CN104557130A - Preparation method of kaolin-based mesoporous silica material - Google Patents
Preparation method of kaolin-based mesoporous silica material Download PDFInfo
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- CN104557130A CN104557130A CN201510027769.7A CN201510027769A CN104557130A CN 104557130 A CN104557130 A CN 104557130A CN 201510027769 A CN201510027769 A CN 201510027769A CN 104557130 A CN104557130 A CN 104557130A
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- metakaolin
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Abstract
The invention relates to the field of mesoporous materials, and in particular relates to a process for preparing a kaolin-based mesoporous silica material by employing a template-free method. A preparation method of the kaolin-based mesoporous silica material is characterized by comprising the following steps: (1) calcinations and activation, namely calcining and activating kaolin to obtain metakaolin; (2) hydrothermal alkali activation, namely activating the metakaolin in a hot solution containing OH<-> and Na<+>; and (3) acid etching, namely etching the metakaolin which is subjected to hydrothermal alkali activation in an acid solution to obtain the kaolin-based mesoporous silica material. The method is low in production cost; and the obtained kaolin-based mesoporous silica material has high specific surface area.
Description
Technical field
The present invention relates to mesoporous materials field, be specifically related to a kind of technique without the kaolin based meso pore silicon oxide material of template synthesis.
Background technology
Mesoporous material, with the pore size distribution of its excellence (2 ~ 50nm) and larger specific surface area, has and applies more and more widely in absorption, separation, catalysis and medicine embedding and conveying etc. are many.
At present, the preparation of mesoporous material mainly adopts template.Template refers to and utilizes tensio-active agent (soft template) or some mesoporous materials (hard template) to form intermediate for pore-forming material or skeleton structure and industrial chemicals, is then obtained a kind of method of meso-hole structure by removing template composition.But due to the template of costliness or the use of mould material and industrial chemicals, the mesoporous material of template synthesis is with high costs, is difficult to Industry Promotion.
Obviously, do not introduce template and mould material and with mineral material cheap and easy to get for the technique of mesoporous material prepared by raw material, namely without template mineral based mesoporous material preparation technology, the production cost of mesoporous material can be reduced, promote the commercial application of mineral based mesoporous material.
Kaolin is used for without template synthesis mesoporous material by numerous investigators as a kind of natural minerals cheap and easy to get.Existing preparation method is mainly acidleach, the steps include: (1) by kaolin starting material at a certain temperature calcining and activating become metakaolin; (2) at hydrothermal reaction condition, utilize strong acid to etch metakaolin thus obtain having the meso pore silicon oxide material of high specific surface area.Lenarda etc. are by the H of the kaolin 1mol/L of 850 DEG C of calcining 2h
2sO
4solution etches, obtaining specific surface area is 288m
2the mesoporous material (Journal of Colloid and Interface Science, 2007,311:537 – 543) based on micropore of/g.Kaolin is first calcined 24h by Okada etc. at 600 DEG C, then uses the H of 2.5mol/L
2sO
4solution etches, and obtaining specific surface area is 330m
2the microporous alumina silicon materials (Microporous and MesoporousMaterials, 1998,21:289-296) of/g.Etched the kaolin after 850 DEG C of calcinings by the hydrochloric acid of 5mol/L, it is 430m that reed etc. of relaxing obtains specific surface area
2the silica material (Applied Clay Science, 2014,102:33-40) based on micropore of/g.
Obviously, there are the kaolin based porous oxidation silicon materials of bibliographical information to be main (aperture <2nm) mainly with micropore at present, and the lower (<430m of its specific surface area
2/ g), the specific surface area being far inferior to template synthesis can reach 1000m
2the mesoporous material of/g.
Summary of the invention
The object of the present invention is to provide a kind of production cost low and there is the preparation method of the kaolin based meso pore silicon oxide material of high-specific surface area.
To achieve these goals, technical scheme of the present invention is: the preparation method of kaolin based meso pore silicon oxide material, it is characterized in that it comprises the steps:
1) calcining and activating: kaolin is placed in 600 ~ 950 DEG C of calcining 0.5 ~ 12h, obtains metakaolin;
2) hydro-thermal alkali activation: by step 1) in the metakaolin that obtains and concentration be 1 ~ 9mol/L contain OH
-and Na
+solution mix in the ratio of 1kg:4 ~ 50L, 0.5 ~ 12h is reacted under the condition of 40 ~ 100 DEG C, then isolate the solid matter in suspension, washing is dry (carrying out washing and drying to solid matter) also, obtains the metakaolin of hydro-thermal alkali activation;
3) acid etch: by step 2) in metakaolin and the concentration of the activation of hydro-thermal alkali that obtain be 1 ~ 10mol/L acid solution mixes in the ratio of 1kg:4 ~ 50L, 0.5 ~ 12h is reacted under the condition of 40 ~ 100 DEG C, then the solid matter in suspension is isolated, washing is also dry, and (its specific surface area can up to 670m to obtain kaolin based meso pore silicon oxide material
2/ g, its most probable pore size is at about 4nm).
Described containing OH
-and Na
+solution be NaOH solution, or the mixture solution of KOH and NaCl, the proportioning of KOH and NaCl is 1mol:0.5-1mol.
Described acid solution can be strong acid (as HCl, HNO
3, H
2sO
4deng) one or two or more kinds mixture by any proportioning in solution, or strong acid solution (one or more) with other weak acid (as acetic acid, HNO
2) by the mixture of any proportioning.
Feature of the present invention: the raw material preparing mesoporous material is kaolin, and in preparation technology, do not use template or mould material (as: hexanediamine, cetyl trimethylammonium bromide etc.).
Step 2) with step 3) in reacted solid liquid phase need to be separated, its means be separated can for filter and centrifugal etc.
It should be noted that, in such scheme, step 1) final purpose be obtain metakaolin, can according to the kaolinic type of difference and the place of production etc. in actually operating, in calcining temperature with carry out suitable process optimization in the time; Step 2) metakaolin activating process in, metakaolin is by OH
-and Na
+common activation, NaOH alkaline solution can with other comparatively highly basic (as KOH) substitute but the OH of suitable concentration must be ensured
-and Na
+existence, as the mixture of KOH and NaCl; Step 2) in activation after its specific surface area of metakaolin not higher than 20m
2/ g, and not there is meso-hole structure, be non-mesoporous material; Step 3) main purpose be utilize H
+the element etchings such as Al and Na in the metakaolin after being activated by alkali, therefore this etching solution can provide H
+, but be good with strong acid or strong acid mixed solution, weakly acidic solution also can be adopted to carry out long period or multiple etching.
Technological principle involved in the present invention is as follows:
A, kaolinic main component are kaolinite (Al
2o
32SiO
22H
2o), through step 1) occur decarboxylation reaction activated, kaolin changes amorphous metakaolin (Al into
2o
32SiO
2).
B, in step 2) in, under hydrothermal conditions, Si and Al in metakaolin is by OH
-corrode and react a kind of amorphous solid of in-situ preparation with Na+.This amorphous solid contains comparatively poly-hydroxy (Si-OH and Al-OH) and has larger loss on ignition, still has the sheet-like morphology similar to metakaolin.
C, in step 3) in, at certain temperature and acidic conditions, the microscopic appearance solid in the form of sheets that step (2) obtains has the textural defect of a series of size at about 4nm because Al and Na element is wherein etched, become the material had without ordered meso-porous structure, i.e. kaolin based meso pore silicon oxide material.
Beneficial effect of the present invention is:
1, this technique is without the need to the template of costliness and mould material, meso pore silicon oxide material is prepared based on kaolin mineral cheap and easy to get and part conventional chemical reagent, without the need to techniques such as template introducing and template removals, production technique is simple, with low cost, is suitable for suitability for industrialized production.
2, this technique prepares the technique of mesoporous material for the direct acidleach of traditional metakaolin, introduces alkali activating process in a creative way, is that a kind of thinking breaks through and technological innovation; And in view of the structural similarity of clay mineral, this technique can be not limited to kaolin based mesoporous material without template synthesis aspect; The specific surface area of kaolin based meso pore silicon oxide material that simultaneously prepared by this technique can up to 670m
2/ g, its most probable pore size can reach 4nm, higher than the 400m of existing technique
2/ g, close to the mesoporous material that segment template legal system is standby.
3, the saturated extent of adsorption of porous material when normal temperature pH=10 for methylene blue that prepared by the present invention can reach 650mg/g, can be used as a kind of sorbing material of excellent property, has application prospect comparatively widely.
Accompanying drawing explanation
Fig. 1 is the nitrogen adsorption-desorption isotherm of example 1 intermediary hole silicon oxide and the pore size distribution (built-in) of utilization BJH model analysis.
Fig. 2 is the transmission electron microscope picture of example 1 intermediary hole silicon oxide.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
The preparation method of kaolin based meso pore silicon oxide material, it comprises the steps:
(1) calcining and activating: kaolin is placed in after calciner calcines 2h under 850 DEG C of conditions, takes out after apparatus cools, obtain unbodied metakaolin;
(2) hydro-thermal alkali activation: the metakaolin of step (1) gained is mixed with the ratio of 1kg:20L with the sodium hydroxide solution of 4mol/L, stir under the condition of 80 DEG C and react 0.5h, then filter and the solid product extremely neutrality obtained with deionized water wash, again through 110 DEG C of dry removal moisture, obtain the metakaolin after alkali activation (activation of hydro-thermal alkali);
(3) acid etch: the metakaolin after being activated by the alkali obtained in step (2) mixes with the ratio of 1kg:20L with the HCl solution of 5mol/L, stir under the condition of 100 DEG C and react 6h, then filter and the solid product extremely neutrality obtained with deionized water wash, again through 110 DEG C of dry removal moisture, obtain the kaolin based meso pore silicon oxide material without template synthesis.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 610m
2/ g, its most probable pore size is 4.45nm.Its nitrogen adsorption-desorption isotherm and the pore size distribution that obtains according to BJH model are as shown in Figure 1.Fig. 2 is its transmission electron microscope observing figure.
Embodiment 2
The preparation method of kaolin based meso pore silicon oxide material, it comprises the steps:
(1) calcining and activating: kaolin is placed in calciner under 600 DEG C of conditions, calcine 12h after high temperature direct sampling, obtain unbodied metakaolin;
(2) hydro-thermal alkali activation: the metakaolin of step (1) gained is mixed with the ratio of 1kg:50L with the sodium hydroxide solution of 1mol/L, stir under the condition of 70 DEG C and react 12h, then the centrifugal and solid product obtained with deionized water wash is to neutral, again through 110 DEG C of dry removal moisture, obtain the metakaolin after alkali activation;
(3) acid etch: the metakaolin after the alkali obtained in step (2) is activated and the H of 1mol/L
2sO
4solution mixes with the ratio of 1kg:50L, stir under the condition of 40 DEG C and react 1h, then filter and the solid product extremely neutrality obtained with deionized water wash, then through 110 DEG C of dry removal moisture, obtain the kaolin based meso pore silicon oxide material without template synthesis.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 656m
2/ g, its most probable pore size is 4.08nm.
Embodiment 3
The preparation method of kaolin based meso pore silicon oxide material, it comprises the steps:
(1) calcining and activating: kaolin is placed in calciner under 950 DEG C of conditions, calcine 0.5h after high temperature direct sampling, obtain unbodied metakaolin;
(2) hydro-thermal alkali activation: the metakaolin of step (1) gained and the sodium hydroxide solution of 9mol/L are mixed with the ratio of 1kg:4L and is placed in resistance to alkali container, stir under the condition of 80 DEG C and react 0.5h, then filter and the solid product extremely neutrality obtained with deionized water wash, again through 110 DEG C of dry removal moisture, obtain the metakaolin after alkali activation;
(3) acid etch: by the metakaolin after the alkali activation that obtains in step (2) with containing 2mol/L HNO
3mix with the ratio of 1kg:4L with the mixing solutions of 1mol/LHCl, stir under the condition of 60 DEG C and react 10h, then filter and the solid product extremely neutrality obtained with deionized water wash, then through 110 DEG C of dry removal moisture, obtain the kaolin based meso pore silicon oxide material without template synthesis.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 670m
2/ g, its most probable pore size is 3.91nm.
Embodiment 4
The preparation method of kaolin based meso pore silicon oxide material, it comprises the steps:
(1) calcining and activating: kaolin is placed in after calciner calcines 6h under 750 DEG C of conditions, samples after naturally cooling to room temperature, obtain unbodied metakaolin;
(2) hydro-thermal alkali activation: the metakaolin of step (1) gained and the mixing solutions containing 4mol/L KOH and 2mol/L NaCl are mixed with the ratio of 1kg:6L and is placed in resistance to alkali container, stir under the condition of 40 DEG C and react 7h, then the centrifugal and solid product obtained with deionized water wash to neutral, then through 110 DEG C dry remove moisture obtain alkali activation after metakaolin;
(3) acid etch: the metakaolin after being activated by the alkali obtained in step (2) mixes with the ratio of 1kg:10L with the HCl solution of 10mol/L, stir under the condition of 100 DEG C and react 0.5h, then filter and the solid product extremely neutrality obtained with deionized water wash, then obtain the kaolin based meso pore silicon oxide material without template synthesis through 110 DEG C of dry removal moisture.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 620m
2/ g, its most probable pore size is 3.96nm.
Embodiment 5
The preparation method of kaolin based meso pore silicon oxide material, it comprises the steps:
(1) calcining and activating: kaolin is placed in calciner under 800 DEG C of conditions, calcine 5h after high temperature direct sampling, obtain unbodied metakaolin;
(2) hydro-thermal alkali activation: the metakaolin of step (1) gained is mixed with the ratio of 1kg:20L with the mixing solutions of the NaCl of KOH and 2mol/L containing 2mol/L, stir under the condition of 100 DEG C and react 3h, then the centrifugal and solid product obtained with deionized water wash to neutral, then through 110 DEG C dry remove moisture obtain alkali activation after metakaolin;
(3) acid etch: the metakaolin after being activated by the alkali obtained in step (2) mixes with the ratio of 1kg:45L with the mixed acid solution of 2mol/L acetic acid with containing 4mol/L HCl, stir under the condition of 95 DEG C and react 12h, then filter and the solid product extremely neutrality obtained with deionized water wash, then obtain the kaolin based meso pore silicon oxide material without template synthesis through 110 DEG C of dry removal moisture.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 630m
2/ g, its most probable pore size is 3.87nm.
Embodiment 6
The preparation method of kaolin based meso pore silicon oxide material, it comprises the steps:
(1) calcining and activating: kaolin is placed in calciner and calcines 7h under 650 DEG C of conditions, sample after naturally cooling, obtain unbodied metakaolin;
(2) hydro-thermal alkali activation: the metakaolin of step (1) gained is mixed with the ratio of 1kg:20L with the NaOH solution of 6mol/L, stir under the condition of 50 DEG C and react 1.5h, then the centrifugal and solid product obtained with deionized water wash to neutral, then through 110 DEG C dry remove moisture obtain alkali activation after metakaolin;
(3) acid etch: the metakaolin after being activated by the alkali obtained in step (2) mixes with the ratio of 1kg:20L with 5mol/L acetum, stirs and reacts 6h, then filter under the condition of 95 DEG C; The solid obtained is mixed with the ratio of 1kg:20L with 5mol/L acetum again, stir under 95 DEG C of conditions and react 5h, then filter and the solid product extremely neutrality obtained with deionized water wash, obtain after 110 DEG C of dryings, removal moisture obtains the kaolin based meso pore silicon oxide material without template synthesis.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 610m
2/ g, its most probable pore size is 4.08nm.
Claims (3)
1. the preparation method of kaolin based meso pore silicon oxide material, is characterized in that it comprises the steps:
1) calcining and activating: kaolin is placed in 600 ~ 950 DEG C of calcining 0.5 ~ 12h, obtains metakaolin;
2) hydro-thermal alkali activation: by step 1) in the metakaolin that obtains and concentration be 1 ~ 9mol/L contain OH
-and Na
+solution mix in the ratio of 1kg:4 ~ 50L, under the condition of 40 ~ 100 DEG C, react 0.5 ~ 12h, then isolate the solid matter in suspension, washing is also dry, obtains the metakaolin of hydro-thermal alkali activation;
3) acid etch: by step 2) in metakaolin and the concentration of the activation of hydro-thermal alkali that obtain be 1 ~ 10mol/L acid solution mixes in the ratio of 1kg:4 ~ 50L, 0.5 ~ 12h is reacted under the condition of 40 ~ 100 DEG C, then the solid matter in suspension is isolated, washing is also dry, obtains kaolin based meso pore silicon oxide material.
2. the preparation method of kaolin based meso pore silicon oxide material according to claim 1, is characterized in that, described containing OH
-and Na
+solution be NaOH solution, or the mixture solution of KOH and NaCl, the proportioning of KOH and NaCl is 1mol:0.5-1mol.
3. the preparation method of kaolin based meso pore silicon oxide material according to claim 1, it is characterized in that, described acid solution can be one or two or more kinds mixture by any proportioning in strong acid solution, or strong acid solution and other weak acid are by the mixture of any proportioning.
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| CN105692627A (en) * | 2016-01-18 | 2016-06-22 | 中国地质大学（武汉） | Method for preparing mesoporous silica material from kaolin through template-free method |
| CN105692628A (en) * | 2016-01-18 | 2016-06-22 | 中国地质大学（武汉） | Method for preparing mesoporous silica material from kaolin through calcination-free template-free method |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006087994A (en) * | 2004-09-22 | 2006-04-06 | Catalysts & Chem Ind Co Ltd | Desulfurization catalyst of catalytic cracked gasoline, and desulfurization method of catalytic cracked gasoline using it |
| CN101176851A (en) * | 2007-11-02 | 2008-05-14 | 中国化学工程集团公司 | Method for synthesizing silicon aluminum orthophosphate molecular sieve using white bole |
| CN101555044A (en) * | 2009-03-25 | 2009-10-14 | 吴帅 | Method for softening hardwater by taking river-sand as raw material |
| CN102557047A (en) * | 2011-10-18 | 2012-07-11 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing mesoporous silica with biomass power plant ash as raw material |
| CN102908982A (en) * | 2012-10-24 | 2013-02-06 | 陕西省石油化工研究设计院 | Preparation method of novel mesoporous material for absorbing heavy metal ions in wastewater |
-
2015
- 2015-01-20 CN CN201510027769.7A patent/CN104557130B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006087994A (en) * | 2004-09-22 | 2006-04-06 | Catalysts & Chem Ind Co Ltd | Desulfurization catalyst of catalytic cracked gasoline, and desulfurization method of catalytic cracked gasoline using it |
| CN101176851A (en) * | 2007-11-02 | 2008-05-14 | 中国化学工程集团公司 | Method for synthesizing silicon aluminum orthophosphate molecular sieve using white bole |
| CN101555044A (en) * | 2009-03-25 | 2009-10-14 | 吴帅 | Method for softening hardwater by taking river-sand as raw material |
| CN102557047A (en) * | 2011-10-18 | 2012-07-11 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing mesoporous silica with biomass power plant ash as raw material |
| CN102908982A (en) * | 2012-10-24 | 2013-02-06 | 陕西省石油化工研究设计院 | Preparation method of novel mesoporous material for absorbing heavy metal ions in wastewater |
Cited By (17)
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| CN105692628A (en) * | 2016-01-18 | 2016-06-22 | 中国地质大学（武汉） | Method for preparing mesoporous silica material from kaolin through calcination-free template-free method |
| CN105692627A (en) * | 2016-01-18 | 2016-06-22 | 中国地质大学（武汉） | Method for preparing mesoporous silica material from kaolin through template-free method |
| CN109422352B (en) * | 2017-08-29 | 2020-11-10 | 湖南大学 | Method for treating antibiotic wastewater by using immobilized laccase |
| CN109423488A (en) * | 2017-08-29 | 2019-03-05 | 湖南大学 | Immobilization laccase and preparation method thereof |
| CN109422270A (en) * | 2017-08-29 | 2019-03-05 | 湖南大学 | Mesoporousization bentonite and preparation method thereof |
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| CN111822057B (en) * | 2019-04-23 | 2022-03-08 | 中国石油化工股份有限公司 | Preparation method of spherical alumina carrier |
| CN111821986B (en) * | 2019-04-23 | 2022-03-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation carbon residue removal catalyst |
| CN110508235A (en) * | 2019-08-23 | 2019-11-29 | 南京理工大学 | A method of porous oxidation silicon materials are prepared using chlorite |
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