CN105621447A - Synthetic method for Na Y type molecular sieve - Google Patents
Synthetic method for Na Y type molecular sieve Download PDFInfo
- Publication number
- CN105621447A CN105621447A CN201410603899.6A CN201410603899A CN105621447A CN 105621447 A CN105621447 A CN 105621447A CN 201410603899 A CN201410603899 A CN 201410603899A CN 105621447 A CN105621447 A CN 105621447A
- Authority
- CN
- China
- Prior art keywords
- accordance
- kaolin
- molecular sieve
- crystallization
- temperature
- 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.)
- Granted
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Paper (AREA)
Abstract
The invention discloses a synthetic method for a Na Y type molecular sieve. The method comprises the following contents: (1) uniformly mixing sodium hydroxide, an aluminum source, water glass and water, and carrying out aging so as to obtain a directing agent; (2) subjecting kaolin materials to hydrothermal treatment so as to obtain modified kaolin; (3) uniformly mixing the directing agent obtained in the step (1), the modified kaolin obtained in the step (2), sodium hydroxide, water and water glass so as to obtain a gel system, and carrying out low-temperature crystallization, high-temperature crystallization, cooling, solid-liquid separation and drying so as to obtain the Na Y type molecular sieve. The method provided by the invention uses hydrothermal modified kaolin as a raw material, and has the characteristics of simple synthetic process, high product crystallinity, good hydrothermal stability, etc.
Description
Technical field
The invention belongs to Zeolite synthesis field, relate in particular to a kind of method synthesizing NaY type molecular sieve.
Background technology
The method generally preparing NaY type molecular sieve is to adopt alkalescence silica-alumina gel system synthesis. The raw material being generally adopted is sodium hydroxide, waterglass, water, aluminum sulfate and sodium metaaluminate, it is eventually adding a certain amount of directed agents, so feature that NaY type molecular sieve has molecular sieve content height, silica alumina ratio is high of synthesis, adopt different method of modifying, modified NaY type molecular sieve can be made to have multiple reaction characteristics.
Kaolin in-situ synthetic method is the important method of NaY type molecular sieve. USP3506594, USP3503900, USP3647718 prepare the method for the in-situ crystallization zeolite of active constituent and substrate with Kaolin for raw material simultaneously, and the FCC catalyst obtained by in-situ crystallization method is called kaolin type catalyst, also known as full clay catalyst. It is active component with the Y type molecular sieve synthesized with gel method, FCC catalyst prepared by semi-synthesizing technology is adopted to compare, it is strong that full clay catalyst has preventing from heavy metal pollution ability, activity index is high, the advantages such as hydrothermal stability, structural stability are good, the adjustable degeneration that shortcoming is active component and substrate is flexible not as semi-synthesis method.
When early stage synthesizes NaY type molecular sieve with Kaolin, generally use metakaolin (hereinafter referred to as soil partially) microsphere. UK1271450 describes and Kaolin roasting below 704 DEG C is become metakaolin, then NaY type molecular sieve is synthesized with sodium silicate etc.; USP3377006 discloses the special thin powder of soil partially of one to synthesize NaY type molecular sieve.
USP3367886, USP3367887, USP3506594, USP3647718, USP3657154, USP3663165, USP3932268 etc. use the silica alumina ratio of NaY type molecular sieve in in-situ crystallization product prepared by 900 DEG C of high temperature above roasting kaolins (hereinafter referred to as high soil) higher, but degree of crystallinity is typically between 20%-30%.
USP4493902 discloses a kind of method simultaneously containing soil, high soil and crystal seed synthesis high zeolite content crystallization product partially in same microsphere, crystallization product degree of crystallinity is higher than 40%, but the method is significantly high to the ingredient requirement used by spray shaping, use super-refinement height soil and super-refinement original soil ASP ~ 600, this ultra-fine soil is expensive, and not easily buys on market.
In said method, the synthesis of NaY type molecular sieve is all at Kaolin spray shaping, carries out after becoming microsphere, and the NaY type molecular sieve crystallinity of preparation is low, modulation very flexible.
Summary of the invention
The features such as the deficiencies in the prior art, the present invention provides a kind of method synthesizing NaY type molecular sieve, and the method is with the Kaolin of hydrothermal modification for raw material, and building-up process is simple, and product degree of crystallinity is high and hydrothermally stable is good.
The method of the synthesis NaY type molecular sieve of the present invention, including following content: (1), by sodium hydroxide, aluminum source, waterglass and water mix homogeneously, ageing, obtains directed agents; (2) kaolin starting material is carried out the modified kaolin that hydrothermal treatment consists obtains; (3) step (1) is obtained directed agents, modified kaolin, sodium hydroxide, water and waterglass mix homogeneously that step (2) obtains, obtain gel rubber system, then through low temperature crystallized, high temperature crystallization, cooling, solid-liquid separation and dry, obtain NaY type molecular sieve.
In the inventive method, the aluminum source described in step (1) is one or more in aluminum chloride, aluminum sulfate, aluminum nitrate or sodium aluminate, it is preferable that sodium aluminate.
In the inventive method, the mol ratio that the material described in step (1) is counted with following material is for Na2O:Al2O3:SiO2:H2O=15~20:1:15~22:300~400��
In the inventive method, the aging condition described in step (1) is: Aging Temperature is 50 ~ 110 DEG C, it is preferable that 60 ~ 110 DEG C, and digestion time is 1 ~ 24 hour, it is preferable that 2 ~ 12 hours.
In the inventive method, the hydrothermal conditions described in step (2) is: hydrothermal treatment consists temperature is 500 ~ 850 DEG C, it is preferable that 600 ~ 800 DEG C, and hydrothermal conditions is 1 ~ 8 hour, it is preferable that 2 ~ 6 hours, and hydrothermal treatment consists pressure is 0 ~ 0.5MPa, it is preferable that 0.05 ~ 0.3MPa; Carrying out when above-mentioned hydrothermal treatment process is preferably in water filling, wherein water injection rate is 20 ~ 800ml/h, it is preferable that 50 ~ 600ml/h.
In the inventive method, the kaolin starting material described in step (2) is commercially available prod, has the property that silica alumina ratio (described silica alumina ratio is the mol ratio of silicon oxide and aluminium oxide, lower with) is 1.8 ~ 2.6, it is preferable that 2.1 ~ 2.4; Potassium oxide and sodium oxide total content are less than 0.8wt%, it is preferable that less than 0.6wt%.
In the inventive method, the mol ratio that in step (3) gel rubber system, each material is counted with following material is (wherein not including the modified kaolin and the directed agents that add): NaOH:SiO2:H2O=14 ~ 17:8 ~ 18:450 ~ 700, it is preferable that NaOH:SiO2:H2O=14.5~16.5:10~16:480~680��
In the inventive method, the quality of the modified kaolin added in step (3) accounts for the 2wt% ~ 14wt% of gel rubber system gross mass, it is preferable that 4wt% ~ 12wt%.
In the inventive method, the quality of the directed agents added in step (3) accounts for the 1wt% ~ 10wt% of gel rubber system gross mass, it is preferable that 3wt% ~ 8wt%.
In the inventive method, the low temperature crystallized condition described in step (3) is: crystallization temperature is 50 ~ 80 DEG C, it is preferable that 60 ~ 70 DEG C, and crystallization time is 4 ~ 24 hours, it is preferable that 8 ~ 12 hours.
In the inventive method, the high temperature crystallization condition described in step (3) is: crystallization temperature is 85 ~ 120 DEG C, it is preferable that 90 ~ 110 DEG C, and crystallization time is 12 ~ 72 hours, it is preferable that 24 ~ 60 hours.
In the inventive method, the baking temperature described in step (3) is 80 ~ 100 DEG C, and drying time is 8 ~ 16 hours.
The inventive method modifiies by Kaolin carries out hydrothermal treatment consists, then utilizes the NaY type molecular sieve of modified kaolin fabricated in situ high-crystallinity. In the inventive method, the connecting key of the silicon oxide in the kaolin component in protokaolin Yu aluminium oxide is opened by kaolinic hydrothermal treatment process completely, making Kaolin be fully converted to unformed silicon oxide and aluminium oxide, the NaY type molecular sieve for synthesizing high-crystallinity lays the foundation. The chemical bond of oxidation sial can not be fully opened by tradition by the method for high-temperature roasting active oxidation silicon and aluminium oxide, and the molecular sieve defect making preparation is more, and in molecular sieve modified process, in hydrothermal treatment process, stability is not high. Relative to traditional method, the present invention utilize hydrothermal treatment consists after the NaY type molecular sieve prepared of Kaolin have that degree of crystallinity is high and the feature of good hydrothermal stability.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction spectrogram of the embodiment of the present invention 6 sintetics.
Detailed description of the invention
Further illustrate the preparation process of the present invention below in conjunction with embodiment, but and be not so limited the present invention.
Embodiment 1
500g Kaolin incubation water heating under 600 DEG C of conditions is processed 3h, and hydrothermal treatment consists pressure is 0.3MPa, and water injection rate is 100ml/h, obtains modified kaolin 1. Kaolinic silica alumina ratio is 2.2, and potassium oxide and sodium oxide total content are 0.58wt%.
Embodiment 2
500g Kaolin incubation water heating under 650 DEG C of conditions is processed 2h, and hydrothermal treatment consists pressure is 0.1MPa, obtains modified kaolin 2. Kaolinic silica alumina ratio is 2.3, and potassium oxide and sodium oxide total content are 0.52wt%.
Embodiment 3
500g Kaolin incubation water heating under 700 DEG C of conditions is processed 5h, and hydrothermal treatment consists pressure is 0.2MPa, and water injection rate is 400ml/h, obtains modified kaolin 3. Kaolinic silica alumina ratio is 2.1, and potassium oxide and sodium oxide total content are 0.56wt%.
Embodiment 4
500g Kaolin incubation water heating under 750 DEG C of conditions is processed 4h, and hydrothermal treatment consists pressure is 0.2MPa, and water injection rate is 300ml/h, obtains modified kaolin 4. Kaolinic silica alumina ratio is 2.3, and potassium oxide and sodium oxide total content are 0.50wt%.
Embodiment 5
(1) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=18:1:16:360, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 2 days at 35 DEG C, prepare directed agents.
(2) when stirring, the directed agents that modified kaolin 1, sodium hydroxide, water, waterglass and step (1) prepare is joined formation gel rubber system in beaker, by first for gel thermostatic crystallization 12 hours under 60 DEG C of conditions, then thermostatic crystallization 60 hours under 95 DEG C of conditions, then cooled, washing, sucking filtration, then at 100 DEG C, after dry 12 hours, NaY type molecular sieve is obtained. In gel rubber system, the mol ratio of (modified kaolin of removing addition and directed agents) each material isn(NaOH):n(SiO2):n(H2O)=15.5:12:570, the quality of the modified kaolin of addition accounts for the 6wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 5wt% of gel rubber system gross mass.
Embodiment 6
(1) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:18:320, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(2) when stirring, the directed agents that modified kaolin 2, sodium hydroxide, water, waterglass and step (1) prepare is joined formation gel rubber system in beaker, by first for gel thermostatic crystallization 10 hours under 60 DEG C of conditions, then thermostatic crystallization 48 hours under 100 DEG C of conditions, then cooled, washing, sucking filtration, then at 90 DEG C, after dry 10 hours, NaY type molecular sieve is obtained. In gel rubber system, the mol ratio of (modified kaolin of removing addition and directed agents) each material isn(NaOH):n(SiO2):n(H2O)=15:13:620, the quality of the modified kaolin of addition accounts for the 5wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 4wt% of gel rubber system gross mass.
Embodiment 7
(1) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:20:380, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(2) when stirring, the directed agents that modified kaolin 3, sodium hydroxide, water, waterglass and step (1) prepare is joined formation gel rubber system in beaker, by first for gel thermostatic crystallization 10 hours under 65 DEG C of conditions, then thermostatic crystallization 36 hours under 105 DEG C of conditions, then cooled, washing, sucking filtration, then at 80 DEG C, after dry 16 hours, NaY type molecular sieve is obtained. In gel rubber system, the mol ratio of (modified kaolin of removing addition and directed agents) each material isn(NaOH):n(SiO2):n(H2O)=15.6:12:520, the quality of the modified kaolin of addition accounts for the 5wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 7wt% of gel rubber system gross mass. The character of molecular sieve is as shown in table 1.
Embodiment 8
(1) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=17:1:17:400, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(2) when stirring, the directed agents that modified kaolin 4, sodium hydroxide, water, waterglass and step (1) prepare is joined formation gel rubber system in beaker, by first for gel thermostatic crystallization 9 hours under 68 DEG C of conditions, then thermostatic crystallization 52 hours under 95 DEG C of conditions, then cooled, washing, sucking filtration, then at 100 DEG C, after dry 8 hours, NaY type molecular sieve is obtained. In gel rubber system, the mol ratio of (modified kaolin of removing addition and directed agents) each material isn(NaOH):n(SiO2):n(H2O)=15.8:13:500, the quality of the modified kaolin of addition accounts for the 10wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 8wt% of gel rubber system gross mass.
Comparative example 1
(1) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:20:380, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(2) when stirring, the directed agents that the Kaolin of roasting, sodium hydroxide, water, waterglass and step (1) prepare is joined formation gel rubber system in beaker, by first for gel thermostatic crystallization 10 hours under 65 DEG C of conditions, then thermostatic crystallization 36 hours under 105 DEG C of conditions, then cooled, washing, sucking filtration, then at 80 DEG C, after dry 16 hours, NaY type molecular sieve is obtained. In gel rubber system, the mol ratio of (roasting kaolin of removing addition and directed agents) each material isn(NaOH):n(SiO2):n(H2O)=15.6:12:520, the quality of the roasting kaolin of addition accounts for the 5wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 7wt% of gel rubber system gross mass. Roasting kaolin is Kaolin constant temperature calcining 5h under 700 DEG C of conditions. The character of molecular sieve is as shown in table 1.
Hydrothermal stability is investigated
NaY type molecular sieve embodiment 7 and comparative example 1 prepared carries out secondary ammonium exchange. Exchange temperature is 95 DEG C; Ammonium salt used is ammonium nitrate, and the concentration of ammonium salt is 2mol/L; The liquid-solid ratio (ml/g) of exchange process is 8; Each swap time is 1.5 hours.
The molecular sieve exchanged by ammonium processes under hydrothermal conditions. Hydrothermal treatment consists temperature is at 600 DEG C; Hydrothermal conditions is 3 hours; Hydrothermal treatment consists pressure is 0.2MPa; Hydrothermal treatment process water injection rate is 200ml/h.
The character of the molecular sieve after hydrothermal treatment consists is as shown in table 1.
The physico-chemical property of table 1 molecular sieve.
The property data of molecular sieve shows, after molecular sieve being carried out hydrothermal treatment consists through identical hydrothermal conditions, the destructiveness of molecular sieve prepared by the inventive method is less, remains more crystal structure, and degree of crystallinity is higher. Absolutely prove that the hydrothermal stability of molecular sieve prepared by the inventive method is better.
Claims (15)
1. the method synthesizing NaY type molecular sieve, it is characterised in that include following content: (1), by sodium hydroxide, aluminum source, waterglass and water mix homogeneously, ageing, obtains directed agents; (2) kaolin starting material is carried out the modified kaolin that hydrothermal treatment consists obtains; (3) step (1) is obtained directed agents, modified kaolin, sodium hydroxide, water and waterglass mix homogeneously that step (2) obtains, obtain gel rubber system, then through low temperature crystallized, high temperature crystallization, cooling, solid-liquid separation and dry, obtain NaY type molecular sieve.
2. in accordance with the method for claim 1, it is characterised in that: the aluminum source described in step (1) is one or more in aluminum chloride, aluminum sulfate, aluminum nitrate or sodium aluminate.
3. in accordance with the method for claim 1, it is characterised in that: the mol ratio that the material described in step (1) is counted with following material is for Na2O:Al2O3:SiO2:H2O=15~20:1:15~22:300~400��
4. in accordance with the method for claim 1, it is characterised in that: the aging condition described in step (1) is: Aging Temperature is 50 ~ 110 DEG C, and digestion time is 1 ~ 24 hour.
5. in accordance with the method for claim 1, it is characterised in that: the hydrothermal conditions described in step (2) is: hydrothermal treatment consists temperature is 500 ~ 850 DEG C, and hydrothermal conditions is 1 ~ 8 hour, and hydrothermal treatment consists pressure is 0 ~ 0.5MPa.
6. in accordance with the method for claim 1, it is characterised in that: the hydrothermal conditions described in step (2) is: hydrothermal treatment consists temperature is 600 ~ 800 DEG C, and hydrothermal conditions is 2 ~ 6 hours, and hydrothermal treatment consists pressure is 0.05 ~ 0.3MPa.
7. the method described in claim 5 or 6, it is characterised in that: hydrothermal treatment process carries out when water filling, and wherein water injection rate is 20 ~ 800ml/h.
8. in accordance with the method for claim 1, it is characterised in that: the kaolin starting material described in step (2) is commercially available prod, has the property that the mol ratio of silicon oxide and aluminium oxide is 1.8 ~ 2.6, and potassium oxide and sodium oxide total content are less than 0.8wt%.
9. in accordance with the method for claim 1, it is characterised in that: the mol ratio that in step (3) gel rubber system, each material is counted with following material for, wherein do not include the modified kaolin and directed agents: the NaOH:SiO that add2:H2O=14~17:8~18:450~700��
10. the method described in claim 1 or 9, it is characterised in that: the mol ratio that in step (3) gel rubber system, each material is counted with following material for, wherein do not include the modified kaolin and directed agents: the NaOH:SiO that add2:H2O=14.5~16.5:10~16:480~680��
11. in accordance with the method for claim 1, it is characterised in that: the quality of the modified kaolin added in step (3) accounts for the 2wt% ~ 14wt% of gel rubber system gross mass.
12. in accordance with the method for claim 1, it is characterised in that: the quality of the directed agents added in step (3) accounts for the 1wt% ~ 10wt% of gel rubber system gross mass.
13. in accordance with the method for claim 1, it is characterised in that: the low temperature crystallized condition described in step (3) is: crystallization temperature is 50 ~ 80 DEG C, and crystallization time is 4 ~ 24 hours.
14. in accordance with the method for claim 1, it is characterised in that: the high temperature crystallization condition described in step (3) is: crystallization temperature is 85 ~ 120 DEG C, and crystallization time is 12 ~ 72 hours.
15. in accordance with the method for claim 1, it is characterised in that: the baking temperature described in step (3) is 80 ~ 100 DEG C, and drying time is 8 ~ 16 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410603899.6A CN105621447B (en) | 2014-11-03 | 2014-11-03 | A kind of method of synthesis NaY type molecular sieves |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410603899.6A CN105621447B (en) | 2014-11-03 | 2014-11-03 | A kind of method of synthesis NaY type molecular sieves |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105621447A true CN105621447A (en) | 2016-06-01 |
| CN105621447B CN105621447B (en) | 2017-07-28 |
Family
ID=56036855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410603899.6A Active CN105621447B (en) | 2014-11-03 | 2014-11-03 | A kind of method of synthesis NaY type molecular sieves |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105621447B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195169A (en) * | 2021-12-31 | 2022-03-18 | 武汉智宏思博环保科技有限公司 | Method for synthesizing NaY molecular sieve by microwave method and hydrothermal method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3506594A (en) * | 1968-06-20 | 1970-04-14 | Engelhard Min & Chem | Microspherical zeolitic molecular sieve composite catalyst and preparation thereof |
| CN1334142A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
| US6350429B1 (en) * | 1997-09-29 | 2002-02-26 | Abb Lummus Global Inc. | Method for making molecular sieves and novel molecular sieve compositions |
| CN101618882A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for in-situ synthesis of Y-type molecular sieve |
| CN102764670A (en) * | 2012-07-31 | 2012-11-07 | 海南出入境检验检疫局检验检疫技术中心 | In-situ crystallization cracking catalyst prepared by polymorph kaolin microspheres and preparation method of in-situ crystallization cracking catalyst |
-
2014
- 2014-11-03 CN CN201410603899.6A patent/CN105621447B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3506594A (en) * | 1968-06-20 | 1970-04-14 | Engelhard Min & Chem | Microspherical zeolitic molecular sieve composite catalyst and preparation thereof |
| US6350429B1 (en) * | 1997-09-29 | 2002-02-26 | Abb Lummus Global Inc. | Method for making molecular sieves and novel molecular sieve compositions |
| CN1334142A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
| CN101618882A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for in-situ synthesis of Y-type molecular sieve |
| CN102764670A (en) * | 2012-07-31 | 2012-11-07 | 海南出入境检验检疫局检验检疫技术中心 | In-situ crystallization cracking catalyst prepared by polymorph kaolin microspheres and preparation method of in-situ crystallization cracking catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195169A (en) * | 2021-12-31 | 2022-03-18 | 武汉智宏思博环保科技有限公司 | Method for synthesizing NaY molecular sieve by microwave method and hydrothermal method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105621447B (en) | 2017-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101249968B (en) | Method for synthesizing Beta molecular sieve by organic-free template | |
| TWI490167B (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
| CN105728019B (en) | A kind of preparation method and application of the ZSM-5 molecular sieve with Jie's micropore | |
| CN106348312B (en) | A kind of synthesis methods for inorganic compounds of regulation and control ZSM-5 molecular sieve pattern | |
| CN103043680A (en) | NaY molecular sieve/natural mineral composite material having multistage pore structure and preparation method thereof | |
| CN104692412A (en) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve | |
| CN105000574B (en) | HZSM-5 molecular sieve with special appearance and preparation method and application thereof | |
| CN110217804B (en) | ZSM-5 molecular sieve and preparation method thereof, hydrogen type ZSM-5 molecular sieve and application thereof, and methanol conversion method | |
| CN108264054B (en) | Method for synthesizing silicon-rich ZSM-22 zeolite molecular sieve by adopting seed crystal guiding method | |
| CN102050466B (en) | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material | |
| CN106315612B (en) | A kind of preparation method of low silica-alumina ratio X-type molecular sieve | |
| US20200071174A1 (en) | Methods for Synthesizing Mesoporous Zeolite ETS-10 Containing Metal Without a Templating Agent | |
| CN105621447A (en) | Synthetic method for Na Y type molecular sieve | |
| CN105084388B (en) | Method for preparing and modifying Y-type molecular sieve | |
| CN102259890B (en) | ZSM-5/ECR-1/mordenite three-phase symbiotic material and preparation method thereof | |
| CN101514008B (en) | Mordenite/Y zeolite coexisting molecular sieve and method for synthesizing same | |
| CN102050465B (en) | Method for preparing Y-type molecular sieve through solid-phase in-situ synthesis | |
| CN103073023B (en) | Method for preparing 13X zeolite molecular sieve by kaolin containing illite | |
| CN111186846B (en) | ITH structure silicon-aluminum molecular sieve and preparation method thereof | |
| CN104649290B (en) | Organic-template-free [beta]-molecular sieve synthesizing method | |
| JP2021526118A (en) | Method for producing ZSM-5 zeolite | |
| CN102452659B (en) | Preparation method of MCM-22 zeolite | |
| CN105621448A (en) | Preparation method of small-grain NaY type molecular sieve | |
| CN105712369A (en) | Modified Y type molecular sieve and preparation method thereof | |
| CN106946269B (en) | A kind of MCM-22/MOR composite molecular screen and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |