CN103242027A - Preparation method of porous mullite block - Google Patents
Preparation method of porous mullite block Download PDFInfo
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- CN103242027A CN103242027A CN2013101798175A CN201310179817A CN103242027A CN 103242027 A CN103242027 A CN 103242027A CN 2013101798175 A CN2013101798175 A CN 2013101798175A CN 201310179817 A CN201310179817 A CN 201310179817A CN 103242027 A CN103242027 A CN 103242027A
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Abstract
The invention discloses a preparation method of a porous mullite block. The preparation method of the porous mullite block comprises the following steps of: (1) dissolving aluminum chloride hexahydrate and polyoxyethylene in a solvent, dropwise adding tetramethyl orthosilicate, and then stirring continuously and reacting for 50-70minutes; (2) under the room temperature, adding epoxypropane in the mixture obtained in the step (1) and stirring uniformly to obtain a homogeneous solution; (3) sealing the homogeneous solution in a container and then gelling at 35-45 DEG C for 8-12minutes to obtain wet gel; (4) aging the wet gel at 35-45 DEG C for 68-76 hours; and (5) drying the aged gel prepared in the step (4) at 70-80 DEG C for 2-3 days, and then carrying out heat treatment at 800-1400 DEG C for 4-6 hours to obtain the porous mullite block. The porous mullite block prepared by the method has the characteristics that the block has a hierarchical porous structure, the size and amount of apertures are controllable, the frameworks are continuous, the specific surface area is large, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of porous mullite block, be specifically related to a kind of sol-gel and follow phase separation method to prepare the method for porous mullite block.
Background technology
Mullite (consists of 3Al usually
2O
32SiO
2) be at SiO
2-Al
2O
3The crystal of unique stable existence in the biphasic system also is one of the most common industrial ceramics.Because mullite has excellent hot strength, creep resistance, low thermal coefficient of expansion, excellent dielectric properties, in the high-transmission rate of middle infrared, good chemical stability and thermostability, can remain on simultaneously mechanical property under the intensification condition and the stability in oxidizing atmosphere, it has important application prospects at aspects such as electronics, optics and thermal structures.
Porous mullite with controllable porous structure has become mullite in a new development of application facet such as support of the catalyst, heat insulation, particle sieve, metal penetration pottery.The technological line of at present existing various synthesizing porous mullites, as gel refrigeration drying, interpolation pore-forming material, gel injection, fusion sediment, reaction formation, hydrothermal treatment consists, calcining, lixiviation process etc., but still do not have the report that preparation has the mullite method that connects vesicular structure, do not have sol-gel to follow phase separation method to prepare the research of porous mullite block yet.
It is a kind of new synthesizing mean that preparation has common continuous structure porous blocks that sol-gel is followed phase separation method.Adopt this method to successfully synthesize the oxide porous block of elements such as silicon, aluminium, titanium, zirconium, carbon, iron.Although theoretical foundation has been set up in the preparation of the porous blocks of one component system, rarely have about two-phase or three-phase system, as SiO
2-Al
2O
3, CaO-Al
2O
3, MgO-Al
2O
3-SiO
2, reach the research of complex oxide porous materials such as mullite, mayenite, trichroite.Because compare with unary system, the cohydrolysis of binary or three-part system, form homogeneous phase complex sol, sol-gel transition and process such as be separated all more complicated, and be difficult to control.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of porous mullite block, the porous mullite block that adopts this method preparation and get has the layer stephanoporate structure, aperture size and controllable number, skeleton is continuous, specific surface area is big, and (the aperture macropore diameter is distributed in 1 ~ 2 micron, and specific surface area is 50 ~ 400 m
2/ characteristics such as g).
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of porous mullite block, with the Aluminium chloride hexahydrate (AlCl of 2g
36H
2O) being the aluminium source, is the silicon source with the methyl silicate (TMOS) of 0.25 ~ 0.3ml, is gel promotor with the propylene oxide (PO) of 1.5 ~ 2.0ml, and (PEO, molecular-weight average are 1 * 10 with the polyoxyethylene of 0.02 ~ 0.03g
6) be the inductor that is separated; May further comprise the steps:
1), under room temperature, earlier Aluminium chloride hexahydrate and polyoxyethylene are dissolved in the solvent, under whipped state, drip methyl silicate then; After dropwising, continue stirring reaction 50 ~ 70min;
2), under room temperature, in the gains of step 1), add after propylene oxide evenly stirs, get homogeneous solution;
3) thereby, homogeneous solution put into container sealing back realize gel conversions in 35 ~ 45 ℃ of gel 8 ~ 12min(), get wet gel;
4), wet gel is placed 35 ~ 45 ℃ of down aging 68 ~ 76h;
5), with the gel behind step 4) gained aging in 70 ~ 80 ℃ of drying 2 ~ 3d; Place 800 ~ 1400 ℃ of thermal treatment 4 ~ 6h then, obtain porous mullite block (the porous mullite block of crystallization).
Improvement as the preparation method of porous mullite block of the present invention: solvent is the mixture of deionized water and dehydrated alcohol, and the volume ratio of deionized water and dehydrated alcohol is 1:0.9 ~ 1.1.The consumption of solvent is 3 ~ 6ml.
Further improvement as the preparation method of porous mullite block of the present invention: thermal treatment temp is 1100 ~ 1400 ℃.
In the present invention, room temperature refers generally to 10 ~ 25 ℃.
The present invention adopts the method that the hydrolysis-polymerization process of common organoalkoxysilane is combined with sol gel reaction that the epoxide of metal-salt mediates, prepared the porous mullite block with continuous altogether through hole and skeleton structure, its aperture size and pore volume etc. are determined by amount and the thermal treatment temp of the PEO that adds.When handling for 800 ℃, then mullite still is amorphous; When 1100 ℃ and above processing, then generate the crystalline state mullite; In the present invention, thermal treatment does not destroy the macroscopic pores structure in the gel, and has just changed phase composite and the little-meso-hole structure of block, has reduced the macroscopic pores size simultaneously slightly.
The invention has the beneficial effects as follows to have prepared a kind of layer stephanoporate mullite block materials with common continuous structure, and can control aperture size and pore volume easily and effectively.Because its unique layer stephanoporate structure, the porous mullite block of preparation is expected to represent important application prospects in fields such as heterogeneous catalyst, separation, absorption, extraction, degraded, curing.Advantages such as simultaneously, this preparation method has organically combined sol-gel principle and the theoretical characteristics separately that are separated, and has the high-purity preparation of wet-chemical, can construct meticulous layer stephanoporate structure, and technology is simple, and equipment is cheap.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is the cut-away view of the porous mullite block that obtains among the embodiment 2.
Embodiment
Stirring in following examples is all carried out under 500 ~ 600 rev/mins rotating speed.
The preparation method of embodiment 1, a kind of porous mullite block is with the Aluminium chloride hexahydrate (AlCl of 2g
36H
2O) being the aluminium source, is the silicon source with the methyl silicate (TMOS) of 0.2805mL, is gel promotor with the propylene oxide (PO) of 1.8mL, and (PEO, molecular-weight average are 1 * 10 with the polyoxyethylene of 0.025g
6) be the inductor that is separated; Carry out following steps successively:
1), earlier with 2g Aluminium chloride hexahydrate (AlCl
36H
2O) and 0.025g polyoxyethylene (PEO) be dissolved in the solvent of being formed by 2.1mL ethanol and 2mL deionized water, under whipped state, drip the methyl silicate (TMOS) of 0.2805mL then; After dropwising in 1 minute, continue stirring reaction 60min; Temperature of reaction is room temperature;
2), under the room temperature, in the gains (being transparent settled solution) of step 1), add 1.8mL propylene oxide (PO) rapidly, evenly stir 1min after, get homogeneous solution;
3), homogeneous solution is put into container sealing back in 40 ℃ of gel 10min; Thereby the realization gel conversion gets wet gel;
4), wet gel is placed 40 ℃ of down aging 72h;
5), with the gel behind step 4) gained aging in 75 ℃ of dry 3d; Place then 800 ℃ heat-treat the 5h(temperature rise rate be 2 ~ 3 ℃/min), obtain the porous mullite block.
The porous mullite block for preparing is amorphous state, owing under these 800 ℃ crystal conversion does not take place as yet.Its N
2Adsorption isothermal line is the IV type, has proved mesoporous existence, and pore size distribution mainly at micropore in the mesoporous interval range, average macropore diameter is 1.4 μ m, specific surface area reaches 400 m
2/ g.
The preparation method of embodiment 2, a kind of porous mullite block,
Make the thermal treatment temp in embodiment 1 step 5) into 1100 ℃ by 800 ℃, all the other are with embodiment 1.
The porous mullite block well-crystallized who prepares, complete, and have continuous altogether macroscopical through-hole structure and intact skeleton (see figure 1), and skeleton is made up of the nano-crystalline granule of plate-like or needle-like.Its pore size distribution is concentrated, and volume density is about 1.34 gcm
-3, calculating relative density is 42%.The N of this porous mullite block
2Suction-desorption curve is the H3 type, shows that block exists slit-shaped mesoporous because of its skeleton structure, mesoporous roughly disappearance, and the macropore mean pore size is 1.2 μ m, specific surface area is 54 m
2/ g.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. the preparation method of porous mullite block, it is characterized in that: the Aluminium chloride hexahydrate with 2g is the aluminium source, methyl silicate with 0.25 ~ 0.3ml is the silicon source, is gel promotor with the propylene oxide of 1.5 ~ 2.0ml, is the inductor that is separated with the polyoxyethylene of 0.02 ~ 0.03g; May further comprise the steps:
1), under room temperature, earlier Aluminium chloride hexahydrate and polyoxyethylene are dissolved in the solvent, under whipped state, drip methyl silicate then; After dropwising, continue stirring reaction 50 ~ 70min;
2), under room temperature, in the gains of step 1), add after propylene oxide evenly stirs, get homogeneous solution;
3), homogeneous solution is put into container sealing back in 35 ~ 45 ℃ of gel 8 ~ 12min, get wet gel;
4), wet gel is placed 35 ~ 45 ℃ of down aging 68 ~ 76h;
5), with the gel behind step 4) gained aging in 70 ~ 80 ℃ of drying 2 ~ 3d; Place 800 ~ 1400 ℃ of thermal treatment 4 ~ 6h then, obtain the porous mullite block.
2. the preparation method of porous mullite block according to claim 1 is characterized in that:
Described solvent is the mixture of deionized water and dehydrated alcohol, and the volume ratio of deionized water and dehydrated alcohol is 1:0.9 ~ 1.1.
3. the preparation method of porous mullite block according to claim 2 is characterized in that:
The consumption of described solvent is 3 ~ 6ml.
4. according to the preparation method of claim 2 or 3 described porous mullite blocks, it is characterized in that: described thermal treatment temp is 1100 ~ 1400 ℃.
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| CN2013101798175A CN103242027A (en) | 2013-05-14 | 2013-05-14 | Preparation method of porous mullite block |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663400A (en) * | 2013-12-15 | 2014-03-26 | 浙江大学 | Preparation method of porous aluminum phosphate block |
| CN103922783A (en) * | 2014-03-19 | 2014-07-16 | 浙江大学 | Porous cordierite block preparation method |
| CN104016666A (en) * | 2014-06-23 | 2014-09-03 | 浙江大学 | Preparation method of porous calcium-aluminum stone block |
| CN110302782A (en) * | 2019-06-25 | 2019-10-08 | 沈阳工大蓝金环保产业技术研究院有限公司 | A kind of preparation method of the layer stephanoporate silicon dioxide hybrid materials with coherent macropore |
| CN115974539A (en) * | 2022-12-13 | 2023-04-18 | 南京工业大学 | Preparation method of blocky high-temperature-resistant mullite ceramic aerogel |
-
2013
- 2013-05-14 CN CN2013101798175A patent/CN103242027A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| XINGZHONG GUO ET AL.: "Preparation of mullite monoliths with well-defined macropores and mesostructured skeletons via the sol–gel process accompanied by phase separation", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663400A (en) * | 2013-12-15 | 2014-03-26 | 浙江大学 | Preparation method of porous aluminum phosphate block |
| CN103663400B (en) * | 2013-12-15 | 2015-07-08 | 浙江大学 | Preparation method of porous aluminum phosphate block |
| CN103922783A (en) * | 2014-03-19 | 2014-07-16 | 浙江大学 | Porous cordierite block preparation method |
| CN104016666A (en) * | 2014-06-23 | 2014-09-03 | 浙江大学 | Preparation method of porous calcium-aluminum stone block |
| CN104016666B (en) * | 2014-06-23 | 2015-11-18 | 浙江大学 | The preparation method of porous calcium aluminium stone body |
| CN110302782A (en) * | 2019-06-25 | 2019-10-08 | 沈阳工大蓝金环保产业技术研究院有限公司 | A kind of preparation method of the layer stephanoporate silicon dioxide hybrid materials with coherent macropore |
| CN110302782B (en) * | 2019-06-25 | 2022-04-12 | 沈阳工大蓝金环保产业技术研究院有限公司 | Preparation method of hierarchical porous silicon dioxide hybrid material with coherent macropores |
| CN115974539A (en) * | 2022-12-13 | 2023-04-18 | 南京工业大学 | Preparation method of blocky high-temperature-resistant mullite ceramic aerogel |
| CN115974539B (en) * | 2022-12-13 | 2023-12-29 | 南京工业大学 | Preparation method of blocky high-temperature-resistant mullite ceramic aerogel |
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Application publication date: 20130814 |