CN101602513B - Method for preparing aluminum phosphate molecular screen in eutectic mixture - Google Patents
Method for preparing aluminum phosphate molecular screen in eutectic mixture Download PDFInfo
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- CN101602513B CN101602513B CN2009100749457A CN200910074945A CN101602513B CN 101602513 B CN101602513 B CN 101602513B CN 2009100749457 A CN2009100749457 A CN 2009100749457A CN 200910074945 A CN200910074945 A CN 200910074945A CN 101602513 B CN101602513 B CN 101602513B
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- eutectic mixture
- phosphate molecular
- quaternary ammonium
- molecular sieve
- ammonium salt
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Abstract
The invention provides a method for preparing an aluminum phosphate molecular screen in a eutectic mixture, and belongs to the field of inorganic chemical synthesis. In particular, the invention relates to a method for an aluminum phosphate molecular screen by the eutectic mixture as a reaction solvent and a template. The method is characterized by using the eutectic mixture prepared by combining alcohol and quaternary ammonium salt as the reaction solvent and the template to prepare the aluminum phosphate molecular screen. In the ion thermal reaction, the eutectic mixture has proper acidity and alkaline, the alcohol organic matters are not decomposed to release extra organic amine in the crystallization reaction process when being heated, and the quaternary ammonium salt in the system can fully complete the structure guide action. Compared with the imidazole ionic liquid, the used eutectic mixture material has the advantages of low price, easy purchase and preparation, hard deliquescence and convenient use.
Description
Technical field
The present invention prepares the method for aluminium phosphate molecular sieve in eutectic mixture, belong to the synthetic field of inorganic chemistry.Specifically relate to a kind of method for preparing aluminium phosphate molecular sieve with eutectic mixture as reaction solvent and template.
Background technology
The ionic liquid thermal synthesis method is a kind of new inorganic crystal material synthetic method by the RussellMorris professor seminar report of Britain St Andrews university in 2004, this method is different with traditional solvent thermal process, be characterized in that at synthetic system intermediate ion liquid be not only solvent, but promptly be that solvent is again a template, the ionic liquid thermal synthesis method has taken the synthetic of inorganic crystal material to a complete brand-new field, thereby is subjected to people's great attention.
The metal phosphate molecular sieve analog has the structure and the performance of traditional zeolite, has the potential using value in fields such as absorption, ion-exchange and catalysis, its synthetic extensive concern that always is subjected to.This seminar has adopted quaternary ammonium salt with ionic liquid characteristic and organic acid reaction to obtain eutectic mixture, and vehicle economy S prepares Zirconium phosphate crystal material as the solvent template of holding concurrently, and has declared Chinese patent.Aluminium phosphate molecular sieve is composition and the abundantest class of topological framework, and since nineteen eighty-two, Wilson reported aluminium phosphate molecular sieve, a large amount of aluminum phosphate compounds with one-dimensional chain, two-dimensional layer and three-dimensional spacious skeleton structure were synthesized out in succession.Usually these aluminium phosphate molecular sieves realize that via hydro-thermal or solvent thermal route of synthesis organic amine or ammonium salt and reaction solvent have significant effects to the crystalline structure and the shape characteristic of final product as structure directing agent with organic amine or ammonium salt.
Yet, be used for the ion thermal response at present and mainly concentrate on imidazoles base class ionic liquid and urea or carboxylic acid and the composite ionic eutectic mixture that forms of quaternary ammonium salt.But for aluminium phosphate molecular sieve, the low-melting mixtures of urea (or urea analog derivative) class can decomposite ammonia or organic amine when high temperature; And the low molten mixture of carboxylic-acid has stronger acidity, often need to add the acid-basicity that organic amine comes regulation system, the organic amine of this " additionally " has very strong template action, cause the template action of the quaternary ammonium salt component in the system to can not get performance, limited the generation of possible aluminium phosphate molecular sieve.
Summary of the invention
The present invention prepares the method for aluminium phosphate molecular sieve in eutectic mixture, purpose is to disclose a kind of in eutectic mixture (DES), by alcohols with quaternary ammonium salt is composite forms, prepare the technical scheme of the method for aluminium phosphate molecular sieve as reaction solvent and template.
The present invention prepares the method for aluminium phosphate molecular sieve in eutectic mixture, it is characterized in that, is the composite eutectic mixture that forms of a kind of alcohols and quaternary ammonium salt, prepares the method for aluminium phosphate molecular sieve as reaction solvent and template, and its concrete steps are:
I, eutectic mixture DES preparation:
Place mortar to grind fully alcohol compound and quaternary ammonium salt, place beaker under 120～130 ℃, to heat then, after become transparent liquid, being cooled to room temperature, become white solid, just can be applied to reaction; Selected alcohol compound comprises tetramethylolmethane or neopentyl glycol; Quaternary ammonium compound comprises chlormequat chloride, 4 bromide or choline chloride 60; The compound proportion of described alcohols and quaternary ammonium salt is at 0.5-2.0;
II, with eutectic mixture DES prepared among the step I, aluminum isopropylate { Al[OCH (CH
3)
2]
3, phosphorus source and hydrofluoric acid (HF) joins successively in the band teflon-lined stainless steel cauldron and reacts, sealed reactor is positioned over temperature and is controlled in 130-200 ℃ the baking oven, react 2-7 days, takes out reactor, at room temperature cools off; Described phosphorus source is ortho-phosphoric acid (H
3PO
4) or tributyl phosphate [(C
4H
9O)
3PO]; The material molar ratio of its described reaction is HF: Al[OCH (CH
3)
2]
3: P
2O
5: DES=(0-3.0): 1: (0.5-2.5): (20-60);
III, the reactor after Step II reaction finished take out, and are cooled to room temperature, take out crystallization product, with ethanol wash, filter, drying, promptly obtain the product of aluminium phosphate molecular sieve.
The product X-ray powder diffraction analysis of institute of the present invention synthetic aluminium phosphate molecular sieve is at Japan motor X-ray diffractometer of science XRD, detect on the Rigaku Mini Flex, test condition: copper target, the K alpha-ray, operating voltage 30kV, working current 15mA, step-length is 0.01 °, sweep limit 2 θ=5 °～40 °, sweep velocity is 1 °/min, sample is tested through behind the careful porphyrize compressing tablet.
The advantage for preparing the method for aluminium phosphate molecular sieve in eutectic mixture of the present invention is:
I, compare with traditional solvent process for thermosynthesizing, employed eutectic mixture in aluminium phosphate molecular sieve synthetic the while as solvent and template.
II, employed eutectic mixture are by high-melting-point alcohols such as tetramethylolmethane or neopentyl glycol and quaternary ammonium salt is composite forms, and have the physical and chemical performance that ionic liquid shows,
For example low melting point, low-steam pressure, electroconductibility, high polarity and to the excellent dissolution ability of inorganics.And have suitable acid-basicity, need not again the reaction system acid-basicity to be regulated and control.And pure type organic can decomposes not discharge extra organic amine in the reaction crystallization process, the quaternary ammonium salt in the system can fully play structure-directing effect.
III, with respect to glyoxaline ion liquid, employed eutectic mixture raw material cheaply is easy to get and prepares simply, is difficult for deliquescence in air, and is easy to use.
IV, eutectic mixture are the extremely low green fine solvents of volatility, so this synthetic method environmental protection, can reduce the pollution to environment.
Description of drawings
Fig. 1-3 is X-ray powder diffraction (XRD) spectrogram of aluminium phosphate molecular sieve of the present invention, and ordinate zou is represented diffraction peak intensity (Intensity), and X-coordinate is represented diffraction peak 2 θ angles.
Fig. 1 is the XRD spectra of ZON type aluminium phosphate molecular sieve;
Fig. 2 is the XRD spectra of ERI type aluminium phosphate molecular sieve;
Fig. 3 is the XRD spectra of AWW type aluminium phosphate molecular sieve.
Embodiment
The present invention illustrates with following example, but the present invention is not limited to following example, under the scope of described aim, changes and implements to be included in the technology of the present invention scope before and after not breaking away from.
Embodiment 1:
2.7g tetramethylolmethane and 1.5g 4 bromide (mol ratio is 2.0) are ground in mortar fully, mixture with the two places beaker to heat under 130 ℃ then, until becoming transparent liquid, just obtain eutectic mixture (DES), become white solid after being cooled to room temperature.Under the room temperature, with the 4.2g DES of preparation, 0.20gAl[OCH (CH
3)
2]
3, 0.23g H
3PO
4, 20 μ l HF join in the 20ml teflon-lined stainless steel cauldron successively, and the mol ratio of end reaction thing is 0.5HF: 1.0Al[OCH (CH
3)
2]
3: 2.0H
3PO
4: 30DES, after the sealing, crystallization temperature is 180 ℃ of crystallization 3 days, takes out reactor after reaction finishes, and is cooled to room temperature.The crystallization product of gained is taken out, with ethanol wash, filter, drying.Final product is a ZON type aluminium phosphate molecular sieve, and its XRD spectra is seen Figure of description 1.
Embodiment 2:
2.0g tetramethylolmethane and 2.2g chlormequat chloride (mol ratio is 1.0) are ground in mortar fully, mixture with the two places beaker to heat under 130 ℃ then, until becoming transparent liquid, just obtain eutectic mixture (DES), become white solid after being cooled to room temperature.Under the room temperature, with the 4.2g DES of preparation, 0.21g Al[OCH (CH
3)
2]
3, 0.23g H
3PO
4, 20 μ l HF join in the 20ml teflon-lined stainless steel cauldron successively, and the mol ratio of end reaction thing is 0.5HF: 1.0Al[OCH (CH
3)
2]
3: 2.0H
3PO
4: 29DES, after the sealing, crystallization temperature is 180 ℃ of crystallization 3 days, takes out reactor after reaction finishes, and is cooled to room temperature.The crystallization product of gained is taken out, with ethanol wash, filter, drying.Final product is an ERI type aluminium phosphate molecular sieve, and its XRD spectra is seen Figure of description 2.
Embodiment 3:
Do not add HF in the initial action system, the mol ratio of end reaction thing is 1.0Al[OCH (CH
3)
2]
3: 2.0H
3PO
4: 29DES, other is with embodiment 2, and final product is an AWW type aluminium phosphate molecular sieve, and its XRD spectra is seen Figure of description 3.
Embodiment 4:
1.0g tetramethylolmethane and 2.0g choline chloride 60 (mol ratio is 0.5) are ground in mortar fully, mixture with the two places beaker to heat under 130 ℃ then, until becoming transparent liquid, just obtain ground eutectic mixture (DES), become white solid after being cooled to room temperature.Under the room temperature, with the 3.0g DES of preparation, 0.20g Al[OCH (CH
3)
2]
3, 0.11g H
3PO
4, 20 μ l HF join in the 20ml teflon-lined stainless steel cauldron successively, and the mol ratio of end reaction thing is 0.5HF: 1.0Al[OCH (CH
3)
2]
3: 1.0H
3PO
4: 20DES, after the sealing, crystallization temperature is 180 ℃ of crystallization 4 days, takes out reactor after reaction finishes, and is cooled to room temperature.The crystallization product of gained is taken out, with ethanol wash, filter, drying.Final product is a ZON type aluminium phosphate molecular sieve.
Embodiment 5:
3.1g neopentyl glycol and 4.4g 4 bromide (mol ratio is 1) are ground in mortar fully, mixture with the two places beaker to heat under 125 ℃ then, until becoming transparent liquid, just obtain eutectic mixture (DES), become white solid after being cooled to room temperature.Under the room temperature, with the 7.5g DES of preparation, 0.20gAl[OCH (CH
3)
2]
3, 0.35g H
3PO
4, 40 μ l HF join in the 20ml teflon-lined stainless steel cauldron successively, and the mol ratio of end reaction thing is 1.0HF: 1.0Al[OCH (CH
3)
2]
3: 3.0H
3PO
4: 60DES, after the sealing, crystallization temperature is 130 ℃, crystallization 7 days is taken out reactor after reaction finishes, and is cooled to room temperature.The crystallization product of gained is taken out, with ethanol wash, filter, drying.Final product is a ZON type aluminium phosphate molecular sieve.
Embodiment 6:
0.77g tributyl phosphate [(C
4H
9O)
3PO] replacement H
3PO
4, the amount of adding phosphoric acid in the system is 20 μ l, the mol ratio of end reaction thing is 1.0HF: 1.0Al[OCH (CH
3)
2]
3: 5.0 (C
4H
9O)
3PO: 30DES, crystallization temperature are 200 ℃, and crystallization time is 2 days, and other is with embodiment 1, and final product is a ZON type aluminium phosphate molecular sieve.
Embodiment 7:
2.1g neopentyl glycol and 3.0g chlormequat chloride (mol ratio is 1.0) are ground in mortar fully, mixture with the two places beaker to heat under 120 ℃ then, until becoming transparent liquid, just obtain eutectic mixture (DES), become white solid after being cooled to room temperature.Under the room temperature, with the 5.1g DES of preparation, 0.21g Al[OCH (CH
3)
2]
3, 0.46g tributyl phosphate [(C
4H
9O)
3PO], 60 μ l HF join in the 20ml teflon-lined stainless steel cauldron successively, and the mol ratio of end reaction thing is 1.5HF: 1.0Al[OCH (CH
3)
2]
3: 3.0 (C
4H
9O)
3PO: 39DES, the sealing back is in 150 ℃, and crystallization 3 days is taken out reactor after reaction finishes, and is cooled to room temperature.The crystallization product of gained is taken out, with ethanol wash, filter, drying.Final product is an ERI type aluminium phosphate molecular sieve.
Embodiment 8:
Do not add HF in the initial action system, the mol ratio of end reaction thing is 1.0Al[OCH (CH
3)
2]
3: 3.0 (C
4H
9O)
3PO: 39DES, other is with embodiment 6, and final product is an AWW type aluminium phosphate molecular sieve.
Embodiment 9:
0.12g tributyl phosphate [(C
4H
9O)
3PO] replacement H
3PO
4, the amount of adding phosphoric acid in the system is 120 μ l, the mol ratio of end reaction thing is 3.0HF: 1.0Al[OCH (CH
3)
2]
3: 1.0 (C
4H
9O)
3PO: 30DES, crystallization temperature are 150 ℃, and crystallization time is 2 days, and other is with embodiment 2, and final product is an ERI type aluminium phosphate molecular sieve.
Embodiment 10:
0.60g tributyl phosphate [(C
4H
9O)
3PO] replacement H
3PO
4, do not add HF in the initial action system, the mol ratio of end reaction thing is 1.0Al[OCH (CH
3)
2]
3: 5.0 (C
4H
9O)
3PO: 30DES, crystallization temperature are 200 ℃, and crystallization time is 3 days, and other is with embodiment 2, and final product is an AWW type aluminium phosphate molecular sieve.
Claims (1)
1. the method for preparing aluminium phosphate molecular sieve in eutectic mixture is characterized in that it being the composite eutectic mixture that forms of a kind of alcohols and quaternary ammonium salt, prepares the method for aluminium phosphate molecular sieve as reaction solvent and template, and its concrete steps are:
I, eutectic mixture DES preparation:
Place mortar to grind fully alcohol compound and quaternary ammonium salt, place beaker under 120～130 ℃, to heat then, after become transparent liquid, being cooled to room temperature, become white solid, just can be applied to reaction; Selected alcohol compound comprises tetramethylolmethane or neopentyl glycol; Quaternary ammonium compound comprises chlormequat chloride, 4 bromide or choline chloride 60; The compound proportion of described alcohols and quaternary ammonium salt is at 0.5-2.0;
II, with eutectic mixture DES prepared in the step I, aluminum isopropylate { Al[OCH (CH
3)
2]
3, phosphorus source and hydrofluoric acid (HF) joins successively in the band teflon-lined stainless steel cauldron and reacts, sealed reactor is positioned over temperature and is controlled in 130-200 ℃ the baking oven, react 2-7 days, takes out reactor, at room temperature cools off; Described phosphorus source is ortho-phosphoric acid (H
3PO
4) or tributyl phosphate; The material molar ratio of its described reaction is HF: Al[OCH (CH
3)
2]
3: P
2O
5: DES=(0-3.0): 1: (0.5-2.5): (20-60);
III, the reactor after step II reaction finished take out, and are cooled to room temperature, take out crystallization product, with ethanol wash, filter, drying, promptly obtain the product of aluminium phosphate molecular sieve.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102139885B (en) * | 2010-01-29 | 2012-10-03 | 中国科学院大连化学物理研究所 | -CLO structural aluminum phosphate molecular sieve and preparation method thereof |
| CN102153106B (en) * | 2010-07-29 | 2012-12-12 | 兰州理工大学 | Quick reparation method for heteroatom phosphorus aluminum molecular sieve in eutectoid |
| CN102476806A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method of synthesizing super large micropore aluminium phosphate molecular sieve in eutectic mixture |
| CN102583436A (en) * | 2011-01-06 | 2012-07-18 | 兰州理工大学 | Quick synthesis method of heteroatomic aluminophosphate molecular sieve SAPO-5 in eutectic body |
| CN102786063A (en) * | 2012-08-10 | 2012-11-21 | 中国海洋石油总公司 | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure |
| CN102807229B (en) * | 2012-08-10 | 2014-03-05 | 中国海洋石油总公司 | Method for synthesizing SAPO-31 (silicoaluminophosphate-31) molecular sieves at ordinary pressure |
| CN103553076A (en) * | 2013-10-28 | 2014-02-05 | 中国海洋石油总公司 | Method for continuously producing silicoaluminophosphate (SAPO-5) molecular sieve |
| CN103708499A (en) * | 2014-01-14 | 2014-04-09 | 兰州理工大学 | Preparation method of hierarchical pore heteroatom aluminophosphate molecular sieve MnAlPO-5 |
| CN103818926A (en) * | 2014-01-14 | 2014-05-28 | 兰州理工大学 | Preparation method of hierarchical-pore CoAlPO-5 molecular sieve |
| CN106366005B (en) * | 2016-08-08 | 2018-10-16 | 河南工业大学 | A kind of method that ball milling prepares eutectic solvent |
| CN106629760B (en) * | 2017-01-03 | 2018-10-02 | 兰州理工大学 | A method of synthesis AFI type silicoaluminophosphamolecular molecular sieves |
| WO2018180539A1 (en) * | 2017-03-31 | 2018-10-04 | 日本碍子株式会社 | Eri-structure zeolite membrane and membrane structure |
| CN107497395A (en) * | 2017-08-31 | 2017-12-22 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared under ion hot system |
| CN114425304B (en) * | 2020-10-10 | 2023-08-29 | 中国石油化工股份有限公司 | Molecular sieve immobilized eutectic solvent material and preparation and application thereof |
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