CN100390059C - High silica/ aluminum ratio octagonal zeolite synthesizing method - Google Patents
High silica/ aluminum ratio octagonal zeolite synthesizing method Download PDFInfo
- Publication number
- CN100390059C CN100390059C CNB2005100475105A CN200510047510A CN100390059C CN 100390059 C CN100390059 C CN 100390059C CN B2005100475105 A CNB2005100475105 A CN B2005100475105A CN 200510047510 A CN200510047510 A CN 200510047510A CN 100390059 C CN100390059 C CN 100390059C
- Authority
- CN
- China
- Prior art keywords
- accordance
- sio
- sodium
- zeolite
- template
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a synthesizing method of high-silicon aluminium rate octahedra zeolite, which is characterized by the following: adopting moulding agent to synthesize the product through hydrothermal crystallizing method under fitful sodium condition directly.
Description
Technical field
The present invention relates to a kind of synthetic method of faujusite, particularly the method for synthesizing high-silicon aluminum ratio faujusite under hydrothermal condition.
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 directing agent method (crystal seed directed agents) 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, need to add certain sodium silicoaluminate crystal seed but it has still used, 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.The faujusite grain morphology that uses crystal seed to synthesize is generally the particle of many ribs, is unfavorable for the diffusion of reaction process molecule, is unfavorable for improving the selectivity of reaction.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of synthetic method of faujusite of high silica alumina ratio, the inventive method alkali consumption is few, and crystallization time is short.
The synthetic method of high silica alumina ratio faujusite of the present invention comprises following process:
(1) aluminium source, silicon source, sodium source and organic bases 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 24-240, preferred 24～120 hours;
(5) will obtain zeolite powder after crystallization product filtration and the drying.
Wherein various raw material molar ratios are: 5～50Si
2O: 1.5～15Na
2O: Al
2O
3: 0.3～3.5 organic bases template: 60～420H
2O.Wherein the mixture silica is best 6～15, and water/alumina molar ratio is best 100～180, template tetraethyl ammonium hydroxide/alumina molar ratio best 0.8～2.5.Na wherein
2O/SiO
2Mol ratio is 0.05～0.8, is preferably 0.1～0.4; H
2O/SiO
2Mol ratio is 6～40, is preferably 10～22; Si
2O/Al
2O
3Mol ratio 6～30, best 6～15.
The organic bases template is an alkyl ammonium hydroxide, specifically can be selected from tetraethyl ammonium hydroxide, TPAOH and the TBAH one or more.
The silicon source 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 the sodium source derives from sodium aluminate and/or sodium hydroxide.
The zeolite powder that the present invention relates to has the faujusite feature, thereby shows faujusite XRD diffractive features in the XRD spectrum analysis, is exactly the XRD diffractive features that shows the y-type zeolite that belongs to the faujusite class equally furtherly.The product zeolite has higher silica alumina ratio, and has different shape characteristics with existing method synthetic product.
The synthesizing high-silicon faujusite mainly adopts directing agent method (is directed agents with the crystal seed) 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 suitable 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.The faujusite that the inventive method obtains has higher silica alumina ratio, more crystalline degree, lower sodium content and bigger acidity.The inventive method synthetic faujusite has the tabular crystal pattern, helps the diffusion of reaction molecular, improves the selectivity of reaction.
Embodiment
Mixing of materials temperature involved in the present invention is generally room temperature～70 ℃, preferred 40～60 ℃.Hydrothermal crystallization process 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 help obtaining uniform product that also can adopt 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.
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 the aluminium source, and TPAOH 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: 1.8: 1.2: 1: 110.Synthetic method: press the reactant ratio of components, sodium hydroxide and sodium aluminate are joined in the 25% TPAOH solution, add silicon sol after mixing again.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 120h.After crystallization finishes, product is filtered, the washing back obtains 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 sodium aluminate is the aluminium source, and TBAH 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: 3.5: 0.8: 1: 180.Synthetic method: press the reactant ratio of components, sodium hydroxide and sodium aluminate are added in the entry, add again in the 25% TBAH solution, add silicon sol after mixing again.With said mixture 60 ℃ down stir 6 hours after again aged at room temperature 24 hours, move in the autoclave of band tetrafluoroethylene, airtight, at 110 ℃ of static crystallization 180h.After crystallization finishes, product is filtered, the washing back obtains sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
Example 3
With water glass and silicon sol serves as to mix the silicon source, and sodium aluminate is the aluminium source, and tetraethyl ammonium hydroxide 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 16: 4.0: 2.5: 1: 320.Synthetic method: press the reactant ratio of components, in the 35% tetraethyl ammonium hydroxide solution that sodium aluminate is joined, add silicon sol and water glass (the silicon source that both provide is 2: 1) after mixing again.With said mixture 30 ℃ down stir 3 hours after, at room temperature place in the autoclave that moves into the band tetrafluoroethylene after 48 hours, airtight, 120 ℃ of static crystallizations 18 hours, dynamic (200 rev/mins of stirring velocitys) crystallization 54h.After crystallization finishes, product is filtered, the washing back obtains 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 Tai-Ace S 150 and sodium aluminate are aluminium source (the aluminium source that both provide is 1: 2), and tetraethyl ammonium hydroxide 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 25: 8.0: 2.0: 1: 190.Synthetic method: press the reaction mass proportioning, sodium aluminate and Tai-Ace S 150 are joined in the 35% tetraethyl ammonium hydroxide solution, add silicon sol after mixing again.Said mixture after stirring 3 hours under 50 ℃, is at room temperature placed in the autoclave that moves into the band tetrafluoroethylene after 24 hours, airtight, at 110 ℃ of dynamic (200 rev/mins of stirring velocitys) crystallization 72h.After crystallization finishes, product is filtered, the washing back obtains sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
Example 5
With the water glass adhesive is the silicon source, and aluminum chloride and sodium aluminate are aluminium source (the aluminium source that both provide is 2: 1), and tetraethyl ammonium hydroxide 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 32: 10.0: 3.0: 1: 300.Synthetic method: by the material proportion requirement, sodium aluminate is joined in the 35% tetraethyl ammonium hydroxide solution, add silicon sol and aluminum chloride after mixing again successively.Said mixture after stirring 3 hours under 50 ℃, is at room temperature placed in the autoclave that moves into the band tetrafluoroethylene after 24 hours, airtight, at 115 ℃ of crystallization 72h.After crystallization finishes, product is filtered, the washing back obtains sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
Example 6
With the solid silicone is the silicon source, and sodium aluminate is the aluminium source, and tetraethyl ammonium hydroxide 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 45: 12.5: 3.2: 1: 400.Synthetic method: press the reaction mass proportioning, in the 35% tetraethyl ammonium hydroxide solution that sodium aluminate is joined, add silica gel then, descend stirring after 16 hours at 50 ℃ said mixture, at room temperature place in the autoclave that moves into the band tetrafluoroethylene after 24 hours, airtight, at 115 ℃ of static crystallization 36h, then at dynamic (100 rev/mins of stirring velocitys) crystallization 36h.After crystallization finishes, product is filtered, the washing back obtains sample of the present invention at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.
Comparative example 1
Press the US5549881 method.At first prepare crystal seed: ratio of components 12.5 (SiO
2): 13.33 (Na
2O): (Al
2O
3): 267 (H
2O); Process for aluminium hydroxide is joined in the water that is dissolved with sodium hydroxide to sodium aluminate colloidal sol, and then slowly add water glass, supply behind the water vigorous stirring evenly after, place under the room temperature and used in 16 days.
Secondly, be the silicon source with the silicon sol, TBAH is for being template, hydrothermal crystallizing synthesizes zeolite of the present invention, reactant batching mol ratio: n (SiO
2): n (template): n (Na
2O): n (Al
2O
3): n (H
2O)=and 18: 3.6: 1.2: 1: 275.Method: successively 59g sodium hydroxide and 75g aluminium hydroxide are joined in the 100g water, supply water again up to 250g after the heated and stirred dissolving, obtain sodium aluminate solution; In addition, 135g is arrived in 42.5g silicon sol (silica content 40%), 16 days crystal seed of the above-mentioned aged at room temperature of 11.9g, 63.7g TBAH and the above-mentioned sodium aluminate solution 5.17g that obtains, 7.44g alum liquor (50% Tai-Ace S 150 concentration) and moisturizing; 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, 110 ℃ of crystallization difference 120h, 240h under static state.120h crystallization product is unformed, and 240h obtains the crystallization product, and product is filtered, and the washing back obtains sample F at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.The SiO of F
2/ Al
2O
3Mol ratio is 6.5.
Comparative example 2
Press the US5716593 method, the 51.6g sodium aluminate joined in the 150.2g silicon sol to mix stirred 10 minutes, add 11.3g sodium hydroxide and 349.6g tetraethyl ammonium hydroxide then successively and continue to mix stirring 4 hours, add 60g water then and become paste, heating makes that volatile matter loss of weight 50% is that gross weight reduces 230g in the mixture under 66 degree again, put into crucible after the airtight night under the room temperature, again crucible is put into the autoclave that 12ml water is arranged at the bottom, at 110 degree difference crystallization 160h.After crystallization finishes, product is filtered, the washing back obtains comparative sample G at 550 ℃ of roasting removed template methods, the SiO of G then 110 ℃ of dryings
2/ Al
2O
3Mol ratio is 5.2.
Each embodiment product main character of table 1
| Embodiment | Product structure | SiO 2/Al 2O 3Mol ratio |
| 1 | Faujusite | 6.1 |
| 2 | Faujusite | 6.3 |
| 3 | Faujusite | 7.1 |
| 4 | Faujusite | 8.5 |
| 5 | Faujusite | 10.3 |
| 6 | Faujusite | 12.6 |
| Comparative example 1 | Faujusite | 6.5 |
| Comparative example 2 | Faujusite | 5.2 |
Claims (9)
1. the synthetic method of a high silica alumina ratio faujusite comprises following process:
(1) aluminium source, silicon source, sodium source and organic bases 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 24-240h;
(5) will obtain zeolite powder after crystallization product filtration and the drying;
Above-mentioned (1) various raw material molar ratios are: 5～50 SiO
2: 1.5～15Na
2O: Al
2O
3: 0.3～3.5 organic bases template: 60～420H
2O; Na wherein
2O/SiO
2Mol ratio is 0.05～0.8, H
2O/SiO
2Mol ratio is 6～40;
Described organic bases template is selected from one or more in tetraethyl ammonium hydroxide, TPAOH and the TBAH.
2. in accordance with the method for claim 1, it is characterized in that the described hydrothermal crystallizing time is 24～120h.
3. in accordance with the method for claim 1, it is characterized in that silica is 6～15 in described (1) middle mixture, water/alumina molar ratio is 100～180, and organic bases template/alumina molar ratio is 0.8～2.5.
4. in accordance with the method for claim 1, it is characterized in that described Na
2O/SiO
2Mol ratio is 0.1～0.4, H
2O/SiO
2Mol ratio is 10～22.
5. 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 derives from sodium aluminate and/or sodium hydroxide.
6. in accordance with the method for claim 1, it is characterized in that the stirring aging temperature described in (2) is 40 ℃～60 ℃.
7. 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.
8. in accordance with the method for claim 1, 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.
9. in accordance with the method for claim 8, it is characterized in that described is 1: 0.1～10 with static time scale in conjunction with hydrothermal crystallization process dynamically.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100475105A CN100390059C (en) | 2005-10-19 | 2005-10-19 | High silica/ aluminum ratio octagonal zeolite synthesizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100475105A CN100390059C (en) | 2005-10-19 | 2005-10-19 | High silica/ aluminum ratio octagonal zeolite synthesizing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1951812A CN1951812A (en) | 2007-04-25 |
| CN100390059C true CN100390059C (en) | 2008-05-28 |
Family
ID=38058401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100475105A Active CN100390059C (en) | 2005-10-19 | 2005-10-19 | High silica/ aluminum ratio octagonal zeolite synthesizing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100390059C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439168B (en) * | 2014-08-28 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of method for preparing high silica alumina ratio Y type molecular sieve |
| CN104528763A (en) * | 2014-12-17 | 2015-04-22 | 上海大学 | Preparation method of X-type zeolite molecular sieve |
| CN106672996B (en) * | 2015-11-09 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of high-stability nano Y molecular sieve and preparation method thereof |
| CN111825100B (en) * | 2019-04-18 | 2023-10-31 | 中国科学院大连化学物理研究所 | High-silicon Y molecular sieve with FAU topological structure and preparation method thereof |
| EP3957603A4 (en) * | 2019-04-18 | 2022-09-28 | Dalian Institute of Chemical Physics, Chinese Academy of Sciences | High-silica y molecular sieve having fau topology and preparation method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716593A (en) * | 1996-07-31 | 1998-02-10 | Chevron U.S.A. Inc. | Preparation of Y-type faujasite using an organic template |
| CN1388063A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Synthesis of Cr-Si molecular sieve in MFI crystal structure |
-
2005
- 2005-10-19 CN CNB2005100475105A patent/CN100390059C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716593A (en) * | 1996-07-31 | 1998-02-10 | Chevron U.S.A. Inc. | Preparation of Y-type faujasite using an organic template |
| CN1388063A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Synthesis of Cr-Si molecular sieve in MFI crystal structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1951812A (en) | 2007-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107001056B (en) | Mesoporous zeolite is prepared with the processing of reduction | |
| CN100390059C (en) | High silica/ aluminum ratio octagonal zeolite synthesizing method | |
| CN100390060C (en) | High-silica octagonal zeolite and synthesizing method thereof | |
| CN102417190A (en) | Method for preparing low-silicon NaX zeolite by applying activated silicon source | |
| CN106145138A (en) | A kind of synthesis has the method for the zeolite molecular sieve of chabazite structure | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| CN115321555A (en) | Method for synthesizing high-silicon AFX zeolite molecular sieve by using small-molecule organic template agent | |
| CN102441425B (en) | Preparation method for Y/MCM-41 composite molecular sieve | |
| CN102198950B (en) | Method for preparing NaY molecular sieve with high aluminum-silicon ratio | |
| CN1267345C (en) | Preparation method of NaY molecular sieve | |
| CN101190795A (en) | Method for preparing NaY molecular screen by solid-phase conversion | |
| CN100431961C (en) | Octagonal zeolite synthesizing method | |
| CN102180478A (en) | Method for synthesizing Beta molecular sieve by using silica gel under the condition without organic template | |
| JP2001058816A (en) | NaY TYPE ZEOLITE | |
| CN100421795C (en) | Catalytic cracking catalyst containing faujasite and preparation method thereof | |
| CN101723395B (en) | Method for preparing double-micropore composite molecular sieve | |
| CN106946266B (en) | A kind of SAPO-34/ZSM-12 composite molecular screens and its synthetic method | |
| CN106946274B (en) | A kind of Beta/ZSM-12 composite molecular screen and its synthetic method | |
| CN100431960C (en) | Octagonal zeolite synthesizing method | |
| US7968079B2 (en) | Ready-to-use seed composition and process thereof | |
| CN101468802B (en) | Method for synthesizing fine grain NaY molecular sieve | |
| CN106946273B (en) | A kind of EU-1/ZSM-5 composite molecular screen and its synthetic method | |
| CN106946269B (en) | A kind of MCM-22/MOR composite molecular screen and its synthetic method | |
| CN102259890A (en) | ZSM-5/ECR-1/mordenite three-phase symbiotic material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |