CN1736867A - Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould - Google Patents
Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould Download PDFInfo
- Publication number
- CN1736867A CN1736867A CN 200510028315 CN200510028315A CN1736867A CN 1736867 A CN1736867 A CN 1736867A CN 200510028315 CN200510028315 CN 200510028315 CN 200510028315 A CN200510028315 A CN 200510028315A CN 1736867 A CN1736867 A CN 1736867A
- Authority
- CN
- China
- Prior art keywords
- weight
- msu
- parts
- molecular sieve
- water
- 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
Abstract
The method for MSU-S-Y mesic molecular sieve belongs to inorganic chemistry synthesis technique field. Wherein, using ion liquid of first-cetyl-third-methyl brominated imidazole or opposite pyridine as template agent, sodium silicate as silicon source and sodium aluminate as aluminium source; preparing the nano prodromal body, assembling the said sieve, hydrothermal crystallizing; filtering, clearing, drying and baking; finally, obtaining the said product. The process is simple, and the product has great special surface, and well hydrothermal stability.
Description
Technical field
The present invention relates to a kind of is the method that template prepares the MSU-S-Y mesopore molecular sieve with the ionic liquid, belongs to inorganic chemical synthesis technical field.
Background technology
1992, the people such as Kresege of Mobil research and development company are at Nature, 1992, the last reported first of 359:710 with tensio-active agent---the chain alkyl trimethyl quaternary ammonium salt is a template, synthetic mesoporous silicate and silico-aluminate under alkaline condition with single aperture, its structure is a long-range order, and specific surface is at 700m
2More than/the g (J.Am.Chem.Soc., 1992,114:10834).This material family is called as M41S, and it comprises hexagonal system (Hexagonal) MCM-41, isometric system (Cubic) MCM-48 and laminate structure (Lamellar) MCM-50.Mesopore molecular sieve MCM-41 has the one-dimensional tunnel structure of hexagonal array, and its aperture can be by the length of the chain alkyl of chain alkyl trimethyl quaternary ammonium salt or by add-on modulation between 1.8～10nm of auxiliary agent such as 1.Have the specific surface height, the big mesopore molecular sieve MCM-41 in aperture can be used as catalyzer, sorbent material or support of the catalyst etc., in the chemical reaction that heavy oil upgrading and macromole are participated in, have broad application prospects especially.The MCM-41 of pure silicon does not have tart, lacks active ingredient in the lattice, and ion-exchange capacity is little, possesses the ability of catalyzed reaction hardly.Therefore, be necessary to study method to its modification.Directly introducing other heteroatomss in the process of synthetic MCM-41 is one of directions of it being carried out modification.When the doped with Al atomic time, the Si in the MCM-41 skeleton is just replaced by Al, generates Al-MCM-41.Tervalent Al four-coordination in skeleton produces Al-O (H)-Si bridge, forms the Lewis acid sites easily.(Applied Catalysis A：General，1999，184：49)。
But, because the hole wall of MCM-41 is in unformed state, cause its hydrothermal stability lower, be difficult to satisfy the requirement of Industrial Catalysis process.Therefore, synthetic high hydrothermal stability also has the mesopore molecular sieve of strong acid center, becomes the research focus in catalytic material field over past ten years.Chinese scholars has been carried out a large amount of research, and has proposed the method for various raising mesopore molecular sieve hydrothermal stabilities.In recent years, people utilize different tensio-active agents to synthesize many different mesopore molecular sieves, as being template synthetic M41S series with long chain alkyl ammonium salt/base cations, bromo chain alkyl pyridine tensio-active agent, with the long-chain primary amine is template synthetic HMS series, with polyoxyethylene groups ethers nonionogenic tenside is template synthetic MSU-X series, and is template synthetic MSU-V, MSU-G etc. with diamines type nonionogenic tenside.
It is that poromerics is made up of the primary and secondary structure elementary cell of zeolite that micro porous molecular sieve has one of reason of strongly-acid and high hydrothermal stability.If at first synthesize sial nano-cluster with molecular sieve primary and secondary structural unit, utilize these nano-clusters and micella template to carry out self-assembly then, just might prepare regular mesoporous silicon aluminum molecular screen material with strong acid center and high hydrothermal stability.
LiuYu etc. utilize the nano-cluster of y-type zeolite, carry out self-assembly with cetyl trimethylammonium bromide as template, and for preparing has a meso-porous molecular sieve material Al-MSU-S that six sides arrange, 800 ℃, contain the N of 20% water vapour
2After handling 5h in the gas, still keep good hexagonal structure, and the material hole structure of traditional method preparation collapses all almost.They also adopt the crystal seed of β zeolite and ZSM-5 and cetyl trimethylammonium bromide to interact, and have prepared to have very the mesopore molecular sieve MSU-S (Beta) and the MSU-S (MFI) of high hydrothermal stability.
Xiao of Jilin University has a good harvest etc. by at first preparing the sial nano-cluster with β zeolite primary and secondary basic structural unit, utilize these nano-clusters and the self-assembly of cetyl trimethylammonium bromide micella again, obtained to have the MAS-5 molecular sieve of regular mesopore, its strength of acid is similar to the β zeolite, and the quantity in B acid site is far longer than MCM-41.They also utilize the directed agents of β zeolite and directed agents and the triblock copolymer self-assembly under strong acidic condition of ZSM-5 respectively, have prepared the hydrothermal stability height and have had highly acid MAS-7 and MAS-9.
Summary of the invention
The purpose of this invention is to provide a kind of is the method that template prepares the MSU-S-Y mesopore molecular sieve with the ionic liquid, and this method has following advantage: preparation process is simple, and the MSU-S-Y mesopore molecular sieve specific surface, aperture, the pore volume that make are big, good hydrothermal stability.
The technical solution used in the present invention is characterised in that: with ionic liquid 1-hexadecyl-3-methyl bromination imidazoles or 1-hexadecyl-3-methyl pyridinium bromide is template, with the water glass is the silicon source, sodium aluminate is the aluminium source, through the preparation of Y zeolite nanometer presoma, the assembling and three steps of hydrothermal crystallizing of mesopore molecular sieve, again through filtration, washing, drying and the roasting of routine, obtain product, the MSU-S-Y mesopore molecular sieve.
Technical scheme of the present invention now is described in detail in detail.A kind of is the method that template prepares the MSU-S-Y mesopore molecular sieve with the ionic liquid, it is characterized in that, be template with ionic liquid 1-hexadecyl-3-methyl bromination imidazoles or 1-hexadecyl-3-methyl pyridinium bromide, is the silicon source with the water glass, sodium aluminate is the aluminium source, operation steps:
The preparation of the first step Y zeolite nanometer presoma
In room temperature with under stirring, the drips of solution of the water of the water glass of 25.5 parts of weight and 26.0 parts of weight is added in the solution that the water of the sodium aluminate of the sodium hydroxide of 0.35 part of weight, 0.21～1.64 part of weight and 16.0 parts of weight forms, drip the back and stir 1～3h, be warmed up to 80～100 ℃, stir 8～12h, get the Y zeolite nanometer presoma of 68.06～69.49 parts of weight;
The assembling of the second step mesopore molecular sieve
In room temperature with under stirring, the Y zeolite nanometer presoma that the first step is made is added drop-wise in the solution of water of the 1-hexadecyl-3-methyl bromination imidazoles of 6.0～9.0 parts of weight or 1-hexadecyl-3-methyl pyridinium bromide and 120～240 parts of weight, 10～25% sulfuric acid is transferred pH=9.0～11.5 of this solution, stir 1～3h, leave standstill;
The 3rd step hydrothermal crystallizing
The mixture that second step was made places autoclave, in 80～100 ℃ of hydrothermal crystallizing 20～30h, the reactant that crystallization is good obtains solid after filtration, deionized water wash, drying gets former powder, 500～550 ℃ of following roasting 5～7h, get the product of 3.2～4.8 parts of weight, the MSU-S-Y mesopore molecular sieve.
Compare with background technology, advantage of the present invention is: preparation process is simple, and the product MSU-S-Y mesopore molecular sieve specific surface, aperture, the pore volume that make are big, good hydrothermal stability.
Description of drawings
The XRD spectra of the MSU-S-Y mesopore molecular sieve that Fig. 1 makes for embodiment 1.
Embodiment
All embodiment operate according to the operation steps of above-mentioned MSU-S-Y method for preparing medium pore molecular sieve.
Embodiment 1
In the first step, the drips of solution of 25.5g water glass and 26.0g water is added in the solution that 0.35g sodium hydroxide, 0.82g sodium aluminate and 16.0g water forms, stirs 1h, 80 ℃ are stirred 12h, the Y zeolite nanometer presoma of 69.0g.In second step, the Y zeolite presoma that the first step is made is added drop-wise in the solution of 8.0g 1-hexadecyl-3-methyl bromination imidazoles and 160g water, and 10% sulfuric acid is transferred the pH=9.0 of this solution.In the 3rd step, 80 ℃ of hydrothermal crystallizing 30h, 500 ℃ of roasting 7h get the 4.1g product, the MSU-S-Y mesopore molecular sieve.
The XRD spectra of the MSU-S-Y mesopore molecular sieve that obtains is seen Fig. 1.XRD determining is to carry out on German Bruker axs type X-ray diffractometer, adopts CuK.From XRD spectra as can be known, about 2 θ=2 °, very strong (a 100) crystal face diffraction peak is arranged, between 3～6 °, also can be observed 3 weak peaks.This has just confirmed that the synthetic sample is a hexagonal system under this suitable condition, and more complete structure is arranged.
The XRD spectra of the MSU-S-Y mesopore molecular sieve that obtains and the XRD spectra of MSU-S are similar.
The specific surface of the MSU-S-Y mesopore molecular sieve that obtains, aperture, pore volume are measured with BET (0210-KR-1), the results are shown in Table 1.
Embodiment 2
In the first step, the drips of solution of 25.5g water glass and 26.0g water is added in the solution that 0.35g sodium hydroxide, 0.21g sodium aluminate and 16.0g water forms, stirs 2h, 90 ℃ are stirred 10h, the Y zeolite nanometer presoma of 68.06g.In second step, the Y zeolite presoma that the first step is made is added drop-wise in the solution of 6.0g 1-hexadecyl-3-methyl bromination imidazoles and 120g water, and 15% sulfuric acid is transferred the pH=10.5 of this solution.In the 3rd step, 90 ℃ of hydrothermal crystallizing 24h, 540 ℃ of roasting 5h get the 3.2g product, the MSU-S-Y mesopore molecular sieve.
The XRD spectra of the MSU-S-Y mesopore molecular sieve that obtains and XRD spectra shown in Figure 1 are similar.
Embodiment 3
In the first step, the drips of solution of 25.5g water glass and 26.0g water is added in the solution that 0.35g sodium hydroxide, 1.64g sodium aluminate and 16.0g water forms, stirs 3h, 100 ℃ are stirred 8h, the Y zeolite nanometer presoma of 69.49g.In second step, the Y zeolite presoma that the first step is made is added drop-wise in the solution of 69.49g 1-hexadecyl-3-methyl bromination imidazoles and 240g water, and 25% sulfuric acid is transferred the pH=11.5 of this solution.In the 3rd step, 100 ℃ of hydrothermal crystallizing 20h, 540 ℃ of roasting 5h get the 4.8g product, the MSU-S-Y mesopore molecular sieve.
The XRD spectra of the MSU-S-Y mesopore molecular sieve that obtains and XRD spectra shown in Figure 1 are similar.
Embodiment 4
The implementation process of present embodiment except for the following differences, all the other are with embodiment 1.
In second step, ionic liquid is 1-hexadecyl-3-methyl pyridinium bromide, and consumption is 8.0g.
In the 3rd step, get the 4.2g product, the MSU-S-Y mesopore molecular sieve.
The XRD spectra of the MSU-S-Y mesopore molecular sieve that obtains and XRD spectra shown in Figure 1 are similar.
The specific surface of MSU-S-Y mesopore molecular sieve, aperture, pore volume the results are shown in Table 1.
Table 1
| Embodiment | Specific surface (m 2/g) | Aperture (nm) | Pore volume (m 3/g) |
| 1 | 996 | 2.9 | 1.148 |
| 4 | 1085 | 2.8 | 1.114 |
| Traditional method | 761 | 2.4 | 0.5965 |
Claims (1)
1, a kind of is the method that template prepares the MSU-S-Y mesopore molecular sieve with the ionic liquid, it is characterized in that, be template with ionic liquid 1-hexadecyl-3-methyl bromination imidazoles or 1-hexadecyl-3-methyl pyridinium bromide, is the silicon source with the water glass, sodium aluminate is the aluminium source, operation steps:
The preparation of the first step Y zeolite nanometer presoma
In room temperature with under stirring, the drips of solution of the water of the water glass of 25.5 parts of weight and 26.0 parts of weight is added in the solution that the water of the sodium aluminate of the sodium hydroxide of 0.35 part of weight, 0.21～1.64 part of weight and 16.0 parts of weight forms, drip the back and stir 1～3h, be warmed up to 80～100 ℃, stir 8～12h, get the Y zeolite nanometer presoma of 68.06～69.49 parts of weight;
The assembling of the second step mesopore molecular sieve
In room temperature with under stirring, the Y zeolite nanometer presoma that the first step is made is added drop-wise in the solution of water of the 1-hexadecyl-3-methyl bromination imidazoles of 6.0～9.0 parts of weight or 1-hexadecyl-3-methyl pyridinium bromide and 120～240 parts of weight, 10～25% sulfuric acid is transferred pH=9.0～11.5 of this solution, stir 1～3h, leave standstill;
The 3rd step hydrothermal crystallizing
The mixture that second step was made places autoclave, in 80～100 ℃ of hydrothermal crystallizing 20～30h, the reactant that crystallization is good obtains solid after filtration, deionized water wash, drying gets former powder, 500～550 ℃ of following roasting 5～7h, get the product of 3.2～4.8 parts of weight, the MSU-S-Y mesopore molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100283158A CN1304290C (en) | 2005-07-29 | 2005-07-29 | Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100283158A CN1304290C (en) | 2005-07-29 | 2005-07-29 | Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1736867A true CN1736867A (en) | 2006-02-22 |
| CN1304290C CN1304290C (en) | 2007-03-14 |
Family
ID=36079857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100283158A Expired - Fee Related CN1304290C (en) | 2005-07-29 | 2005-07-29 | Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1304290C (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400419C (en) * | 2006-10-24 | 2008-07-09 | 南开大学 | Process for synthesizing nano zirconium-containing super micro porous molecular sieve using ionic liquid as template agent |
| CN101767796B (en) * | 2009-01-07 | 2011-07-20 | 中国石油化工股份有限公司 | Preparation method of pure silicon MSU molecular sieve |
| CN102936018A (en) * | 2012-10-07 | 2013-02-20 | 青岛科技大学 | Preparation method for high stability mesoporous molecular sieve under ionothermal system |
| CN104445243A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for synthesizing MSU molecular sieve |
| WO2015085462A1 (en) | 2013-12-09 | 2015-06-18 | 中国科学院大连化学物理研究所 | Method for preparing nay molecular sieve of high silica-alumina ratio and product thereof |
| EP2417061A4 (en) * | 2009-04-09 | 2016-04-20 | California Inst Of Techn | Molecular sieves and related methods and structure directing agents |
| CN105642334A (en) * | 2016-01-29 | 2016-06-08 | 山东多友科技有限公司 | Catalytic cracking catalyst for blending tight oil and preparing method thereof |
| CN106589457A (en) * | 2016-12-16 | 2017-04-26 | 衢州普信新材料有限公司 | Phosphorus-nitrogen type flame retardant containing synergist |
| CN106633185A (en) * | 2016-12-20 | 2017-05-10 | 衢州普信新材料有限公司 | Preparation method of organosilicone-modified phosphorus-nitrogen fire retardant |
| US9738538B2 (en) | 2013-12-09 | 2017-08-22 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing NaY molecular sieve of high silica-alumina ratio and product thereof |
| CN104692413B (en) * | 2013-12-09 | 2017-12-15 | 中国科学院大连化学物理研究所 | A kind of method of NaY molecular sieve for preparing high silica alumina ratio and products thereof |
| CN108298549A (en) * | 2018-02-05 | 2018-07-20 | 南通龙翔新材料科技股份有限公司 | A kind of preparation method aoxidizing sial with ionic liquid one-step synthesis method composite mesopore |
| CN109647365A (en) * | 2017-10-12 | 2019-04-19 | 中国石油天然气股份有限公司 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
| CN109650422A (en) * | 2017-10-12 | 2019-04-19 | 中国石油天然气股份有限公司 | A method of improving mesoporous aluminum oxide material hydrothermal stability |
| CN111825101A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院大连化学物理研究所 | High-silicon Y molecular sieve and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257839C (en) * | 2004-09-16 | 2006-05-31 | 华东师范大学 | Process of preparing mesoporous molecular sieve with ionic liquid as template agent |
-
2005
- 2005-07-29 CN CNB2005100283158A patent/CN1304290C/en not_active Expired - Fee Related
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400419C (en) * | 2006-10-24 | 2008-07-09 | 南开大学 | Process for synthesizing nano zirconium-containing super micro porous molecular sieve using ionic liquid as template agent |
| CN101767796B (en) * | 2009-01-07 | 2011-07-20 | 中国石油化工股份有限公司 | Preparation method of pure silicon MSU molecular sieve |
| EP2417061A4 (en) * | 2009-04-09 | 2016-04-20 | California Inst Of Techn | Molecular sieves and related methods and structure directing agents |
| US9957166B2 (en) | 2009-04-09 | 2018-05-01 | California Institute Of Technology | Molecular sieves and related methods and structure directing agents |
| CN102936018A (en) * | 2012-10-07 | 2013-02-20 | 青岛科技大学 | Preparation method for high stability mesoporous molecular sieve under ionothermal system |
| CN102936018B (en) * | 2012-10-07 | 2014-10-15 | 青岛科技大学 | Preparation method for high stability mesoporous molecular sieve under ionothermal system |
| CN104445243A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for synthesizing MSU molecular sieve |
| US9738538B2 (en) | 2013-12-09 | 2017-08-22 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing NaY molecular sieve of high silica-alumina ratio and product thereof |
| WO2015085462A1 (en) | 2013-12-09 | 2015-06-18 | 中国科学院大连化学物理研究所 | Method for preparing nay molecular sieve of high silica-alumina ratio and product thereof |
| EP3081532A1 (en) * | 2013-12-09 | 2016-10-19 | Dalian Institute Of Chemical Physics, Chinese Academy of Sciences | Method for preparing nay molecular sieve of high silica-alumina ratio and product thereof |
| CN104692413B (en) * | 2013-12-09 | 2017-12-15 | 中国科学院大连化学物理研究所 | A kind of method of NaY molecular sieve for preparing high silica alumina ratio and products thereof |
| EP3081532A4 (en) * | 2013-12-09 | 2017-05-10 | Dalian Institute Of Chemical Physics, Chinese Academy of Sciences | Method for preparing nay molecular sieve of high silica-alumina ratio and product thereof |
| CN105642334B (en) * | 2016-01-29 | 2018-06-29 | 山东多友科技有限公司 | A kind of catalytic cracking catalyst for mixing the fine and close oil of refining and preparation method thereof |
| CN105642334A (en) * | 2016-01-29 | 2016-06-08 | 山东多友科技有限公司 | Catalytic cracking catalyst for blending tight oil and preparing method thereof |
| CN108339564A (en) * | 2016-01-29 | 2018-07-31 | 山东多友科技有限公司 | A kind of preparation method of catalytic cracking catalyst that mixing the fine and close oil of refining |
| CN108339564B (en) * | 2016-01-29 | 2020-07-17 | 山东多友科技有限公司 | Preparation method of catalytic cracking catalyst blended with dense oil |
| CN106589457A (en) * | 2016-12-16 | 2017-04-26 | 衢州普信新材料有限公司 | Phosphorus-nitrogen type flame retardant containing synergist |
| CN106633185A (en) * | 2016-12-20 | 2017-05-10 | 衢州普信新材料有限公司 | Preparation method of organosilicone-modified phosphorus-nitrogen fire retardant |
| CN109647365A (en) * | 2017-10-12 | 2019-04-19 | 中国石油天然气股份有限公司 | A kind of preparation method of catalyst for heavy oil catalytic cracking |
| CN109650422A (en) * | 2017-10-12 | 2019-04-19 | 中国石油天然气股份有限公司 | A method of improving mesoporous aluminum oxide material hydrothermal stability |
| CN108298549A (en) * | 2018-02-05 | 2018-07-20 | 南通龙翔新材料科技股份有限公司 | A kind of preparation method aoxidizing sial with ionic liquid one-step synthesis method composite mesopore |
| CN111825101A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院大连化学物理研究所 | High-silicon Y molecular sieve and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1304290C (en) | 2007-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1304290C (en) | Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould | |
| CN1257839C (en) | Process of preparing mesoporous molecular sieve with ionic liquid as template agent | |
| CN102001678B (en) | Middle hole ZSM-5 zeolite microsphere and preparation method thereof | |
| CN103539153B (en) | The preparation method of nanometer hierarchical pore ZSM-11/ZSM-5 eutectic zeolite | |
| CN104245585B (en) | The method preparing aluminosilicate zeolite SSZ-33 | |
| CN102649574B (en) | Preparation method for mesoporous ZSM-11 zeolite | |
| US20170157598A1 (en) | A method for preparing mesoporous microporous crystalline materials involving a recoverable and recyclable mesopore-templating agent | |
| CN102689910B (en) | Synthetic method of mesoporous-microporous Y-type molecular sieve | |
| CN102602958B (en) | Preparation method of mesoporous mordenite | |
| CN103880036A (en) | Synthetic method of mesoporous mordenite | |
| CN104760974A (en) | Method for one step synthesis of hierarchical porous structured ZSM-5 zeolite with open pores | |
| CN107140656A (en) | The preparation method of mesopore NaY type zeolite molecular sieves | |
| CN101746775B (en) | Preparation method for organic functional ordered mesoporous titanium oxide silicon molecular sieve | |
| CN103318910A (en) | Method for preparing large-size analcite by utilizing hydrothermal crystallization of geopolymer | |
| CN110615445B (en) | Method for synthesizing ZSM-5 zeolite monobloc without template and adhesive | |
| CN108975352A (en) | A kind of preparation method of nano pure silicone ZSM-5 zeolite | |
| CN104326484B (en) | A kind of molecular sieve nanotube aeroge and preparation method thereof | |
| CN1749161A (en) | Hard template synthetic composite hole zeolite molecular sieve and its preparing method | |
| Hoang et al. | Study on using cellulose derivatives as pore directing agent for preparation of hierarchical ZSM-5 zeolite catalyst | |
| CN113060743A (en) | Synthesis method of micro-mesoporous molecular sieve | |
| CN1298625C (en) | Double metaporous silicon dioxide material and its preparing method | |
| CN1155519C (en) | SAPO-11 molecualr sieve and its preparing method | |
| CN1214978C (en) | Ordered mesoporous molecnlar sieve material with wltrahigh hydrothermal stability and synthesis method thereof | |
| CN105174284B (en) | Efficient two-silicon-source amine-free synthesis method for morphology-controllable large-size mordenite | |
| CN101279745B (en) | Method for preparing a zeolite having mel structure |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070314 Termination date: 20100729 |