CN1299987C - Method for preparing MWW molecular screen material with variable silicon-aluminium proportion - Google Patents
Method for preparing MWW molecular screen material with variable silicon-aluminium proportion Download PDFInfo
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- CN1299987C CN1299987C CNB2004100038895A CN200410003889A CN1299987C CN 1299987 C CN1299987 C CN 1299987C CN B2004100038895 A CNB2004100038895 A CN B2004100038895A CN 200410003889 A CN200410003889 A CN 200410003889A CN 1299987 C CN1299987 C CN 1299987C
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- molecular sieve
- aluminium
- silicon
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Abstract
The present invention relates to a method for preparing an MWW molecular sieve material with a variable silicon-aluminium ratio. Firstly, a boron-silicon MWW molecular sieve is prepared, and a preparing process of the boron-silicon MWW molecular sieve comprises that silicon compounds, boric acid, template agents and secondary deionized water are used as a raw material, and the raw material is prepared into a molecular sieve ERB-1 of a boron-silicon MWW structure through hydrothermal synthesis. A proper amount of the boron-silicon MWW molecular sieve, compounds with aluminium and the secondary deionized water are used as a raw material for carrying out hydrothermal treatment. Then, a mixture which is obtained is transferred into a stainless steel reaction kettle to carry out heat treatment under certain temperature, and after cooling, the mixture is filtered and washed to obtain a reaction product. The present invention not only can be used for exchanging and obtaining an MWW molecular sieve with a variable silica alumina ratio under a dynamic condition, but also can be used for obtaining the MWW molecular sieve with a variable silica alumina ratio under the condition of static water heat exchange.
Description
Technical field
The present invention relates to a kind of preparation method of molecular screen material, relate in particular to the preparation method of the variable MWW molecular sieve of a kind of silica alumina ratio.
Background technology
Zeolite molecular sieve is the crystalline material that a class has accurate repetition microcrystalline texture, and a large amount of holes is arranged in its crystalline structure, has many ducts to be interconnected between hole and the hole.Because pore size distribution is very narrow and even, can select to adsorb the molecule of specific dimensions, and repel the molecule of other large-size.The little inner vesicular structure of this class material can optionally allow molecule enter the very large internal surface of material, with catalysis and the adsorption activity that strengthens them.Therefore be widely used in catalysis in petrochemical complex and the fine chemistry industry, separate and process such as ion-exchange.
Molecular sieve catalyst generally has good shape selectivity.Simultaneously meaning that also molecular sieve catalyst is difficult to more macromolecular catalytic process, seek and both had the acid and stable of general molecular sieve to have the porous crystalline material of the larger aperture of rule again, is unusual exigence in the present petrochemical complex research.MCM-22 family molecular sieves with special construction is exactly that a class has and can allow the molecular screen material of the approaching acidic site of big organic molecule.The MCM-22 molecular sieve is synthetic first in nineteen ninety by Mobil company, different according to structure and preparation method, MCM-22 (USP4,954,325), MCM-49 (USP5,236,575), PSH-3 (USP4,439,409), SSZ-25 (USP4,826,667), ITQ-1, ERB-1 belong to this skeleton structure type, MCM-36, MCM-56, ITQ-2 belong to the material that is made of the MWW molecular layer.Be called the MCM-22 family molecular sieves with the MCM-22 molecular sieve.Studies show that, be converted into alkene and fields such as aromatic hydrocarbons, catalytic cracking, isomerisation of olefin and hydro carbons alkylation have shown good catalytic performance because its particular structure that has and chemical property are carrier or catalyzer with it at alkane, the MCM-22 molecular sieve has very big application potential.The catalytic activity of MCM-22 molecular sieve and unique catalysis behavior make it synthesize a focus that becomes catalytic field with catalyzed reaction research.
It is the critical nature of molecular sieve catalyst that the acidity of molecular sieve and strength of acid distribute, and plays important effect in catalytic process, and acidity and the strength of acid distribution of therefore controlling molecular sieve are the important goals of preparation molecular sieve catalyst.B acid derives from the four-coordination aluminium in the skeleton structure in the Si-Al molecular sieve, and L acid is mainly derived from non-skeleton hexa-coordinate aluminium, and the surface acidity of the content of the Al in the molecular sieve and distribution thereof and molecular sieve is closely related.In sieve synthesis procedure, can change the Si/Al ratio of crystallization mixture, synthetic have the molecular sieve of desirable Si/Al ratio, but the variation of Si/Al ratio in the synthetic system, will inevitably influence synthesis condition, and by the hydrothermal method synthesis of molecular sieve can not be unlimited the silica alumina ratio of change molecular sieve.For the MCM-22 molecular sieve with, can only between Si/Al is than 10 to 15, obtain the molecular sieve of MWW structure, change Si/Al in the reactant system than the molecular sieve that can generate other structure.
The silica alumina ratio that changes in the molecular sieve can adopt dealuminzation and mend the aluminium treatment process, obtains having the molecular sieve of ideal framework si-al ratio, to satisfy the requirement of different catalyzed reactions.The method of molecular sieve dealuminzation comprises steam treatment, high-temperature roasting, mineral acid treatment and other chemical process processing etc.Discover that the aluminium in the MCM-22 molecular sieve is highly stable, the concentrated nitric acid with 14.5M under the 373K condition is handled the synthetic MCM-22 molecular sieve that obtains, and the silica alumina ratio of the product that obtains and molecular screen primary powder silica alumina ratio difference are little.The Japan scientist utilizes high-temperature water thermal treatment and the processing of concentrated nitric acid subsequently that the MCM-22 molecular sieve is carried out dealuminzation, MCM-22 molecular sieve silica alumina ratio behind the dealuminzation is doubled than former powder molecular sieve, but is difficult to obtain the more MWW molecular screen material of high silica alumina ratio (Si/Al＞100).Above-mentioned studies show that by sial MCM-22 molecular sieve being carried out not only condition harshness of dealuminzation, the process complexity, and be difficult to obtain MWW molecular sieve than high silica alumina ratio.
Summary of the invention
The objective of the invention is to develop the route and the method for new more convenient simple synthetic MWW structure Si-Al molecular sieve, be laying the first stone of MWW structure Si-Al molecular sieve at catalytic science and application in engineering.The present invention handles under hydrothermal condition the synthetic borosilicate MWW molecular sieve ERB-1 that obtains, and by utilizing aluminium to replace to the boron in the framework of molecular sieve structure, obtained the Si-Al molecular sieve of the adjustable MWW structure of silica alumina ratio.The aluminium atom that boron atom in the borosilicate zeolite is compared in the aluminium si molecular sieves is more active relatively, is exchanged and takes off easily.Present method can be at different reactions, control the ratio that aluminium replaces the boron in the borosilicate zeolite skeleton by the ratio of control gelling system and the temperature of hydrothermal treatment consists, obtain the different MWW Si-Al molecular sieve material of silica alumina ratio, thereby the acidity of adjusting molecular sieve is to obtain catalytic activity preferably.
The method for preparing sial MWW molecular sieve provided by the invention, its key step is:
A) water and template stir into solution, add boric acid and are stirred to whole dissolvings, add the compound and the stirring of silicon again, get gel; The mol ratio of its various compositions is SiO
2: xNa
2O: yB
2O
3: zR: wH
2O;
Wherein: R is a template; Y=0.1-1.0, z=0.8-2, w=15-40;
X=0, or x=0.01-0.5,
Described template is hexamethylene imine or piperidines;
B) gel that step a is made moves to reactor, and in 150-200 ℃ of crystallization 1-10 days, cooling was filtered, and gets crystallized product;
C) crystallized product that step b is made got borosilicate MWW molecular sieve ERB-1 in 450-650 ℃ of roasting 1-15 hour;
D) with the compound dissolution of aluminium in water, add molecular sieve and stir, the molar ratio of gained reactant solution system is:
ERB-1∶xAl
2O
3∶yH
2O
X=0.1-3.0 wherein, y=10-100;
E) with steps d gained mixture in reactor 60-200 ℃ following hydrothermal treatment consists 1-8 days, cooling is filtered, and washs to such an extent that mend the aluminium product.
Wherein the compound of the silicon among the step a is white carbon black, water glass, silicon sol or alkoxyl group estersil.
Wherein the compound of the aluminium in the steps d is Al (NO
3)
3, Al
2(SO
4)
3, NaAlO
2Or AlCl
3
Wherein the benefit aluminium process among the step e is that dynamic hydro-thermal is mended aluminium or Static Water is vulcanized aluminium.
Embodiment
Below by the following example the present invention is further specified, but the present invention uses the restriction that is not subjected to these embodiment.
Embodiment 1
Under the room temperature to 171g H
2O adds the 50g hexamethylene imine formation solution A that stirs, and adds H to above-mentioned solution then
3BO
341.4g and be stirred to complete moltenly and continue to stir half hour, in 1 hour, add white carbon black 30g then and keep vigorous stirring, add the back and continued vigorous stirring 2 hours, the molar ratio of gained system is: SiO
2: 0.67B
2O
3: 1.0HMI: 19H
2O.
Then the gained gel is transferred in the stainless steel cauldron in 175 ℃ of vibration crystallization 7 days, cooled and filtered, wash crystallized product fully, former powder 540 ℃ of following roastings 10 hours the MWW molecular sieve.With 2.4g Al (NO
3)
3Be dissolved in 36gH
2Form uniform solution among the O, and then the molecular sieve of the above-mentioned preparation of 1.2g joined in the solution stir, the mixture that obtains is transferred in the stainless steel cauldron in 200 ℃ of hydro-thermals replacement processing 3 days, cooled and filtered, distilled water and the washing of 500ml dilute hydrochloric acid with 500ml heat obtains the MWW molecular sieve product that aluminium exchanges respectively.
Embodiment 2
Under the room temperature to 171g H
2O adds the 50g hexamethylene imine formation solution A that stirs, and adds H to above-mentioned solution then
3BO
341.4g and be stirred to complete moltenly and continue to stir half hour, in 1 hour, add white carbon black 30g then and keep vigorous stirring, add the back and continued vigorous stirring 2 hours, the molar ratio of gained system is: SiO
2: 0.67B
2O
3: 1.0HMI: 19H
2O.
Then the gained gel is transferred in the stainless steel cauldron in 175 ℃ of vibration crystallization 7 days, cooled and filtered, wash crystallized product fully, former powder 540 ℃ of following roastings 10 hours the MWW molecular sieve.With 2.4g Al (NO
3)
3Be dissolved in 36gH
2Form uniform solution among the O, and then the molecular sieve of 1.2g preparation joined in the solution stir, the mixture that obtains is transferred in the stainless steel cauldron in 180 ℃ of hydro-thermals replacement processing 3 days, cooled and filtered, distilled water and the washing of 500ml dilute hydrochloric acid with 500ml heat obtains the MWW molecular sieve product that aluminium exchanges respectively.
Embodiment 3
Under the room temperature to 171g H
2O adds the 50g hexamethylene imine formation solution A that stirs, and adds H to above-mentioned solution then
3BO
341.4g and be stirred to complete moltenly and continue to stir half hour, in 1 hour, add white carbon black 30g then and keep vigorous stirring, add the back and continued vigorous stirring 2 hours, the molar ratio of gained system is: SiO
2: 0.67B
2O
3: 1.0HMI: 19H
2O.
Then the gained gel is transferred in the stainless steel cauldron in 175 ℃ of vibration crystallization 7 days, cooled and filtered, wash crystallized product fully, former powder 540 ℃ of following roastings 10 hours the MWW molecular sieve.With 2.4g Al
2(SO
4)
3Be dissolved in 36gH
2Form uniform solution among the O, and then the molecular sieve of 1.2g preparation joined in the solution stir, the mixture that obtains is transferred in the stainless steel cauldron in 110 ℃ of hydro-thermals replacement processing 3 days, cooled and filtered, distilled water and the washing of 500ml dilute hydrochloric acid with 500ml heat obtains the MWW molecular sieve product that aluminium exchanges respectively.
Embodiment 4
Under the room temperature to 171g H
2O adds the 50g hexamethylene imine formation solution A that stirs, and adds H to above-mentioned solution then
3BO
341.4g and be stirred to complete moltenly and continue to stir half hour, in 1 hour, add white carbon black 30g then and keep vigorous stirring, add the back and continued vigorous stirring 2 hours, the molar ratio of gained system is: SiO
2: 0.67B
2O
3: 1.0HMI: 19H
2O.
Then the gained gel is transferred in the stainless steel cauldron in 175 ℃ of vibration crystallization 7 days, cooled and filtered, wash crystallized product fully, former powder 540 ℃ of following roastings 10 hours the MWW molecular sieve.With 2.4g Al (NO
3)
3Be dissolved in 36gH
2Form uniform solution among the O, and then the molecular sieve of 1.2g preparation joined in the solution stir, the mixture that obtains is transferred in the stainless steel cauldron in 90 ℃ of hydro-thermals replacement processing 3 days, cooled and filtered, distilled water and the washing of 500ml dilute hydrochloric acid with 500ml heat obtains the MWW molecular sieve product that aluminium exchanges respectively.
Embodiment 5
Under the room temperature to 171g H
2O adds the 50g hexamethylene imine formation solution A that stirs, and adds H to above-mentioned solution then
3BO
341.4g and be stirred to complete moltenly and continue to stir half hour, in 1 hour, add alkoxyl group estersil 104g then and keep vigorous stirring, add the back and continued vigorous stirring 2 hours, the molar ratio of gained system is: SiO
2: 0.67B
2O
3: 1.0HMI: 19H
2O.
Then the gained gel is transferred in the stainless steel cauldron in 175 ℃ of vibration crystallization 7 days, cooled and filtered, wash crystallized product fully, former powder 540 ℃ of following roastings 10 hours the MWW molecular sieve.With 3g NaAlO
2Be dissolved in 36gH
2Form uniform solution among the O, and then the molecular sieve of 1.2g preparation joined in the solution stir, the mixture that obtains is transferred in the stainless steel cauldron in 180 ℃ of hydro-thermals replacement processing 1 day, cooled and filtered, distilled water and the washing of 500ml dilute hydrochloric acid with 500ml heat obtains the MWW molecular sieve product that aluminium exchanges respectively.
Embodiment 6
Under the room temperature to 111g H
2O adds the 50g hexamethylene imine formation solution A that stirs, and adds H to above-mentioned solution then
3BO
341.4g and be stirred to complete moltenly and continue to stir half hour, in 1 hour, add silicon sol (30%) 90g then and keep vigorous stirring, add the back and continued vigorous stirring 2 hours, the molar ratio of gained system is: SiO
2: 0.67B
2O
3: 1.0HMI: 19H
2O.
Then the gained gel is transferred in the stainless steel cauldron in 175 ℃ of vibration crystallization 7 days, cooled and filtered, wash crystallized product fully, former powder 540 ℃ of following roastings 10 hours the MWW molecular sieve.With 3g NaAlO
2Be dissolved in 24gH
2Form uniform solution among the O, and then the molecular sieve of 1.2g preparation joined in the solution stir, the mixture that obtains is transferred in the stainless steel cauldron in 180 ℃ of hydro-thermals replacement processing 8 days, cooled and filtered, distilled water and the washing of 500ml dilute hydrochloric acid with 500ml heat obtains the MWW molecular sieve product that aluminium exchanges respectively.
Embodiment 7
Under the room temperature to 81g H
2O adds the 50g piperidines formation solution A that stirs, and adds H to above-mentioned solution then
3BO
341.4g and be stirred to complete moltenly and continue to stir half hour, in 1 hour, add water glass (25%) 120g then and keep vigorous stirring, add the back and continued vigorous stirring 2 hours, the molar ratio of gained system is: SiO
2: 0.67B
2O
3: 1.0HMI: 19H
2O.
Then the gained gel is transferred in the stainless steel cauldron in 175 ℃ of vibration crystallization 7 days, cooled and filtered, wash crystallized product fully, former powder 540 ℃ of following roastings 10 hours the MWW molecular sieve.With 3g AlCl
3Be dissolved in 36gH
2Form uniform solution among the O, and then the molecular sieve of 1.2g preparation joined in the solution stir, the mixture that obtains is transferred in the stainless steel cauldron in 200 ℃ of hydro-thermals replacement processing 3 days, cooled and filtered, distilled water and the washing of 500ml dilute hydrochloric acid with 500ml heat obtains the MWW molecular sieve product that aluminium exchanges respectively.
Claims (4)
1. method for preparing the variable MWW molecular screen material of silica alumina ratio, its key step:
A) water and template stir into solution, add boric acid and are stirred to whole dissolvings, add the compound and the stirring of silicon again, get gel; The mol ratio of its various compositions is SiO
2: xNa
2O: yB
2O
3: zR: wH
2O;
Wherein: R is a template; Y=0.1-1.0, z=0.8-2, w=15-40;
X=0 or x=0.01-0.5;
Described template is hexamethylene imine or piperidines;
B) gel that step a is made moves to reactor, and in 150-200 ℃ of crystallization 1-10 days, cooling was filtered, and gets crystallized product;
C) crystallized product that step b is made got borosilicate MWW molecular sieve ERB-1 in 450-650 ℃ of roasting 1-15 hour;
D) with the compound dissolution of aluminium in water, add molecular sieve and stir, the molar ratio of gained reactant solution system is:
ERB-1∶xAl
2O
3∶yH
2O
X=0.1-3.0 wherein, y=10-100;
E) with steps d gained mixture in reactor 60-200 ℃ following hydrothermal treatment consists 1-8 days, cooling is filtered, and washs to such an extent that mend the aluminium product.
2. method according to claim 1 is characterized in that, the compound of the silicon among the step a is white carbon black, water glass, silicon sol or alkoxyl group estersil.
3. method according to claim 1 is characterized in that, the compound of the aluminium in the steps d is Al (NO
3)
3, Al
2(SO
4)
3, NaAlO
2Or AlCl
3
4. method according to claim 1 is characterized in that, the benefit aluminium process among the step e is that dynamic hydro-thermal is mended aluminium or Static Water is vulcanized aluminium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100460324C (en) * | 2006-09-30 | 2009-02-11 | 华东师范大学 | Method for synthesizing alkali modified molecular sieve containing titanium |
| CN100582003C (en) * | 2007-05-25 | 2010-01-20 | 中国科学院上海硅酸盐研究所 | Sol-gel process for preparing Yb2SiO5 powder |
| CN107226474A (en) * | 2016-03-23 | 2017-10-03 | 中国石化扬子石油化工有限公司 | Mend aluminium method of modifying in a kind of ZSM-5 original positions |
| CN112429745B (en) * | 2019-08-26 | 2023-04-07 | 中国石油化工股份有限公司 | H-type MCM-22 molecular sieve and preparation method and application thereof |
| CN113620308B (en) * | 2020-05-06 | 2022-10-21 | 中国石油化工股份有限公司 | Preparation method of hydrogen type ZSM-48 molecular sieve |
Citations (1)
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|---|---|---|---|---|
| JP2003327425A (en) * | 2002-03-07 | 2003-11-19 | Showa Denko Kk | Mww type zeolite substance, precursory substance thereof and their production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003327425A (en) * | 2002-03-07 | 2003-11-19 | Showa Denko Kk | Mww type zeolite substance, precursory substance thereof and their production method |
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