CN1951811A - Octagonal zeolite synthesizing method - Google Patents
Octagonal zeolite synthesizing method Download PDFInfo
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- CN1951811A CN1951811A CN 200510047509 CN200510047509A CN1951811A CN 1951811 A CN1951811 A CN 1951811A CN 200510047509 CN200510047509 CN 200510047509 CN 200510047509 A CN200510047509 A CN 200510047509A CN 1951811 A CN1951811 A CN 1951811A
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Abstract
The invention discloses a synthesizing method of high-silicon aluminium rate octahedra zeolite, which is characterized by the following: synthesizing under alkaline condition to do hydrothermal crystallization; adopting low-molecular polyalcohol compound as moulding agent without zeolite seed; synthesizing the product in the hydrothermal condition directly.
Description
Technical field
The present invention relates to a kind of synthetic method of faujusite, particularly under hydrothermal condition, adopt the method for template synthetic faujasites.
Background technology
Zeolite molecular sieve is the regular crystalline structure with unique pore structure, mainly is crystal aluminosilicate.Zeolite molecular sieve has many types, and each all has the duct of specific dimensions and shape.Zeolite molecular sieve forms ring texture by silicon-oxy tetrahedron or aluminum-oxygen tetrahedron by oxo bridge, further is coupled to various basket structures then.Faujusite (FAU type zeolite) is exactly to be made of β cage and hexagonal column cage, surrounds octahedral zeolite cage by them and gains the name.Faujusite comprises X type and Y type, and both difference are aluminium content difference, just silica alumina ratio (SiO
2/ Al
2O
3) difference, general X type is greatly about 2-3, and the Y type is at 3-5, and they all adopt hydrothermal crystallization method synthetic usually.
Because octahedral zeolite cage can further form the supercage structure with big cavity, make faujusite in heterogeneous catalysis process, especially need to have obtained widespread use in the macromole heterogeneous catalysis process of good diffusion, for example heavy oil catalytic cracking process in the petrochemical technology field and hydrocracking process etc.Though belong to faujusite, the X zeolite is because silica alumina ratio is low, structural instability not only, and also its acid matter does not reach the catalyzed reaction requirement yet, therefore many as sorbent material or siccative, and Y zeolite has structural stability relatively preferably and be widely used as the component of various cracking catalyst.
The Y zeolite that synthesizes under alkaline medium is to come the balance skeleton electric charge by basic metal such as sodium ion, and the molecule number of sodium and aluminium is an equivalent in the faujusite skeleton, and the former powder of synthetic Y zeolite is the sodium type, about the about 10w% of its sodium oxide content.Because the existence of a large amount of sodium ions, the acidity of sodium type Y zeolite is very low, therefore in the practical application of Y zeolite, convert it into the Hydrogen product, adopts methods such as ammonium salt exchange usually.
On the other hand, for the thermostability that improves Y zeolite especially hydrothermal stability, will further improve the silica alumina ratio of the former powder of Y zeolite usually, the raising of silica alumina ratio also can improve the strength of acid of single acid sites and bring better catalytic pyrolysis performance.To improve the silica alumina ratio of the former powder of Y zeolite, method mainly contains chemical dealuminization and physics dealuminzation, the former is as gas phase silicon tetrachloride dealumination complement silicon, ammonium silicofluoride dealumination complement silicon, sour dealuminzation etc., the latter such as hydrothermal treatment consists etc., but whatsoever method all is that this a series of last handling process all is very loaded down with trivial details in actual production.
Belong to the NaY of faujusite, adopt the directing agent method preparation under the alkaline water thermal environment usually.For synthesizing of NaY, specifically be exactly under high basicity environment, to prepare the Y zeolite crystal seed earlier, join then in the NaY synthetic mixed gel system.We know that crystal seed glue is meant and contains as yet the not colloid of complete crystalline nucleus precursor, the aging quantity that can increase the nucleus precursor of crystal seed glue, and these nucleus precursors have served as nucleation centre in the gel sol system.This method is difficult to synthesize the faujasite than high silica alumina ratio usually, and if can directly synthesize the faujasite with high silica alumina ratio and will save a lot of last handling processes.Therefore, whether can adopt the FAU zeolite of template method synthesizing high-silicon aluminum ratio, cause concern gradually as some non-faujasites.
US5716593 discloses a kind of first extrusion moulding crystallization synthetic zeolite catalyst preparation method again, relate to the FAU prepare zeolite, but method is dry again up to the paste that forms a kind of extrusion moulding after organic formwork agent, silicon source, aluminium source and water are mixed, and putting into the bottom in the bottle of then it being packed into has the autoclave crystallization of water synthetic.Though the silica alumina ratio that feeds intake of this patent is at 6-15, but this does not also mean that its product has high silica alumina ratio, though patent does not have to disclose the silica alumina ratio of its product, but patent has pointed out not enter in a series of removing molecular sieves the last handling process of the silicon oxide of framework of molecular sieve, and the silica alumina ratio that therefore can infer its products molecule sieve should be lower than the silica alumina ratio that feeds intake.Patent synthetic water/silicon oxide is lower than very for this, requires to be no more than 6, therefore can not make amorphous silicon in the raw material be attached in the framework of molecular sieve well and guarantees good degree of crystallinity.The large usage quantity of alkali in this patented method, as the middle M that feeds intake
+/ SiO
2=0.2-1.0 (mol ratio), M
+Be basic metal, the consumption of alkali is scaled Na
2O/SiO
2Mol ratio be 0.4～2.0, too high meeting causes the rapid decline of product silica alumina ratio by being beneficial to forming of y-type zeolite though alkali number is too high, the actual framework si-al ratio of the zeolite product that this method obtains is generally not high.
US5549881 discloses a kind of faujusite preparation method, this patent also adopts synthetic certain of organic formwork agent to have the molecular screen composite of faujasite constitutional features, but it still needs to add certain sodium silicoaluminate crystal seed, and crystallization time reaches 8-14 days.The sodium silicoaluminate crystal seed prepares under the high alkalinity condition, and in embodiment, the sodium silicoaluminate crystal seed prepares Na in the material
2O/Al
2O
3Mol ratio be 13.33, do not use template in the seed crystal production process, and need for a long time aging.Use crystal seed faujusite grain morphology that synthesizes and the faujusite that synthesizes with the pure method of template of the present invention by obviously different, the former is generally the particle of many ribs, and the latter is for tending to sheet, and the sheet pattern helps the diffusion of catalytic reaction process molecule.
In addition, it is template that above-mentioned prior art all adopts organic ammonium, and building-up process is had certain restriction, and building-up process has certain environmental problem (waste gas and waste water).
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of synthetic method of high silica alumina ratio faujusite, by the template of selecting to suit, shorten crystallization time, improve the combined coefficient of zeolite.
High silica alumina ratio faujusite building-up process of the present invention may further comprise the steps:
(1) aluminium source, silicon source, sodium source and template are mixed according to a certain percentage;
(2) stir and formed in aging 1-100 hour even gel being no more than under 70 ℃ of conditions;
(3) mixed gel is moved into reactor and airtight;
(4) under 90-130 ℃ of condition under the reactor autogenous pressure hydrothermal crystallizing 40～180 hours;
(5) will obtain zeolite powder after crystallization product filtration and the drying.
The zeolite powder molar ratio with faujusite feature that the present invention relates to is: 5～20 SiO
2: 1.0～6.0Na
2O: Al
2O
3: 0.05～0.8 high molecular weight polyethylene glycol: 60～420: H
2O.Mixing of materials and aging generally carry out under room temperature～70 ℃ is preferably carried out under 40～60 ℃.
The template that the inventive method is used is in the high molecular weight polyethylene glycol one or more, its molecular weight is 2000～20000, preferred molecular weight is＞2000～10000 polyoxyethylene glycol, one or more in macromolecule polyethylene glycol commonly used such as Macrogol 2000, Macrogol 4000, polyethylene glycol 6000, the cetomacrogol 1000 0 etc.
The zeolite preparation method that the present invention relates to faujusite feature, according to needed proportioning aluminium source, silicon source, sodium source and template are mixed according to a certain percentage earlier, wherein the mixture silica best 6～15, water/alumina molar ratio is best 100～180, template high molecular weight polyethylene glycol/alumina molar ratio best 0.1～0.5.
The related silicon source of mixed gel is selected from a kind of or mixture of water glass, silica gel and silicon sol, and the aluminium source is selected from a kind of or mixture of sodium aluminate, Tai-Ace S 150, aluminum chloride and aluminum nitrate, and sodium oxide derives from sodium aluminate and/or sodium hydroxide.
According to the zeolite preparation method with faujusite feature that the present invention relates to, the hydrothermal crystallizing temperature is at best 100～120 ℃.
The zeolite powder that the present invention relates to has the faujusite feature, thereby shows faujusite XRD diffractive features in the XRD spectrum analysis, furtherly, shows the XRD diffractive features of the y-type zeolite that belongs to the faujusite class equally exactly.
The synthesizing high-silicon faujusite mainly adopts directing agent method in the prior art, promptly prepares faujasite seeds under high sodium condition, is the synthetic final faujusite product of directed agents with this crystal seed; Or under high sodium condition direct synthetic faujasites.The present invention adopts template agent method directly to synthesize the faujusite of high silica alumina ratio under hydrothermal condition, by adopting special template, under the relatively low situation of sodium consumption, need under high sodium condition, not make zeolite seed crystal earlier, can obtain the faujusite of high silica alumina ratio.And the inventive method generated time is short, can improve combined coefficient greatly, does not have special environmental issue.The faujusite that the inventive method obtains has higher silica alumina ratio, more crystalline degree, lower sodium content and bigger acidity.
Embodiment
Hydrothermal crystallization process involved in the present invention can be a kind of dynamic process of following stirring, or does not have the static process of stirring.Best, according to the hydrothermal crystallization process of process of the present invention be stir does not earlier have then stir dynamically and static state in conjunction with hydrothermal crystallization process.Statically advantageous is in nucleation, and the dynamic crystallization process promotes mass-and heat-transfer and helps obtaining uniform product, also can adopt dynamic and static bonded mode, and when adopting dynamic and static combination, both time scales can be 1: 0.1～10.No matter take any mode, all be scope of the present invention, and specifically adopt what mode, be decided by the practical situation of synthetic scale or production-scale size and equipment.
Because preparation method's difference, be that it adopts special template rather than adopts the Y zeolite crystal seed for preparing under the high sodium condition to do crystal-directing-agent, the zeolite powder that the present invention relates to has the feature of y-type zeolite, just belong to faujusite, and have the supercage structure, but its silica alumina ratio surpasses common NaY zeolite, according to the difference of feed ratio, generally at 6-20, usually at 6-12.
Further specify prepare zeolite method of the present invention by the following examples,, be not construed as limiting the invention though the scheme among the embodiment is the specific embodiments in scope of the invention claim scope.(per-cent wherein, w% are all represented weight percent)
Example 1
With the silicon sol is the silicon source, and sodium aluminate is aluminium source (containing sodium hydroxide), and polyethylene glycol 6000 is a template, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (Na
2O): n (template): n (Al
2O
3): n (H
2O)=and 6: 1.4: 0.1: 1: 80.Synthetic method: press the reaction mass proportioning, sodium hydroxide and sodium aluminate are added in the entry, stir and add polyethylene glycol 6000 after 30 minutes, add silicon sol again after continuing to be stirred to dissolving.Stirring is after 24 hours down at 50 ℃ with said mixture, and immigration is with in the autoclave of tetrafluoroethylene, and is airtight, at 100 ℃ of static crystallization 180h.After crystallization finishes, product is filtered, the washing back obtains zeolite sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
Example 2
With the silicon sol is the silicon source, and aluminum nitrate and sodium aluminate (containing sodium hydroxide) are aluminium source (both provide aluminium source ratio is 1: 2), and Macrogol 4000 is a template, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (Na
2O): n (template): n (Al
2O
3): n (H
2O)=and 6: 2.0: 0.16: 1: 130.Synthetic method: press the reaction mass proportioning, sodium hydroxide and sodium aluminate, aluminum nitrate are added to the water, stir and add Macrogol 4000 after 30 minutes, add silicon sol again after continuing to be stirred to dissolving.Stirring is after 12 hours down at 30 ℃ with said mixture, and room temperature moves in the autoclave of band tetrafluoroethylene after placing a night, and is airtight, at 110 ℃ of dynamic (80 rev/mins of stirring velocitys) crystallization 30h, and static crystallization 60h.After crystallization finishes, product is filtered, the washing back obtains zeolite sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
Example 3
With water glass is the silicon source, and Tai-Ace S 150 and sodium aluminate (containing sodium hydroxide) are aluminium source (ratio that both provide the aluminium source is 1: 2), and Macrogol 2000 is a template, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (Na
2O): n (template): n (Al
2O
3): n (H
2O)=and 12: 4.0: 0.5: 1: 200.Synthetic method: press the reaction mass proportioning, sodium aluminate and Tai-Ace S 150 are added to the water, stir and add Macrogol 2000 after 30 minutes, add silicon sol again after continuing to be stirred to dissolving.After said mixture at room temperature stirred 24 hours, move in the autoclave of band tetrafluoroethylene, airtight, at 120 ℃ of dynamic (200 rev/mins of stirring velocitys) crystallization 24h, static crystallization 60h then.After crystallization finishes, product is filtered, the washing back obtains zeolite sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
Example 4
With the silicon sol is the silicon source, and sodium aluminate (containing sodium hydroxide) is the aluminium source, and Macrogol 4000 is a template, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (Na
2O): n (template): n (Al
2O
3): n (H
2O)=and 18: 5.0: 0.25: 1: 220.Synthetic method: press the reaction mass proportioning, sodium aluminate is added to the water, stir and add Macrogol 4000 after 30 minutes, add silicon sol again after continuing to be stirred to dissolving.After said mixture at room temperature stirred 24 hours, move in the autoclave of band tetrafluoroethylene, airtight, under dynamically (150 rev/mins of stirring velocitys) in 110 ℃ of crystallization 96h.After crystallization finishes, product is filtered, the washing back obtains zeolite sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
Example 5
With silica gel is the silicon source, and aluminum chloride is the aluminium source, and sodium hydroxide is the sodium source, and Macrogol 4000 and Macrogol 2000 are mixed templates (weight ratio 2: 1), and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (Na
2O): n (template): n (Al
2O
3): n (H
2O)=20: 6.0: O.08: 1: 200.Synthetic method: press the reaction mass proportioning, aluminium hydroxide sodium is added to the water, stir after 30 minutes and to add Macrogol 4000 and Macrogol 2000 mixed templates, add silicon sol again after continuing to be stirred to dissolving, add aluminum chloride subsequently.After said mixture at room temperature stirred 24 hours, move in the autoclave of band tetrafluoroethylene, airtight.Earlier be 110 ℃ of crystallization 24h, be that dynamically 105 ℃ of crystallization 78h (150 rev/mins of stirring velocitys) are at 110 ℃ of crystallization 96h then in static state.After crystallization finishes, product is filtered, the washing back obtains zeolite sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
The main character of each embodiment preparing product of table 1
| Embodiment | Product structure | SiO 2/Al 2O 3Mol ratio |
| 1 | Faujusite | 6.3 |
| 2 | Faujusite | 7.2 |
| 3 | Faujusite | 9.6 |
| 4 | Faujusite | 11.8 |
| 5 | Faujusite | 12.1 |
Claims (10)
1, a kind of synthetic method of faujusite may further comprise the steps:
(1) aluminium source, silicon source, sodium source and template are mixed according to a certain percentage, template is high component polyoxyethylene glycol;
(2) stir and formed in aging 1-100 hour even gel being no more than under 70 ℃ of conditions;
(3) mixed gel is moved into reactor and airtight;
(4) under 90-130 ℃ of condition under the reactor autogenous pressure hydrothermal crystallizing 40～180 hours;
(5) will obtain zeolite powder after crystallization product filtration and the drying;
The raw material molar ratio is: 5～20SiO
2: 1.0～6.0Na
2O: Al
2O
3: 0.05～0.8 high molecular weight polyethylene glycol: 60～420: H
2O.
2, in accordance with the method for claim 1, the molecular weight that it is characterized in that described high molecular weight polyethylene glycol is 2000～20000.
3, in accordance with the method for claim 1, the molecular weight that it is characterized in that described high molecular weight polyethylene glycol is 2000～10000.
4, in accordance with the method for claim 1, it is characterized in that described template is one or more in Macrogol 2000, Macrogol 4000, polyethylene glycol 6000, the cetomacrogol 1000 0.
5, in accordance with the method for claim 1, it is characterized in that the described SiO that feeds intake
2/ Al
2O
3Mol ratio is 6～15, H
2O/Al
2O
3Mol ratio is 100～180, template high molecular weight polyethylene glycol/Al
2O
3Mol ratio is 0.1～0.5.
6, in accordance with the method for claim 1, it is characterized in that described silicon source is selected from a kind of or mixture of water glass, silica gel and silicon sol, the aluminium source is selected from a kind of or mixture of sodium aluminate, Tai-Ace S 150, aluminum chloride and aluminum nitrate, and the sodium source comes from sodium aluminate and/or sodium hydroxide.
7, in accordance with the method for claim 1, it is characterized in that described hydrothermal crystallizing temperature is 100～120 ℃.
8, in accordance with the method for claim 1, it is characterized in that mixing of materials and aging temperature are 40 ℃～60 ℃.
9, in accordance with the method for claim 1, it is characterized in that described hydrothermal crystallization process is a kind of dynamic process of following stirring, or do not have the static process of stirring.
10,, it is characterized in that described hydrothermal crystallization process is to stir earlier not have stir dynamic and static in conjunction with hydrothermal crystallization process then according to claim 1 or 9 described methods.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9359216B2 (en) | 2010-11-23 | 2016-06-07 | Reliance Industries Limited | Method for the preparation of MWW type zeolite |
| CN112850742A (en) * | 2019-11-12 | 2021-05-28 | 中国石油天然气股份有限公司 | Hierarchical pore Y-type molecular sieve and synthesis method thereof |
-
2005
- 2005-10-19 CN CNB2005100475092A patent/CN100431961C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9359216B2 (en) | 2010-11-23 | 2016-06-07 | Reliance Industries Limited | Method for the preparation of MWW type zeolite |
| CN112850742A (en) * | 2019-11-12 | 2021-05-28 | 中国石油天然气股份有限公司 | Hierarchical pore Y-type molecular sieve and synthesis method thereof |
| CN112850742B (en) * | 2019-11-12 | 2023-02-10 | 中国石油天然气股份有限公司 | Hierarchical pore Y-type molecular sieve and synthesis method thereof |
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