CN102463135A - EU-1/MOR composite molecular sieve and its preparation method - Google Patents
EU-1/MOR composite molecular sieve and its preparation method Download PDFInfo
- Publication number
- CN102463135A CN102463135A CN2010105361972A CN201010536197A CN102463135A CN 102463135 A CN102463135 A CN 102463135A CN 2010105361972 A CN2010105361972 A CN 2010105361972A CN 201010536197 A CN201010536197 A CN 201010536197A CN 102463135 A CN102463135 A CN 102463135A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- composite molecular
- sio
- mor
- molecular screen
- 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
Images
Abstract
The invention discloses an EU-1/MOR composite molecular sieve and its preparation method. The composite molecular sieve simultaneously has EU-1 molecular sieve crystal phase and MOR zeolite crystal phase. The pore volume of the composite molecular sieve's mesopore accounts for 30-75% of the total pore volume. The mesopore aperture ranges from 30nm to 70nm. A synthetic method of the composite molecular sieve provided by the invention comprises the following steps of: fully and uniformly mixing the EU-1 molecular sieve, a silicon source, alkali, water and a template, carrying out hydrothermal crystallization at the temperature of 140-170 DEG C for 1-4 days, and recovering to obtain the EU-1/MOR composite molecular sieve. The composite molecular sieve provided by the invention has two molecular sieve crystal phases, namely the EU-1 and MOR molecular sieve crystal phases, and simultaneously has large-aperture pore channels. According to the invention, application problems of the microporous molecular sieve are solved.
Description
Technical field
The present invention relates to a kind of double-micropore composite molecular sieve and preparation method thereof, a kind of specifically preparation method of EU-1/MOR double-micropore composite molecular sieve.
Background technology
Modenite (MOR) is one of human knowledge's zeolite the earliest.1948, HOW etc. used sodium carbonate to be mineralizer, used silicic acid gel and sodium aluminate aqueous solution to make the raw water thermal crystallisation, and manual work first synthesizes modenite.Heat-resisting, the acidproof and anti-steam function admirable of modenite.Modenite has good xylene isomerization performance, is the main acidic components that xylene isomerization catalyst is gone up in industry at present.Chinese patent CN1044053, CN1110630 and CN1156642 have embodied the performance of modenite on xylene isomerization.
The EU-1 molecular sieve is a kind of mesopore high-silica zeolite; Have-the netted micropore canals structure of Wei; Contain the straight-through duct of ten-ring (orifice diameter be 0.58 * 0.41nm) and with it the twelve-ring side pocket of vertical UNICOM (being of a size of 0.68 * 0.58 * 0.81nm) structure, is one type of molecular sieve that characteristics are arranged on pore passage structure very much.The EU-1 molecular sieve in xylene isomerization, has good catalytic performance as the catalyst applications of acid constituent element.Under identical condition, adopting EUO topological structure molecular sieve is that the xylene isomerization catalyst of acid constituent element has higher activity and selectivity, has favorable industrial application prospect.Chinese patent CN01121423.6, CN01121442.2 and CN200610112735.9 have embodied the performance of EU-1 molecular sieve on the xylenes isomery.
The above-mentioned EU-1 of showing molecular sieve and MOR zeolite have important purposes at petrochemical industry, are the important acidic components of xylene isomerization catalyst.Because the characteristics of EU-1 type zeolite molecular sieve and MOR zeolite molecular sieve; EU-1 type zeolite molecular sieve and MOR zeolite molecular sieve are combined with each other; Both learn from other's strong points to offset one's weaknesses to make it; Replenish each other, synthetic a kind of composite zeolite molecular sieve with dual structure and acidity can distribute with acid to both structures and regulate, and better meets the demand of commercial Application.
Two kinds of molecular sieves all are micro porous molecular sieves, and the micropore canals significant adverse is in the diffusion of absorption, reaction and the product of reactant, and the pore properties of molecular sieve has limited the carrying out of reaction.Exist bigger duct, aperture effectively to address the above problem.And existing composite molecular screen; " preset the synthetic EU-1/MOR composite molecular screen of crystal seed " having introduced a kind of like 2008 10 phases of Industrial Catalysis is that template, modenite (MOR) are crystal seed with C6 (HMBr2); Crystal seed method synthetic composite molecular screen EU-1/MOR in the dense system of height is preset in employing, and the composite molecular screen product that it obtains does not have the duct of larger aperture.
Summary of the invention
The purpose of this invention is to provide a kind of EU-1 molecular sieve of combination and composite molecular screen of MOR zeolite and preparation method thereof; Composite molecular screen of the present invention is when having above-mentioned two kinds of molecular sieve crystalline phases; Duct with larger aperture has solved the problem that micro porous molecular sieve runs in application.
EU-1/MOR composite molecular screen of the present invention has EU-1 molecular sieve crystalline phase and MOR zeolite crystalline phase simultaneously, and the mesoporous pore volume of composite molecular screen accounts for 30%～75% of total pore volume, and mesoporous aperture (bore dia) concentrates on 30～70nm.
EU-1/MOR composite molecular screen of the present invention has the XRD characteristic spectrogram of EU-1 molecular sieve and MOR zeolite simultaneously.Show that through ESEM (SEM) and X-ray diffraction (XRD) analysis the structure of this composite molecular screen is that EU-1 molecular sieve and MOR zeolite closely are embedded in composite molecular screen particle together, the particle size of composite molecular screen is generally 1～4 μ m.The weight content of EU-1 molecular sieve in composite molecular screen is 25%～70%.The SiO of EU-1/MOR composite molecular screen
2/ Al
2O
3Mol ratio is 30～60.
Significantly different with conventional MOR zeolite and EU-1 molecular sieve, the diffraction maximum at 2 θ=9.7 ± 0.5 places that belongs to the MOR phase among the present invention significantly strengthens.The diffraction maximum in 2 θ=27 ± 0.5 that belongs to the EU-1 molecular sieve significantly strengthens, and belongs to enlarging markedly in 2 θ=22 ± 0.5 place's diffraction maximum d values of EU-1 molecular sieve.The two micro porous molecular sieves that make all increase at aspects such as acid strength, heat and hydrothermal stabilities.
The preparation method of EU-1/MOR composite molecular screen provided by the invention comprises the steps:
(1) EU-1 molecular sieve, silicon source, alkali, water and template are fully mixed, each component is following by the ratio of its oxide in the gel, wherein SiO
2Be SiO in the silicon source
2Content, do not comprise the silicon in the EU-1 molecular sieve:
EU-1/SiO
2(gram/gram)=1～10
R/SiO
2(moles/mole)=0.06～0.38
Na
2O/SiO
2(moles/mole)=0.69～4.6
H
2O/SiO
2(moles/mole)=33～166
Be preferably:
EU-1/SiO
2(gram/gram)=1.2～7.5
R/SiO
2(moles/mole)=0.07～0.28
Na
2O/SiO
2(moles/mole)=0.86～3.45
H
2O/SiO
2(moles/mole)=40～95
R represents template
(2) crystallization: the reaction mixture gel of step (1) preparation is warming up to 140 ℃～170 ℃, and hydrothermal crystallizing 1～4 day;
(3) after crystallization is accomplished, make the EU-1/MOR composite molecular screen through filtration, washing, drying and roasting.
Wherein said template is selected from tetraethyl ammonium hydroxide or tetraethylammonium bromide.Be preferably tetraethylammonium bromide.
Described silicon source can be white carbon black, Ludox, waterglass, silicic acid or ethyl orthosilicate, preferred white carbon black.
Described crystal seed is the EU-1 molecular sieve.The EU-1 molecular sieve can be the sodium type molecular sieve of roasting or the molecular sieve of roasting not, is preferably the sodium type EU-1 molecular sieve of roasting.
Hydrothermal crystallizing described in the step (2) is to place pressure vessel under temperature constant state, to carry out the reaction mixture gel that is mixed with, i.e. thermostatic crystallization.Hydrothermal crystallizing can be static crystallization or dynamic crystallization.
Composite molecular screen provided by the present invention can be used for reactions such as especially polymerization, aromatisation, isomerization in the different hydrocarbon conversion reactions, for example to C
8The aromatics isomerization reaction table reveals very high reactivity.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the composite molecular screen of the embodiment of the invention 1 preparation.
Fig. 2 is the stereoscan photograph of the composite molecular screen of the embodiment of the invention 1 preparation.
The specific embodiment
The x-ray diffractometer that the thing of EU-1/MOR composite molecular screen of the present invention is measured mutually and the mensuration of degree of crystallinity adopts is that the D/max-2500 type that Japanese Co., Ltd. of science produces automatically rotates the target x-ray diffractometer.During experiment, sample is ground to the above compressing tablet of 300 orders, the machine of going up then characterizes.Experiment condition: the Cu target, K α radiation source, graphite monochromator, operating voltage 40kV, tube current 80mA, sweep limits is 5-40 °, and sweep speed is 8 °/min, and step-length is 0.01 °.
Below in conjunction with embodiment the present invention is further explained.
Embodiment 1
In beaker, successively add 2.0g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water, stir, add 7.5gEU-1 molecular sieve crystal seed again, stir 10min, add the white carbon black of 1.75g at last, the synthesis reactor of packing into behind the stirring 30min.170 ℃ of heating 96h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains the EU-1/MOR composite molecular screen at 550 ℃ of following roasting 5h.
The XRD spectra of this EU-1/MOR composite molecular screen and stereoscan photograph are like Fig. 1, shown in 2.As can beappreciated from fig. 1, the characteristic peak of EU-1 molecular sieve and MOR zeolite is quite obvious in this composite molecular screen.As can beappreciated from fig. 2, the structure of this composite molecular screen is that EU-1 molecular sieve and MOR zeolite closely are embedded in composite molecular screen particle together, and the size of composite molecular screen integral particle is at 1～2 μ m.The silica alumina ratio of this composite molecular screen is 42.EU-1 molecular sieve weight content is 25% in the composite molecular screen.Mesoporous pore volume accounts for 43% of total pore volume, and mesoporous aperture concentrates on 55nm.
Embodiment 2
In beaker, successively add 1.8g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water, stir, add 7.5gEU-1 molecular sieve crystal seed again, stir 10min, add the white carbon black of 1.75g at last, the synthesis reactor of packing into behind the stirring 30min.170 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains the EU-1/MOR composite molecular screen at 550 ℃ of following roasting 5h.
The silica alumina ratio of this composite molecular screen is 42.EU-1 molecular sieve weight content is 60% in the composite molecular screen.Mesoporous pore volume accounts for 64% of total pore volume, and mesoporous aperture concentrates on 50nm.
Embodiment 3
In beaker, successively add 1.35g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water, stir, add 2gEU-1 molecular sieve crystal seed again, stir 10min, add the white carbon black of 1.75g at last, the synthesis reactor of packing into behind the stirring 30min.170 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains the EU-1/MOR composite molecular screen at 550 ℃ of following roasting 5h.
The silica alumina ratio of this composite molecular screen is 60.EU-1 molecular sieve weight content is 50% in the composite molecular screen.Mesoporous pore volume accounts for 57% of total pore volume, and mesoporous aperture concentrates on 50nm.
Embodiment 4
In beaker, successively add 2.3g NaOH, 1g tetraethylammonium bromide, 50ml distilled water, stir, add 7.5gEU-1 molecular sieve crystal seed again, stir 10min, add the white carbon black of 1.5g at last, the synthesis reactor of packing into behind the stirring 30min.140 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains the EU-1/MOR composite molecular screen at 550 ℃ of following roasting 5h.
The silica alumina ratio of this composite molecular screen is 41.EU-1 molecular sieve weight content is 25% in the composite molecular screen.Mesoporous pore volume accounts for 36% of total pore volume, and mesoporous aperture concentrates on 50nm.
In beaker, successively add 1.8g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water, stir, add 7.5gEU-1 molecular sieve crystal seed again, stir 10min, add the white carbon black of 1.75g at last, the synthesis reactor of packing into behind the stirring 30min.170 ℃ of heating 72h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains the EU-1/MOR composite molecular screen at 550 ℃ of following roasting 5h.
The silica alumina ratio of this composite molecular screen is 42.EU-1 molecular sieve weight content is 65% in the composite molecular screen.Mesoporous pore volume accounts for 67% of total pore volume, and mesoporous aperture concentrates on 48nm.
Embodiment 6
In beaker, successively add 1.35g NaOH, 1.55g tetraethylammonium bromide, 50ml distilled water, stir, add 7.5gEU-1 molecular sieve crystal seed again, stir 10min, add at last and contain 1.75g SiO
2Ludox, stir the synthesis reactor of packing into behind the 30min.170 ℃ of heating 24h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains the EU-1/MOR composite molecular screen at 550 ℃ of following roasting 5h.
The silica alumina ratio of this composite molecular screen is 42.EU-1 molecular sieve weight content is 70% in the composite molecular screen.Mesoporous pore volume accounts for 66% of total pore volume, and mesoporous aperture concentrates on 50nm.
Comparative example
Prepare composite molecular screen by existing method, 2g MOR zeolite is joined NaOH (1.2mol/L) aqueous solution of 10ml, stirring at room 30min adds 2g C6 (HMBr more successively
2), the white carbon black of 5g and 2g silicon aluminium microsphere (silica alumina ratio is 10), continue to be stirred to evenly.The colloidal solution that forms is transferred to the stainless steel still, takes out after 2 days in 175 ℃ of static crystallization, water is washed till neutrality after quenching to the room temperature, and drying promptly obtains the EU-1/MOR composite molecular screen at 550 ℃ of following roasting 5h.
The silica alumina ratio of this composite molecular screen is 24.EU-1 molecular sieve weight content is 55% in the composite molecular screen.The micropore pore volume accounts for 92% of total pore volume.
Claims (10)
1. EU-1/MOR composite molecular screen, composite molecular screen has EU-1 molecular sieve crystalline phase and MOR zeolite crystalline phase simultaneously, it is characterized in that: the mesoporous pore volume of composite molecular screen accounts for 30%～75% of total pore volume, and mesoporous aperture concentrates on 30～70nm.
2. according to the described composite molecular screen of claim 1, it is characterized in that: the structure of composite molecular screen is that EU-1 molecular sieve and MOR zeolite closely are embedded in composite molecular screen particle together, and the particle size of composite molecular screen is 1～4 μ m.
3. according to claim 1 or 2 described composite molecular screens, it is characterized in that: the weight content of EU-1 molecular sieve in composite molecular screen is 25%～70%.
4. according to claim 1 or 2 described composite molecular screens, it is characterized in that: the SiO of EU-1/MOR composite molecular screen
2/ Al
2O
3Mol ratio is 30～60.
5. the synthetic method of the said EU-1/MOR composite molecular screen of claim 1 is characterized in that comprising the steps:
(1) EU-1 molecular sieve, silicon source, alkali, water and template are fully mixed, each component is following by the ratio of its oxide in the gel, wherein SiO
2Be SiO in the silicon source
2Content, do not comprise the silicon in the EU-1 molecular sieve:
In gram/gram, EU-1/SiO
2=1～10
In moles/mole, R/SiO
2=0.06～0.38, R represents template
In moles/mole, Na
2O/SiO
2=0.69～4.6
In moles/mole, H
2O/SiO
2=33～166
(2) crystallization: the reaction mixture gel of step (1) preparation is warming up to 140 ℃～170 ℃, and hydrothermal crystallizing 1～4 day;
(3) after crystallization is accomplished, make the EU-1/MOR composite molecular screen through filtration, washing, drying and roasting.
6. according to the described method of claim 5, it is characterized in that each component in the gel by the ratio of its oxide is:
In gram/gram, EU-1/SiO
2=1.2～7.5
In moles/mole, R/SiO
2=0.07～0.28
In moles/mole, Na
2O/SiO
2=0.86～3.45
In moles/mole, H
2O/SiO
2=40～95
R represents template.
7. according to claim 5 or 6 described methods, it is characterized in that: template is selected from tetraethyl ammonium hydroxide or tetraethylammonium bromide.
8. want 5 described methods according to right, it is characterized in that: the silicon source is white carbon black, Ludox, waterglass, silicic acid or ethyl orthosilicate.
9. according to the described method of claim 5, it is characterized in that: the EU-1 molecular sieve is the sodium type molecular sieve of roasting or the molecular sieve of roasting not.
10. according to the described method of claim 5, it is characterized in that: the hydrothermal crystallizing in the step (2) is to place pressure vessel under temperature constant state, to carry out the reaction mixture gel that is mixed with, and hydrothermal crystallizing is static crystallization or dynamic crystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105361972A CN102463135B (en) | 2010-11-04 | 2010-11-04 | EU-1/MOR composite molecular sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105361972A CN102463135B (en) | 2010-11-04 | 2010-11-04 | EU-1/MOR composite molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102463135A true CN102463135A (en) | 2012-05-23 |
| CN102463135B CN102463135B (en) | 2013-11-20 |
Family
ID=46067430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105361972A Active CN102463135B (en) | 2010-11-04 | 2010-11-04 | EU-1/MOR composite molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102463135B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803575A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Synthetic method for EU-1/MOR symbiotic molecular sieve |
| CN103803574A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of EU-1/MOR (mordenite) co-crystallized molecular sieve |
| CN104556095A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing Y/Silicalite-1 composite molecular sieve |
| CN104556094A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Y/Silicalite-1 composite molecular sieve and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6342200B1 (en) * | 1998-11-02 | 2002-01-29 | Institut Francais Du Petrole | Process for preparing a zeolite with structure type EUO |
| CN1772611A (en) * | 2005-09-28 | 2006-05-17 | 中国科学院大连化学物理研究所 | Composite molecular sieve in ten-element cyclic structure and its synthesis process |
| CN101340976A (en) * | 2005-12-22 | 2009-01-07 | 法国石油公司 | Dual zeolite catalyst comprising a group VIII metal and a group IIIV metal and its use in isomerization of aromatic C8 compounds |
-
2010
- 2010-11-04 CN CN2010105361972A patent/CN102463135B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6342200B1 (en) * | 1998-11-02 | 2002-01-29 | Institut Francais Du Petrole | Process for preparing a zeolite with structure type EUO |
| CN1772611A (en) * | 2005-09-28 | 2006-05-17 | 中国科学院大连化学物理研究所 | Composite molecular sieve in ten-element cyclic structure and its synthesis process |
| CN101340976A (en) * | 2005-12-22 | 2009-01-07 | 法国石油公司 | Dual zeolite catalyst comprising a group VIII metal and a group IIIV metal and its use in isomerization of aromatic C8 compounds |
Non-Patent Citations (1)
| Title |
|---|
| 周朋燕等: "预置晶种合成EU-1/MOR复合分子筛", 《工业催化》, vol. 16, no. 10, 31 October 2008 (2008-10-31) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803575A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Synthetic method for EU-1/MOR symbiotic molecular sieve |
| CN103803574A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of EU-1/MOR (mordenite) co-crystallized molecular sieve |
| CN103803574B (en) * | 2012-11-08 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of preparation method of EU-1/MOR coexisting molecular sieve |
| CN104556095A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing Y/Silicalite-1 composite molecular sieve |
| CN104556094A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Y/Silicalite-1 composite molecular sieve and preparation method thereof |
| CN104556094B (en) * | 2013-10-22 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of Y/Silicalite-1 composite molecular screen and preparation method thereof |
| CN104556095B (en) * | 2013-10-22 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of preparation method of Y/Silicalite-1 composite molecular screen |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102463135B (en) | 2013-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019144253A1 (en) | Preparation method for hollow single crystal beta molecular sieve | |
| TWI490167B (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
| CN102452666B (en) | Method for synthesizing IM-5 molecular sieve | |
| US20200038848A1 (en) | Zsm-35 molecular sieve and preparation method thereof | |
| KR101950552B1 (en) | Synthesis of zsm-5 crystals with improved morphology | |
| CN102815718B (en) | One-step method for preparing 3A type zeolite molecular sieve by kaoline | |
| CN102463135B (en) | EU-1/MOR composite molecular sieve and preparation method thereof | |
| CN107285332B (en) | Synthesis method of ZSM-22 molecular sieve and ZSM-22 molecular sieve synthesized by same | |
| CN106517239B (en) | A kind of pillared layered modenite and preparation method thereof | |
| CN103301875B (en) | A kind of MFI type Si-Al molecular sieve/aluminum fiber composite and its preparation method and application | |
| JP2010260777A (en) | Method for producing phosphorus-containing beta type zeolite | |
| CN109607563A (en) | Zinc modification multi-stage porous ZSM-5 nano zeolite and preparation method thereof | |
| CN103043681A (en) | Preparation method of nano layered ZSM (Zeolite Molecular Sieve)-5 zeolite molecular sieve | |
| CN106809859A (en) | The synthetic method and ZSM-5 molecular sieve of a kind of ZSM-5 molecular sieve | |
| CN110510628A (en) | A kind of Beta zeolite of big crystal grain and its preparation method and application | |
| CN109694083B (en) | Preparation method of DDR zeolite molecular sieve | |
| CN102861606B (en) | Double-micropore composite molecular sieve, preparation method of double-micropore composite molecular sieve and application of double-micropore composite molecular sieve | |
| CN107497480B (en) | A kind of synthetic method of Jie's mesoporous-microporous composite molecular sieve catalyst | |
| CN102259890B (en) | ZSM-5/ECR-1/mordenite three-phase symbiotic material and preparation method thereof | |
| CN106946266B (en) | A kind of SAPO-34/ZSM-12 composite molecular screens and its synthetic method | |
| CN107572547A (en) | A kind of synthetic method of multilevel ordered mesoporous Si-Al molecular sieve | |
| CN105621439B (en) | A kind of synthetic method of Beta zeolites | |
| CN111186846B (en) | ITH structure silicon-aluminum molecular sieve and preparation method thereof | |
| CN113336240A (en) | Method for preparing single/double crystal ZSM-5 zeolite based on kaolin mineral regulation and control | |
| CN109704358B (en) | Synthesis method of EU-1/ZSM-5 composite molecular sieve |
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 |