CN103922783A - Porous cordierite block preparation method - Google Patents
Porous cordierite block preparation method Download PDFInfo
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- CN103922783A CN103922783A CN201410100724.3A CN201410100724A CN103922783A CN 103922783 A CN103922783 A CN 103922783A CN 201410100724 A CN201410100724 A CN 201410100724A CN 103922783 A CN103922783 A CN 103922783A
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Abstract
The present invention discloses a porous cordierite block preparation method, which sequentially comprises: 1) at a room temperature, dissolving magnesium chloride hexahydrate, aluminum chloride hexahydrate and polyacrylamide in a solvent, adding tetramethyl orthosilicate in a dropwise manner, and continuously carrying out a stirring reaction for 50-70 min at a temperature of 50-70 DEG C; 2) naturally cooling the transparent clear solution obtained in the step 1) to a room temperature, adding propylene oxide, and uniformly stirring; 3) placing the homogeneous solution obtained in the step 2) into a container, sealing, and carrying out gelation for 3-5 min at a temperature of 35-45 DEG C; 4) placing the wet gel obtained in the step 3) in an environment with a temperature of 35-45 DEG C, and aging for 60-80 h; and 5) placing the aged gel obtained in the step 4) in an environment with a temperature of 50-70 DEG C, carrying out normal pressure drying for 72-96 h, and carrying out a heat treatment for 4-6 h at a temperature of 900-1300 DEG C. The porous cordierite block prepared by using the preparation method has characteristics of porous structure, high porosity and the like.
Description
Technical field
The present invention relates to a kind of preparation method of porous cordierite block, be specifically related to a kind of epoxide regulation and control sol-gel and follow phase separation method to prepare the preparation method of porous cordierite block.
Background technology
Trichroite (consists of 2MgO2Al conventionally
2o
35SiO
2) be MgO-Al
2o
3-SiO
2a kind of crystal in three-part system.Because trichroite has lower thermal expansivity and specific inductivity, good heat-shock resistance, resistivity against fire and mechanical property, it at ceramic industry material, the filtering material of High Temperature Gas liquid, there is important application prospect aspect the catalysis of vehicle exhaust, purifying carrier and electronic package material etc.
Having the controlled porous cordierite of pore structure has become a kind of development cordierite material rapidly, and it can be used as particulate filter, support of the catalyst, heat insulator lagging material etc., under the critical conditions of the high thermal shock of high temperature, shows good stability.The technological line of synthesizing porous cordierite has multiple at present, as gel refrigeration drying method, gel injection, in-situ consolidation colloidal forming, solid state reaction etc., but there is no the report that preparation has the trichroite block method that connects vesicular structure in microtexture, also do not have sol-gel to follow phase separation method to prepare the research of porous cordierite block.
It is a kind of novel synthesizing mean that preparation has common continuous structure porous blocks that sol-gel is followed phase separation method.Adopted the oxide porous block of elements such as successfully synthesizing in this way silicon, aluminium, titanium, zirconium, iron.For the porous blocks preparation of unary system, Chinese scholars has been set up more complete theoretical system, but rarely has about two yuan or three-part system, as SiO
2-Al
2o
3, CaO-Al
2o
3, MgO-Al
2o
3-SiO
2, and the research of the complex oxide porous material 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 the process such as be separated all more complicated, and be difficult to control.
In sol-gel process, epoxide adds as gel promotor, by irreversible ring-opening reaction, whole system pH is evenly improved, the hydrolysis of Promotion system, polyreaction and sol-gel conversion, this principle is to porous blocks, and particularly the design of multicomponent system porous blocks and preparation are very useful.
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of preparation method of porous cordierite block, and the porous cordierite block that adopts the method to prepare has layer stephanoporate structure, porosity high.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of porous cordierite block, first according to following ratio preparation main raw material: with the magnesium chloride hexahydrate (MgCl of 0.75～0.85g
26H
2o) be magnesium source, with the Aluminum Chloride Hexahydrate (AlCl of 1.9～2.1g
36H
2o) be aluminium source, methyl silicate (TMOS with 0.9～1.0ml, also claim tetramethoxy-silicane)) be silicon source, with 1.4～1.6g polyacrylamide (PAAm, molecular-weight average is 10000) be the inductor that is separated, with the propylene oxide of 0.5～0.8ml (PO,, 1,2 epoxy prapane) be gel promotor; Then carry out successively following steps:
1), at room temperature, first respectively magnesium chloride hexahydrate, Aluminum Chloride Hexahydrate and polyacrylamide are dissolved in solvent, then drip (time for adding is about 2min) methyl silicate; After dropwising, in 50～70 ℃ (being placed in 50～70 ℃ of water-baths), continue stirring reaction 50～70min, obtain transparent settled solution;
2), the transparent settled solution of step 1) gained is naturally cooled to room temperature, then add (adding rapidly) propylene oxide uniform stirring 0.5～2min, obtain homogeneous solution;
3), by step 2) homogeneous solution of gained inserts in container after sealing in 35～45 ℃ of gel 3～5min, obtains wet gel (for the opaque wet gel of oyster white);
4) wet gel of step 3) gained is placed in to aging 60～80h at 35～45 ℃;
5) gel after step 4) gained aging is placed in to 50～70 ℃ of constant pressure and dry 72～96h; Then in 900～1300 ℃ of thermal treatment 4～6h, obtain porous cordierite block.
Remarks explanation: in described step 5), after dry end, be preferably 2 ℃/min with 1.5～2.5 ℃/min() temperature rise rate is warming up to 900～1300 ℃ of then heat preservation hot processing 4～6h, thereby obtains porous cordierite block.
The porous cordierite block that above-mentioned porous cordierite block is crystallization, comprises controlled multiple crystal formation.
Improvement as the preparation method of porous cordierite 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.Solvent load is 4～8ml.
Further improvement as the preparation method of porous cordierite block of the present invention: the thermal treatment temp in step 5) is 1200～1300 ℃.
In the present invention, room temperature refers generally to 20～25 ℃.
The present invention adopts the method that the hydrolysis-polymerization process of organoalkoxysilane is combined with the metal inorganic salt sol gel reaction being regulated and controled by epoxide, prepared the porous cordierite block altogether continuously with through hole and skeleton structure, and the polyacrylamide amount that can add by adjustment and thermal treatment temp obtain required aperture size, pore volume and porosity etc.When carrying out 800 ℃ and following thermal treatment, trichroite is still amorphous; When heat-treating above for 900 ℃, can obtain crystalline state trichroite.Especially, between 900～1000 ℃, thermal treatment can obtain sapphire crystal formation; 1100 ℃ of thermal treatments, can obtain β type trichroite; 1200 ℃ of thermal treatments, can obtain the mixture phase of α type trichroite and β type trichroite; When carrying out 1300 ℃ of thermal treatment, generate single α type trichroite thing phase.In the present invention, thermal treatment does not destroy microcosmic macroporous structure and macroscopical block pattern of gel, has just completed the transformation of jello phase and inner micro--meso-hole structure, has slightly increased original large hole dimension simultaneously.
The invention has the beneficial effects as follows and prepared a kind of layer stephanoporate trichroite block materials with common continuous structure, and can control easily and effectively aperture size, pore volume and porosity.Due to its unique layer stephanoporate structure, the porous cordierite block of preparation is expected to represent important application prospect in fields such as particulate filter, support of the catalyst.Meanwhile, this preparation method has organically combined sol gel processing and the theoretical features that is separated, and has the high-purity preparation of wet-chemical, controlled structure layer stephanoporate structure, the advantage such as equipment is cheap, and technique is simple.
Adopt the inventive method preparation and porous cordierite block, the feature such as hole quantity and aperture size are controlled, and skeleton is continuous, porosity high (macropore diameter is distributed in 3～5 microns, and porosity is 50～60%).
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the internal microstructure figure of the porous cordierite block of embodiment 2 gained.
Fig. 2 is the internal microstructure figure of the porous cordierite block (not heat-treating) of comparative example 1-1 gained.
Fig. 3 is the internal microstructure figure of the porous cordierite block (not heat-treating) of comparative example 1-2 gained.
Fig. 4 is the X-ray diffractogram of trichroite block at different heat treatment temperature.
Embodiment
Stirring in following examples is all carried out under the rotating speed of 300～400r/min.
The preparation method of embodiment 1, a kind of porous cordierite block, first according to following ratio preparation main raw material: with the magnesium chloride hexahydrate (MgCl of 0.80g
26H
2o) be magnesium source, with the Aluminum Chloride Hexahydrate (AlCl of 2.0g
36H
2o) be aluminium source, the methyl silicate (TMOS) of 0.96ml of take is silicon source, with 1.5g polyacrylamide (PAAm, molecular-weight average is 10000), is the inductor that is separated, and the propylene oxide (PO) of 0.6ml of take is gel promotor; Carry out successively following steps:
1), at room temperature, 0.80g magnesium chloride hexahydrate, 2.0g Aluminum Chloride Hexahydrate and 1.5g polyacrylamide be dissolved in the solvent that 3.0ml deionized water and 2.8ml dehydrated alcohol consist of, then under agitation slowly drip 0.96ml methyl silicate (time for adding is about 2min) first respectively; After dropwising, gained solution is placed in 60 ℃ of water-baths and continues stirring reaction 60min, obtains transparent settled solution;
2), the transparent settled solution of step 1) gained is naturally cooled to room temperature, then add rapidly 0.6ml propylene oxide uniform stirring 1min, obtain homogeneous solution;
3), by step 2) homogeneous solution of gained inserts in container after sealing in 40 ℃ of gel 4min, obtains the opaque wet gel of oyster white;
4), the wet gel of step 3) gained is placed in to aging 72h at 40 ℃;
5), the aging rear gel of step 4) gained is placed in to 60 ℃ of constant pressure and dry 72h; Then the temperature rise rate with 2 ℃/min rises to 800 ℃ of heat preservation hot processing 5h, obtains porous cordierite block.
The porous cordierite block of preparation is unformed shape, because not yet there is crystal conversion after 800 ℃ of thermal treatment.Unformed porous cordierite piece practical ranges is limited.
The preparation method of embodiment 2, a kind of porous cordierite block,
By 800 ℃, make the thermal treatment temp in embodiment 1 step 5) into 1300 ℃, all the other are with embodiment 1.
The porous cordierite block preparing retains complete, and block surface flawless, only has a small amount of contraction; Better crystallinity degree, thing is single α type trichroite mutually.Porous cordierite block inside has continuous altogether macroporous structure and intact skeleton (see figure 1), and macropore mean pore size is 5 microns, and block apparent density density is about 0.82g/cm
3, calculating relative density is 32%, porosity is 54%.The N of this porous cordierite block
2suction-desorption curve is H3 type, show that block exists the slit-shaped of some amount mesoporous because of its skeleton structure, so this trichroite block has layer stephanoporate structure.
Test 1, by 800 ℃, make respectively the thermal treatment temp in embodiment 1 step 5) into 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, all the other are with embodiment 1.
By X-ray diffraction, the thing rule that thermal treatment temp changes that accompanies is analyzed, result as shown in Figure 4.
Comparative example 1-1, by 1.5g, make polyacrylamide (PAAm) into 1.0g, all the other are with embodiment 2.As shown in Figure 2, macroporous structure is not obvious for the porous mullite block internal microstructure preparing, and only has a small amount of macropore that connects, and this structure is separated and not exclusively causes in sol-gel process.
Comparative example 1-2, by 1.5g, make polyacrylamide (PAAm) into 2.0g, all the other are with embodiment 2.As shown in Figure 3, skeleton is formed by a large amount of particle packings the porous mullite block internal microstructure preparing, and skeleton structure disappears continuously, and this structure is separated and excessively causes in sol-gel process.
Comparative example 2-1, using the Aluminium chloride hexahydrate (AlCl as aluminium source
36H
2o) make common inorganic aluminate nine water aluminum nitrate (Al (NO into
3)
39H
2o), and with etc. amount of substance add after calculating, all the other are with embodiment 2.Wet gel after system gel is creamy white translucent, and dry rear gel is fragmented into fritter, finally cannot obtain the porous cordierite block in embodiment 2.
Comparative example 2-2, make the methyl silicate as silicon source (TMOS) into tetraethoxy (TEOS), and with etc. amount of substance add after calculating, all the other are with embodiment 2.There is obvious layering in the wet gel after system gel, finally also cannot obtain the porous cordierite block in embodiment 2.
The use of comparative example 3-1, cancellation propylene oxide, all the other are with embodiment 2.
Be placed in 40 ℃ of 12h under the sealed state of step 3) after, still there is not gel in it.Cannot carry out subsequent step.
Comparative example 3-2, the propylene oxide in embodiment 2 is made into the ammoniacal liquor (volume is constant) of 0.1mol/L, all the other are with embodiment 2.
Because system gel time is too fast, there is deposit seeds in subregion, finally cannot obtain the porous cordierite block described in embodiment 2.
Comparative example 3-3, make the propylene oxide in embodiment 2 into butylene oxide ring (volume is constant), all the other are with embodiment 2.
System gel time approaches when adopting propylene oxide, but gained xerogel intensity is low, is very easily broken into fritter, finally cannot obtain the porous cordierite block described in embodiment 2.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. the preparation method of porous cordierite block, it is characterized in that: first according to following ratio preparation main raw material: the magnesium chloride hexahydrate of 0.75～0.85g of take is magnesium source, the Aluminum Chloride Hexahydrate of 1.9～2.1g of take is aluminium source, the methyl silicate of 0.9～1.0ml of take is silicon source, with 1.4～1.6g polyacrylamide, for the inductor that is separated, the propylene oxide of 0.5～0.8ml of take is gel promotor; Then carry out successively following steps:
1), at room temperature, first magnesium chloride hexahydrate, Aluminum Chloride Hexahydrate and polyacrylamide are dissolved in solvent, then drip methyl silicate; After dropwising, in 50～70 ℃ of continuation stirring reaction 50～70min, obtain transparent settled solution;
2), the transparent settled solution of step 1) gained is naturally cooled to room temperature, then add propylene oxide uniform stirring 0.5～2min, obtain homogeneous solution;
3), by step 2) homogeneous solution of gained inserts in container after sealing in 35～45 ℃ of gel 3～5min, obtains wet gel;
4), the wet gel of step 3) gained is placed in to aging 60～80h at 35～45 ℃;
5), the gel after step 4) gained aging is placed in to 50～70 ℃ of constant pressure and dry 72～96h; Then in 900～1300 ℃ of thermal treatment 4～6h, obtain porous cordierite block.
2. the preparation method of porous cordierite 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 cordierite block according to claim 2, is characterized in that:
The consumption of described solvent is 4～8ml.
4. according to the preparation method of the porous cordierite block described in claim 1,2 or 3, it is characterized in that: the thermal treatment temp in step 5) is 1200～1300 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673688A (en) * | 2016-12-06 | 2017-05-17 | 浙江大学 | Preparation method of porous zinc aluminate gahnite block |
| CN107399962A (en) * | 2017-06-16 | 2017-11-28 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of low bulk fireproof thermal insulation plate |
| 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 |
| CN111333412A (en) * | 2020-03-09 | 2020-06-26 | 中国人民解放军国防科技大学 | Porous cordierite and preparation method and application thereof |
| CN112079647A (en) * | 2020-10-13 | 2020-12-15 | 阿尔赛(苏州)无机材料有限公司 | Ceramic fiber board and preparation method thereof |
| CN115231913A (en) * | 2022-07-07 | 2022-10-25 | 宜兴王子制陶有限公司 | Wall-flow honeycomb ceramic filter with adjustable porosity and preparation process thereof |
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| CN103242027A (en) * | 2013-05-14 | 2013-08-14 | 浙江大学 | Preparation method of porous mullite block |
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2014
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| CN103242027A (en) * | 2013-05-14 | 2013-08-14 | 浙江大学 | Preparation method of porous mullite block |
Non-Patent Citations (1)
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| XINGZHONG GUO ET AL.: "Preparation of macroporous cordierite monoliths via the sol–gel process processaccompanied by phase separation", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673688A (en) * | 2016-12-06 | 2017-05-17 | 浙江大学 | Preparation method of porous zinc aluminate gahnite block |
| CN106673688B (en) * | 2016-12-06 | 2019-09-20 | 浙江大学 | The preparation method of porous gahnite block |
| CN107399962A (en) * | 2017-06-16 | 2017-11-28 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of low bulk fireproof thermal insulation plate |
| 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 |
| CN111333412A (en) * | 2020-03-09 | 2020-06-26 | 中国人民解放军国防科技大学 | Porous cordierite and preparation method and application thereof |
| CN112079647A (en) * | 2020-10-13 | 2020-12-15 | 阿尔赛(苏州)无机材料有限公司 | Ceramic fiber board and preparation method thereof |
| CN112079647B (en) * | 2020-10-13 | 2023-10-10 | 阿尔赛(苏州)无机材料有限公司 | Preparation method of ceramic fiber board |
| CN115231913A (en) * | 2022-07-07 | 2022-10-25 | 宜兴王子制陶有限公司 | Wall-flow honeycomb ceramic filter with adjustable porosity and preparation process thereof |
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Application publication date: 20140716 |