CN102259885A - porous material and synthesis method thereof - Google Patents
porous material and synthesis method thereof Download PDFInfo
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- CN102259885A CN102259885A CN201010183188XA CN201010183188A CN102259885A CN 102259885 A CN102259885 A CN 102259885A CN 201010183188X A CN201010183188X A CN 201010183188XA CN 201010183188 A CN201010183188 A CN 201010183188A CN 102259885 A CN102259885 A CN 102259885A
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- porous material
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Abstract
The invention relates to a porous material and a synthesis method thereof, and mainly solves the problem of a new layered porous material which is not involved in the prior art. In the invention, the problem is better solved by using a technical scheme in the synthesis method. According to the invention, the porous material is used, wherein the porous material comprises the following components in a molar correlation: Al2O3:nSiO2 (n = 10-80) and is characterized in that the XRD (X-ray diffraction) spectrum of the material has d-spacing maximum values at 97+/-0.2 angstroms, 6.9+/-0.2 angstroms, 4.6+/-0.2 angstroms, 3.9+/-0.1 angstroms, 3.7+/-0.1 angstroms and 3.4+/-0.3 angstroms. The synthesis method of the porous material provided by the invention can be used for industrial production of porous materials.
Description
Technical field
The present invention relates to a kind of porous material and synthetic method thereof.
Background technology
Industrial, porous inorganic material is widely used as catalyzer and support of the catalyst.Porous material has higher relatively specific surface and unimpeded pore passage structure, is good catalytic material or support of the catalyst therefore.Porous material roughly can comprise: unformed porous material, crystalline molecular sieve and modified layered material etc.
The basic skeleton structure of crystalline microporous zeolite is based on the three-dimensional TO of inflexible
4(SiO
4, AlO
4Deng) modular construction; TO in this structure
4Be to share Sauerstoffatom, skeleton tetrahedron such as AlO in the tetrahedron mode
4Charge balance be by surperficial positively charged ion such as Na
+, H
+Existence keep.This shows the skeleton character that can change zeolite by the cationic exchange mode.Simultaneously, in the structure of zeolite, exist pore canal system abundant, that the aperture is certain, the interlaced formation tridimensional network in these ducts.
The artificial crystalline micro-pore zeolite usually is to adopt hydrothermal method synthetic, and often adopts specific template or directed agents to synthesize specific zeolite molecular sieve.These template or directed agents usually are organic compounds containing nitrogen.Yet there is corresponding relation between template or directed agents and the specific zeolite molecular sieve.As: for having micropore MFI structure ZSM-5, US3702886 finds to adopt tetrapropyl ammonium (TPA) to synthesize as directed agents, and US4151189 finds to adopt C
2～C
9Primary amine be that directed agents also can be synthesized.Other disclose the method for Tetrabutylammonium bromide as the synthetic ZSM-11 of directed agents that adopt as US3709979, US3832449 discloses and adopted tetraethyl ammonium is the method for the synthetic ZSM-12 of directed agents, US4016245 discloses and adopted quadrol is the method for the synthetic ZSM-35 of directed agents, Zeolite (1991, Vol 11, and P202) having introduced and having adopted tetraethyl ammonium hydroxide is the method for the synthetic Beta zeolite of directed agents.Adopt same template or directed agents also can synthesize zeolitic material with different structure feature.The method that adopts the synthetic PSH-3 zeolite of hexamethylene imine is disclosed as US4439409, US4954325 discloses the method that adopts the synthetic MCM-22 of hexamethylene imine, it is directed agents that US5362697 and ZL94192390.8 disclose with the hexamethylene imine, has the method for stable stratiform MWW structure MCM-56 by the control crystallization time is synthetic, it is the method for the synthetic non-stratiform MCM-49 of directed agents with the hexamethylene imine that US5236575 has introduced, Nature (1998, Vol396, P353) to disclose with the hexamethylene imine be directed agents to magazine, adopt the demixing technology preparation to have the method for the ITQ-2 of MWW structure.
Summary of the invention
One of technical problem to be solved by this invention provides the new porous material that does not relate in a kind of prior art.This material is a stratified material, has relative higher specific surface area.
Two of technical problem to be solved by this invention provides synthetic method a kind of and one of technical solution problem corresponding porous material.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of porous material comprises the composition of following molar relationship: Al
2O
3: n SiO
2, n=10 in the formula～80, the XRD diffracting spectrum of wherein said porous material is 9.7 ± 0.2, and there is d-spacing maximum value at 6.9 ± 0.2,4.6 ± 0.2,3.9 ± 0.1,3.7 ± 0.1 and 3.4 ± 0.3 dust places.
In the technique scheme, the preferable range of n is 13～70.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: silicon source, aluminium source, template R, alkali and water are mixed, and mixture is with molar ratio computing SiO
2/ Al
2O
3=13～70, H
2O/SiO
2=10～70, R/SiO
2=0.01～0.5, OH
-/ SiO
2=0.2～0.6, be under 140～170 ℃ of conditions with said mixture in temperature, crystallization was taken out after 18～120 hours, made described porous material through washing, drying.Wherein said template R is selected from least a of (ETMAOH) in tetraethyl ammonium hydroxide (TEAOH), hexahydropyridine, pyridine, dimethyl diethyl ammonium hydroxide (DMDEAOH) or the ethyl-trimethyl ammonium hydroxide.Described silicon source is selected from least a in soft silica, silicon sol, silica gel, diatomite or the water glass; Described aluminium source is selected from least a in aluminium hydroxide, aluminum isopropylate, aluminium secondary butylate, sodium aluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride or the aluminum oxide, and described alkali is selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide; Mixture is as follows with the molar ratio computing preferable range: SiO
2/ Al
2O
3=14～65, more preferably scope is SiO
2/ Al
2O
3=15～60, H
2O/SiO
2=12～65, more preferably scope is H
2O/SiO
2=15～60, R/SiO
2=0.03～0.4, more preferably scope is R/SiO
2=0.04～0.3, OH
-/ SiO
2=0.25～0.55, more preferably scope is OH
-/ SiO
2=0.3～0.5.
The present invention is by having synthesized the layered porous material with specific XRD diffraction data to the modulation of each component relative content in the reaction mixture with to the surprised discovery of the control of crystallization process, can be used for having obtained better technical effect in the industrial production of porous material.
Description of drawings
Fig. 1 is the XRD diffraction spectrogram of poromerics.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With sodium hydroxide 2.2 gram, silicon sol (40 weight %) 16 grams, aluminium secondary butylate 1.4 grams, dimethyl diethyl ammonium hydroxide (20 weight %) 6.4 grams, distilled water 26 grams, to mix and stir, the mol ratio of each component is SiO
2/ Al
2O
3=36, H
2O/SiO
2=20, OH
-/ SiO
2=0.43, R/SiO
2=0.1.Said mixture, elevated temperature to 160 ℃ crystallization rotating the baking oven dynamic crystallization after 48 hours, with the crystallizing kettle cool to room temperature, through centrifugal, washing, filtration, was put into 100 ℃ of dryings of baking oven 8 hours with product again.X-ray powder diffraction data see Table 1.
Table 1
[embodiment 2～8]
The synthesis step of [embodiment 2～8] is identical with [embodiment 1] with method, just changes the add-on of crystallization temperature, crystallization time, template and alkali.The concrete synthesis condition and the proportioning of [embodiment 2～8] see Table 2.Synthetic product X-ray powder diffraction data see Table 3～9 respectively.
Table 2
Silicon sol: contain SiO
240 weight %
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
Claims (6)
1. porous material comprises the composition of following molar relationship: Al
2O
3: n SiO
2, n=10 in the formula～80, the XRD diffracting spectrum that it is characterized in that described material is 97 ± 0.2, and there is d-spacing maximum value at 6.9 ± 0.2,4.6 ± 0.2,3.9 ± 0.1,3.7 ± 0.1 and 3.4 ± 0.3 dust places.
2. porous material according to claim 1 is characterized in that n=13～70.
3. the synthetic method of the described porous material of claim 1 is mixed silicon source, aluminium source, template R, alkali and water, and mixture is with molar ratio computing SiO
2/ Al
2O
3=13～70, H
2O/SiO
2=10～70, R/SiO
2=0.01～0.5, OH
-/ SiO
2=0.2～0.6, is under 140～170 ℃ of conditions with said mixture in temperature, crystallization was taken out after 18～120 hours, through washing, drying makes described porous material, wherein said template R is selected from least a in tetraethyl ammonium hydroxide, hexahydropyridine, pyridine, dimethyl diethyl ammonium hydroxide or the ethyl-trimethyl ammonium hydroxide.
4. the synthetic method of porous material according to claim 3 is characterized in that described silicon source is selected from least a in soft silica, silicon sol, silica gel, diatomite or the water glass; Described aluminium source is selected from least a in aluminium hydroxide, aluminum isopropylate, aluminium secondary butylate, sodium aluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride or the aluminum oxide, and described alkali is selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide.
5. the synthetic method of porous material according to claim 3 is characterized in that mixture is with molar ratio computing SiO
2/ Al
2O
3=14～65, H
2O/SiO
2=12～65, R/SiO
2=0.03～0.4, OH
-/ SiO
2=0.25～0.55.
6. the synthetic method of porous material according to claim 5 is characterized in that mixture is with molar ratio computing SiO
2/ Al
2O
3=15～60, H
2O/SiO
2=15～60, R/SiO
2=0.04～0.3, OH
-/ SiO
2=0.3～0.5.
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|---|---|---|---|
| CN201010183188XA CN102259885A (en) | 2010-05-26 | 2010-05-26 | porous material and synthesis method thereof |
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|---|---|---|---|
| CN201010183188XA CN102259885A (en) | 2010-05-26 | 2010-05-26 | porous material and synthesis method thereof |
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|---|---|
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Family
ID=45006760
Family Applications (1)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084383A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Porous material preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362697A (en) * | 1993-04-26 | 1994-11-08 | Mobil Oil Corp. | Synthetic layered MCM-56, its synthesis and use |
| CN101239728A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Micro-pore zeolite, preparation method and application thereof |
-
2010
- 2010-05-26 CN CN201010183188XA patent/CN102259885A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362697A (en) * | 1993-04-26 | 1994-11-08 | Mobil Oil Corp. | Synthetic layered MCM-56, its synthesis and use |
| CN101239728A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Micro-pore zeolite, preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084383A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Porous material preparation method |
| CN105084383B (en) * | 2014-05-14 | 2017-09-26 | 中国石油化工股份有限公司 | The preparation method of porous material |
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Application publication date: 20111130 |