CN1118432C - Composite dual-pure Si-Al molecular sieve and its preparing process - Google Patents
Composite dual-pure Si-Al molecular sieve and its preparing process Download PDFInfo
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- CN1118432C CN1118432C CN 00128055 CN00128055A CN1118432C CN 1118432 C CN1118432 C CN 1118432C CN 00128055 CN00128055 CN 00128055 CN 00128055 A CN00128055 A CN 00128055A CN 1118432 C CN1118432 C CN 1118432C
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Abstract
The present invention relates to a double mesoporous silicon aluminum composite molecular sieve whose molar ratio of silicon to aluminium is 2 to 100:1, macroporous pore diameter is from 10 to 30 nm, and microporous pore diameter is from 2 to 3 nm. The silicon aluminum composite moleculer sieve with catalytic activity and double mesoporous distributions is synthesized under the moderate reaction conditions in a collosol-gelatin way. The present invention is characterized in that raw materials are cheap and easy to get, reaction conditions are mild, and the operation is simple, convenient and easy; the silica alumina ratio and the pore size of the molecular sieve can be regulated by changing the proportion of the raw materials and the reaction conditions.
Description
The invention belongs to a kind of molecular sieve and preparation method thereof, relate in particular to a kind of composite dual-pure Si-Al molecular sieve and preparation method thereof.
Pore distribution is narrow because of having for mesopore molecular sieve, specific surface area is big and characteristics such as high adsorption capacity, so it has a wide range of applications and research value at aspects such as catalysis, ion-exchange, fractionation by adsorption and high inorganic materials.Novel mesopore molecular sieve MCM-41 from 1992 by U.S. Mobil oil company synthetic first since, caused the very big concern (J.Amer.Chem.Soc., 1992,114,10834) of zeolite and catalysis circle.The much more synthetic of this molecular sieve analog adopted the high-temperature water thermal synthesis methods, and institute's synthetic molecular sieve has single pore size distribution, but it is restricted to some macromolecular catalyzed reaction and in the application of pharmacy field.Employing ammoniacal liquor or sodium hydroxide are made catalyzer, can synthesize to have two mesoporous pure silicon molecular sieve (Chem.Commun., 1995,2367 under cold condition; Chem.Commun., 1998,1035), its aperture mainly concentrates on about 2.6nm and 19nm, but this molecular sieve is because of containing metal atom aluminium not, thereby does not have catalytic activity in catalyzed reaction.
Goal of the invention of the present invention provides a kind of double mesopore molecular sieve with catalytic activity and preparation method thereof.
The silicon of double mesopore molecular sieve of the present invention and al mole ratio are Si: Al=2-100: 1, and macropore diameter is 10-30nm, small aperture is 2-3nm.
The preparation method of double mesopore molecular sieve of the present invention comprises the steps:
(1) preparation of mother liquor
Silicon source, aluminium source, dehydrated alcohol, deionized water, template after 1-8 hour, are added catalyzer in mixing under the whipped state according to a certain ratio, continue to stir 1-3 hour, mole proportioning of its each composition is:
Si: Al=2-100: 1 dehydrated alcohol: Si=1-20: 1
Deionized water: Si=10-120: 1 template: Si=0.1-0.8: 1
Catalyzer: Si=0.5-20: 1
(2) crystallization, the mother liquor that (1) is made under 20-80 ℃ of temperature crystallization 4-144 hour;
(3) removal of template
Product after (2) crystallization is adopted ethanol Soxhlet extraction method extraction 24-96h, remove template, or adopt, remove template, make described composite molecular screen at 500-600 ℃ of roasting temperature 5-12 hour.
The optimum mole ratio of aforesaid deionized water and silicon should be 20-90: 1.
The optimum mole ratio of aforesaid catalyzer and silicon is 2.5-12: 1.
Aforesaid silicon source is tetraethoxy (TEOS) or methyl silicate (TMOS).
Aforesaid template is cetyl trimethylammonium bromide (CTAB), bromohexadecane yl pyridines (CPBr), lauryl amine (DDA).
Aforesaid catalyzer is ammoniacal liquor, NaOH.
The present invention compared with prior art has following advantage:
(1) raw material is cheap and easy to get, and the reaction conditions gentleness is easy to operation.
(2) the later institute of crystallization synthetic molecular sieve has the feature of diplopore distribution and higher catalytic reaction activity at low temperatures.
(3) by changing proportioning raw materials and reaction conditions, the sial of adjustable change molecular sieve is pore size when.
The embodiment of the invention is as follows:
Embodiment 1
With 5mlTEOS+0.84g Al (NO
3)
39H
2O+20ml H
2O+6.25ml C
2H
5OH+2.04g CTAB is after stirring 2h under the room temperature, and in 50 ℃ of crystallization 96h, 550 ℃ of roasting 6h get sieve sample.Adopt nitrogen adsorption one desorption method that pore distribution is characterized, the pore size distribution of product concentrates on 2.5nm and 12nm, with molecular sieve 250 ℃ of reaction 4h in naphthalene one Virahol one perhydronaphthalene system, be 91% to the transformation efficiency that decalin base reacts with the gas chromatographic detection molecular sieve.
Embodiment 2
With 5ml TMOS+9ml 0.5M Al
2(SO
4)
3Solution+10ml H
2O+1.25ml C
2H
5OH+3.32gDDA is after stirring 6h under the room temperature, in system, add the 37.5ml strong aqua and continue to stir 1h, in 80 ℃ of crystallization 36h, alcohol extraction 96h gets sieve sample, the pore size distribution of product concentrates on 3nm and 29nm, molecular sieve is 92% to the transformation efficiency of decalin base reaction, and all the other are with embodiment 1.
Embodiment 3
With 5ml TEOS+0.18g Al (O
iPr)
3+ 4ml H
2O+25ml C
2H
5OH+0.82g CTAB is after stirring 8h under the room temperature, in system, add 4.5g NaOH and continue to stir 3h, in 25 ℃ of crystallization 144h, 550 ℃ of roasting 6h get sieve sample, the pore size distribution of product concentrates on 2.6nm and 21nm, molecular sieve is 90% to the transformation efficiency of decalin base reaction, and all the other are with embodiment 1.
Embodiment 4
With 5mlTEOS+0.17g Al (NO
3)
39H
2O+40ml H
2O+12.5ml C
2H
5OH+1.04g DDA is after stirring 4h under the room temperature, in system, add the 18.75ml strong aqua, continue to stir 2.5h, in 60 ℃ of crystallization 72h, alcohol extraction 30h gets sieve sample, the pore size distribution of product concentrates on 2.8nm and 23nm, and molecular sieve is 90.2% to the transformation efficiency of decalin base reaction, and all the other are with embodiment 1.
Embodiment 5
With 3.33ml TMOS+2.24m10.5M AlCl
3Solution+24ml H
2O+15ml C
2H
5OH+1.8gCPBr is after stirring 5h under the room temperature, in system, add 3.15g NaOH, continue to stir 1.5h, in 40 ℃ of crystallization 48h, 550 ℃ of roasting 12h get sieve sample, the pore size distribution of product concentrates on 2.3nm and 18nm, and molecular sieve is 90.5% to the transformation efficiency of decalin base reaction, and all the other are with embodiment 1.
Embodiment 6
With 5mlTEOS+0.42g Al (NO
3)
39H
2O+48ml H
2O+3.13ml C
2H
5OH+4.08g CTAB is after stirring 1h under the room temperature, in system, add the 30ml strong aqua and continue to stir 2h, in 50 ℃ of crystallization 5h, alcohol extraction 87h gets sieve sample, the pore size distribution of product concentrates on 2.0hm and 16nm, molecular sieve is 92.5% to the transformation efficiency of decalin base reaction, and all the other are with embodiment 1.
Claims (7)
1. composite dual-pure Si-Al molecular sieve, it is characterized in that: the silicon of double mesopore molecular sieve and al mole ratio are Si: Al=2-100: 1, macropore diameter is 10-30nm, small aperture is 2-3nm.
2. the preparation method of a composite dual-pure Si-Al molecular sieve is characterized in that comprising the steps:
(1) preparation of mother liquor
Silicon source, aluminium source, dehydrated alcohol, deionized water, template after 1-8 hour, are added catalyzer in mixing under the whipped state according to a certain ratio, continue to stir 1-3 hour, mole proportioning of its each composition is:
Si: Al=2-100: 1 dehydrated alcohol: Si=1-20: 1
Deionized water: Si=10-120: 1 template: Si=0.1-0.8: 1
Catalyzer: Si=0.5-20: 1
(2) crystallization, the mother liquor that (1) is made under 20-80 ℃ of temperature crystallization 4-144 hour;
(3) removal of template
Product after (2) crystallization is adopted ethanol Soxhlet extraction method extraction 24-96h, remove template, or adopt, remove template, make described composite molecular screen at 500-600 ℃ of roasting temperature 5-12 hour.
3. the preparation method of a kind of composite dual-pure Si-Al molecular sieve as claimed in claim 2, the mol ratio that it is characterized in that described deionized water and silicon is 20-90: 1.
4. the preparation method of a kind of composite dual-pure Si-Al molecular sieve as claimed in claim 2, the mol ratio that it is characterized in that described catalyzer and silicon is 2.5-12: 1.
5. the preparation method of a kind of composite dual-pure Si-Al molecular sieve as claimed in claim 2 is characterized in that described silicon source is tetraethoxy or methyl silicate.
6. the preparation method of a kind of composite dual-pure Si-Al molecular sieve as claimed in claim 2 is characterized in that described template is cetyl trimethylammonium bromide, bromohexadecane yl pyridines, lauryl amine.
7. the preparation method of a kind of composite dual-pure Si-Al molecular sieve as claimed in claim 2 is characterized in that described catalyzer is ammoniacal liquor, NaOH.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100447085C (en) * | 2004-10-16 | 2008-12-31 | 太原理工大学 | Mesoporous Zr-Si molecular sieve and its synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314589C (en) * | 2004-09-24 | 2007-05-09 | 中国石油化工股份有限公司 | Porous material and its synthesis method |
| CN100369672C (en) * | 2005-12-14 | 2008-02-20 | 中国科学院山西煤炭化学研究所 | Organic and inorganic conjugated solid acid preparation method |
| CN103769192B (en) * | 2012-10-24 | 2016-07-20 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN103482634B (en) * | 2013-09-09 | 2015-07-01 | 辽宁石油化工大学 | Preparation method of silicon-based dual mesoporous material |
| CN105344338A (en) * | 2015-12-08 | 2016-02-24 | 无锡拓能自动化科技有限公司 | Preparation method of hydrogen sulfide gas adsorbing agent |
| CN108767240B (en) * | 2018-06-11 | 2021-03-19 | 河源云创新能源实业有限公司 | Preparation method of lithium ion battery negative electrode material |
| CN110698349A (en) * | 2019-10-21 | 2020-01-17 | 西南化工研究设计院有限公司 | Recovery method of dimethyl ether carbonylation MOR molecular sieve catalyst template agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100447085C (en) * | 2004-10-16 | 2008-12-31 | 太原理工大学 | Mesoporous Zr-Si molecular sieve and its synthesis |
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