-17 | 2021-12-10 | 安徽东至广信农化有限公司 | Methyl chloride pickling process for glyphosate production |
| CN113941358A (en) * | 2021-10-19 | 2022-01-18 | 河南建筑材料研究设计院有限责任公司 | Preparation method of catalytic material for degrading formaldehyde, catalytic material prepared by preparation method and application of catalytic material |
-
2009
- 2009-09-07 CN CN2009100442909A patent/CN101643217B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761241A (en) * | 2018-12-27 | 2019-05-17 | 济南大学 | A method of utilizing alkaline matter activated clays pore-creating |
| CN112707405A (en) * | 2021-01-08 | 2021-04-27 | 北京建筑材料科学研究总院有限公司 | Modified phyllosilicate, preparation method and application thereof |
| CN112707405B (en) * | 2021-01-08 | 2023-01-17 | 北京建筑材料科学研究总院有限公司 | Modified phyllosilicate, and preparation method and application thereof |
| CN113769550A (en) * | 2021-09-17 | 2021-12-10 | 安徽东至广信农化有限公司 | Methyl chloride pickling process for glyphosate production |
| CN113941358A (en) * | 2021-10-19 | 2022-01-18 | 河南建筑材料研究设计院有限责任公司 | Preparation method of catalytic material for degrading formaldehyde, catalytic material prepared by preparation method and application of catalytic material |
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| CN101643217B (en) | 2012-02-22 |
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