CN105776240A - Method for synthesizing AlPO-18 molecular sieve by means of segmented crystallization method - Google Patents
Method for synthesizing AlPO-18 molecular sieve by means of segmented crystallization method Download PDFInfo
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- CN105776240A CN105776240A CN201410797257.4A CN201410797257A CN105776240A CN 105776240 A CN105776240 A CN 105776240A CN 201410797257 A CN201410797257 A CN 201410797257A CN 105776240 A CN105776240 A CN 105776240A
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Abstract
The invention provides a method for synthesizing an AlPO-18 molecular sieve by means of a segmented crystallization method. The method comprises the steps that phosphoric acid serves as a phosphorus source, pseudo-boehmite serves as an aluminum source, triethylamine serves as a template agent, phosphoric acid, the aluminum source, the organic template agent and water are prepared into synthesized gel on the condition that the molar ratio of Al2O3 to H3PO4 to R to H2O is 1.0:2.0:3.0:50, the gel is crystallized for 2 h-10 h at 120 DEG C and then crystallized for 38 h-46 h at 150 DEG C-180 DEG C, the crystallized gel is cooled, water-washed, separated and air-dried at room temperature, and then the AlPO-18 molecular sieve is obtained. By means of the method, the AlPO-18 molecular sieve product with high crystallinity is obtained.
Description
Technical field
The present invention relates to the synthesis of aluminum phosphate molecular sieve analog, be specifically related to a kind of method synthesizing AlPO-18 molecular sieve by segmentation crystallization method
Background technology
The material with skeleton electric neutrality structure that AlPO-18 molecular sieve is made up of phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron, has three-dimensional octatomic ring pore canal system, and octatomic ring sky footpath is 3.8A × 3.8A, this and CO2(kinetic diameter 3.3A) and CH4(kinetic diameter 3.3A) is suitable, to CO2/CH4The separation of mixing gas system has very big prospect.Owing to having close crystallization synthesis condition, it is often accompanied by the generation of AlPO-5 molecular sieve during water heat transfer AlPO-18 molecular sieve, and synthesizing pure phase AlPO-18 molecular sieve is the problem not yet needing at present to solve.
Segmentation crystallization sources of law are in the exploration to crystal crystallization process, first gel decomposition becomes the little construction unit of four-membered ring, selectivity followed by four-membered ring unit piles up formation stratiform intermediate, the i.e. formation of precursor, along with temperature raises, precursor resolves into the different types of four-membered ring construction unit relevant to Al ligancy, is finally that four-membered ring is connected with each other and obtains AlPO with nucleation and crystallization4Molecular sieve analog, the crystallization temperature that molecular sieve precursor according to different types of structure is formed is different, first stablize a fixed structure presoma formation again under suitable crystallization temperature crystallization farthest avoid the generation of dephasign, therefore avoid the dephasign AlPO-5 molecular sieve in synthesis AlPO-18 molecular sieve process to be our research direction by segmentation crystallization method.
Summary of the invention
The invention provides a kind of method utilizing segmentation crystallization method synthesis AlPO-18 molecular sieve, with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 2-10h at 120 DEG C, proceeding to crystallization 38-46h at 150 DEG C-180 DEG C again, then cooling, washing, separation, room temperature are dried, and both obtain the AlPO-18 zeolite product that degree of crystallinity is higher.
Segmentation crystallization method i.e. pre-crystallization several hours at a lower temperature, to guarantee formation and the nucleation of target crystal precursor construction, the method then transferring to high temperature crystallization.According to above Research Thinking, fixing synthesizing formula is n (Al2O3)∶n(H3PO4)∶n(R)∶n(H2O)=1.0: 2.0: 3.0: 50, crystallization total time is 48h simultaneously, and low temperature control is at 120 DEG C, and high-temperature control is at 150 DEG C-180 DEG C.
Experiment finds to obtain pure phase AlPO-18 molecular sieve when the pre-crystallization time of low temperature is longer, still has AlPO-5 dephasign time shorter.Preferably, making synthesized gel rubber according to above-mentioned raw materials molar ratio, by this gel first crystallization 10h at 120 DEG C, then proceed to crystallization 38h at 150 DEG C, then cooling, washing, separation, room temperature are dried, and obtain AlPO-18 zeolite product degree of crystallinity the highest.
Detailed description of the invention
Embodiment 1 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 2h at 120 DEG C, then proceeds to crystallization 46h at 150 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Embodiment 2 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 6h at 120 DEG C, then proceeds to crystallization 42h at 150 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Embodiment 3 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 10h at 120 DEG C, then proceeds to crystallization 38h at 150 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Embodiment 4 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 2h at 120 DEG C, then proceeds to crystallization 46h at 170 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Embodiment 5 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 6h at 120 DEG C, then proceeds to crystallization 42h at 170 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Embodiment 6 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 10h at 120 DEG C, then proceeds to crystallization 38h at 170 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Embodiment 7 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 2h at 120 DEG C, then proceeds to crystallization 46h at 180 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Embodiment 8 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 6h at 120 DEG C, then proceeds to crystallization 42h at 180 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Embodiment 9 one kinds utilizes the method for segmentation crystallization method synthesis AlPO-18 molecular sieve, and with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 2h at 120 DEG C, then proceeds to crystallization 38h at 180 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
Product under the different crystallization condition of table one
The results show, the pre-crystallization time of low temperature is more long, when high temperature crystallization time subtracts more few, can obtain pure phase AlPO-18 molecular sieve.
Claims (2)
1. the method utilizing segmentation crystallization method synthesis AlPO-18 molecular sieve, it is characterised in that through following step: with phosphoric acid for phosphorus source, boehmite is aluminum source, and triethylamine is template, and by phosphoric acid, aluminum source, organic formwork agent, water is according to Al2O3∶H3PO4∶R∶H2The molar ratio of O=1.0: 2.0: 3.0: 50 makes synthesized gel rubber, by this gel first crystallization 2-10h at 120 DEG C, then proceeds to crystallization 38-46h at 150 DEG C-180 DEG C, and then cooling, washing, separation, room temperature are dried, and both obtain product.
2. a kind of method utilizing segmentation crystallization method synthesis AlPO-18 molecular sieve according to claim 1, by this gel first crystallization 10h at 120 DEG C, then proceeds to crystallization 38h at 150 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0293939A2 (en) * | 1987-06-04 | 1988-12-07 | Union Carbide Corporation | Crystalline aluminophosphate composition |
| EP1511687B1 (en) * | 2002-06-12 | 2008-05-14 | ExxonMobil Chemical Patents, Inc. a Corporation of the State of Delaware | Synthesis of molecular sieves having the cha framework type |
| CN101559956A (en) * | 2009-05-22 | 2009-10-21 | 中国科学院过程工程研究所 | Method for preparing Lewis acid SAPO-34 molecular sieve |
| CN102530989A (en) * | 2011-12-15 | 2012-07-04 | 神华集团有限责任公司 | Method for preparing large-crystal SAPO-34 molecular sieve, product obtained by the method and application of the product |
-
2014
- 2014-12-19 CN CN201410797257.4A patent/CN105776240A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0293939A2 (en) * | 1987-06-04 | 1988-12-07 | Union Carbide Corporation | Crystalline aluminophosphate composition |
| EP1511687B1 (en) * | 2002-06-12 | 2008-05-14 | ExxonMobil Chemical Patents, Inc. a Corporation of the State of Delaware | Synthesis of molecular sieves having the cha framework type |
| CN101559956A (en) * | 2009-05-22 | 2009-10-21 | 中国科学院过程工程研究所 | Method for preparing Lewis acid SAPO-34 molecular sieve |
| CN102530989A (en) * | 2011-12-15 | 2012-07-04 | 神华集团有限责任公司 | Method for preparing large-crystal SAPO-34 molecular sieve, product obtained by the method and application of the product |
Non-Patent Citations (1)
| Title |
|---|
| BANGHAO CHEN ET AL.: "Formation fo microporous materials AlPO-18 under dry-gel conversion conditions", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
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