CN103288100B - A kind of multi-stage porous ZSM-5 molecular sieve and synthetic method thereof - Google Patents
A kind of multi-stage porous ZSM-5 molecular sieve and synthetic method thereof Download PDFInfo
- Publication number
- CN103288100B CN103288100B CN201310201578.9A CN201310201578A CN103288100B CN 103288100 B CN103288100 B CN 103288100B CN 201310201578 A CN201310201578 A CN 201310201578A CN 103288100 B CN103288100 B CN 103288100B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- stage porous
- solution
- hours
- porous zsm
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a kind of multi-stage porous ZSM-5 molecular sieve and synthetic method thereof, multi-stage porous ZSM-5 molecular sieve is piled up by the crystal grain with ordered nano laminated structure to form and for one-piece construction, synthetic method take quaternary ammonium salt as structure directing agent (SDA), tetraethoxy (TEOS) is silicon source, aluminum isopropylate (AIP) is aluminium source, potassium hydroxide (KOH) is alkali source, add cats product (CSF), be mixed with mol ratio and meet (20-100) SiO
2: (1-3) Al
2o
3: (10-30) SDA: (10-50) KOH: (1000-3000) H
2o: the synthesis liquid of (1-10) CSF, and the Silicalite-1 molecular sieve crystal seed gel adding 10 ~ 20%, hydrothermal crystallizing according to a conventional method, product obtains ZSM-5 molecular sieve through washing, drying, roasting.This molecular sieve is the congeries with lamella and multi-stage artery structure of the interaction self-assembly between cats product and crystal seed gel, inorganic species, has larger specific surface area, shorter the evolving path and stability preferably.This preparation method also has that degree of crystallinity is high, productive rate is high, operation steps is simple, be easy to the advantages such as separation.
Description
Technical field
The present invention relates to Zeolite synthesis technical field, especially relate to a kind of multi-stage porous ZSM-5 molecular sieve and the synthetic method thereof with nanoscale twins one-piece construction.
Background technology
Mobil company of the U.S., in reported first in 1972 synthesis of ZSM-5 molecular sieve (USP3702886), becomes one of maximum catalyzer of industrial application because it has the excellent properties such as orderly microvoid structure, larger specific surface area, higher heat and hydrothermal stability, skeleton acid site, tradable positively charged ion.But the micropore canals that micropore ZSM-5 molecular sieve is less hinders comparatively macromole and enters in zeolite cavity and carry out adsorbing and catalyzed reaction, limits macromolecular diffusion.In order to overcome the restriction in single duct, investigators consider the solution route that ducts at different levels feature is combined, as introduced meso-hole structure or nanocrystal is piled into molecular sieve congeries in the synthetic system of conventional microporous ZSM-5 molecular sieve, thus improve the rate of diffusion of reactant and product, improve the hydrothermal stability of hole wall, improve catalytic reaction activity.
Multi-stage porous molecular sieve has the composite holes of more than two-stage or two-stage, has larger specific surface area and flourishing multi-stage porous gap structure, in diffusion, mass transfer etc., has the characteristic being better than single microvoid structure molecular sieve.In recent years, prepare the multi-stage porous ZSM-5 molecular sieve with nano-lamellar structure and become one of focus of catalytic material research field.In prior art, there is a kind of multi-stage porous ZSM-5 molecular sieve using homemade special surface promoting agent C22 hour 45-N (CH3) 2-C6H12-N (CH3) 2-C6H13 to synthesize interlamellar spacing to be about the interlaced structure of lamella of 2nm.Subsequently, this research group controls the thickness of nanoscale twins and the pattern of crystal by the length and amino number changing linear alkyl chain, and applying it in the reaction of preparing gasoline by methanol, the existence of nano-lamellar structure makes catalyzer show stronger anti-coking performance, hydrothermal stability and acidity.
But the synthesis of nano laminated structure multi-stage porous ZSM-5 molecular sieve of bibliographical information is the powder of micron-scale size, binding agent need be added and make its shaping or raising intensity.The use of additive can block molecular sieve pore passage, causes catalyst activity component concentration to reduce, thus reduces its catalytic performance.Although also there is investigator to prepare integral catalyzer, needs multi step strategy or add special carrier in building-up process, complicated schedule of operation, higher synthesis cost etc. remain the difficult point needing customer service.Therefore, developing a kind of method relatively simply, without the need to using additive preparation to have the monoblock type multi-stage porous ZSM-5 molecular sieve catalyzer of nano-lamellar structure, becoming the key issue that patent of the present invention solves.
Summary of the invention
First technical problem to be solved by this invention is: the deficiency existed for prior art, provides the multi-stage porous ZSM-5 molecular sieve that a kind of relative crystallinity is high, crystal formation is complete.
Second technical problem to be solved by this invention is: the deficiency existed for prior art, provides the preparation method with the multi-stage porous ZSM-5 molecular sieve of nanoscale twins one-piece construction that a kind of synthesis step is simple, combined coefficient is high.
For solving above-mentioned first technical problem, technical scheme of the present invention is: a kind of multi-stage porous ZSM-5 molecular sieve, and described molecular sieve has nanoscale twins and is one-piece construction.
Preferably, described nanoscale twins is that the phenyl ring sheet being about 4.0hm by thickness is piled up in order along b direction of principal axis and formed.
Preferably, described one-piece construction is the congeries of the cm size piled up by the zeolite crystal with laminated structure.
For solving above-mentioned second technical problem, technical scheme of the present invention is:
Synthesize a method for multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, comprise the following steps:
(1) with tetraethoxy, TPAOH (20%), deionized water for starting raw material, in 80 DEG C of hydrothermal crystallizings 2 ~ 24 hours, after cooling, take out crystallization thing, for subsequent use as crystal seed gel;
(2) potassium hydroxide is dissolved in deionization H
2wiring solution-forming A in O, adds load weighted quaternary ammonium salt structure directed agents and aluminum isopropylate in the solution A of 20-40% and stirs 2 ~ 4 hours formation solution B;
(3) appropriate tetraethoxy is slowly added rapid stirring in the solution A of 20-40% and form solution C in 2 ~ 4 hours;
(4) B is joined rapid stirring in C and form solution D in 5 hours;
(5) appropriate cats product is added in the solution A of 20-40%, after 1 hour in 50 DEG C of heating, join in solution D and continue stirring 1 hour forming reactions mixture;
(6) the crystal seed gel prepared is joined in reaction mixture, to stir after 1 hour at 175 DEG C hydrothermal crystallizing 48 hours;
(7), after reaction terminates, sample is taken out, in 120 DEG C of oven dry of spending the night after large water gaging rinses, then 500 ~ 650 DEG C of roastings 5 ~ 8 hours under oxygen atmosphere in tube furnace.
Preferably, crystal seed gel described in step (1) is Silicalite-1 molecular sieve crystal seed gel, and synthesis liquid proportioning is: 9TPAOH: 25SiO
2: 480H
2o: 100EtOH.
Preferably, the quaternary ammonium salt structure directed agents described in step (2) is any one in TPAOH, 4-propyl bromide, benzyl triethyl ammonium bromide and benzyl tributyl brometo de amonio.
Preferably, quaternary ammonium salt structure directed agents and aluminum isopropylate described in step (2) add in the alkaline solution of 30% stir 2 ~ 4 hours.
Preferably, tetraethoxy described in step (3) slowly to add in the alkaline solution of 30% rapid stirring 2 ~ 4 hours.
Preferably, described in step (4), the proportioning of reaction mixture D is: 40SiO
2: 2Al
2o
3: 15SDA:25KO hour: 3000 hours
2o.
Preferably, described in step (5), cats product is cetyl trimethylammonium bromide, and addition is: n (TEOS): n (CTAB)=30 ~ 10.
Preferably, the content of crystal seed gel described in step (6) is 10 % by weight to 20 % by weight of described reaction mixture, and described crystallization adopts autoclave crystallization.
Preferably, roasting condition described in step (7) is in 500 ~ 650 DEG C of roastings 5 ~ 8 hours in tube furnace.
Have employed technique scheme, beneficial effect of the present invention is: the invention has the advantages that with organic quaternary ammonium salt structure directing agent cheap and easy to get, under conventional hydrothermal synthesis condition, a step obtains the integral catalyzer with micropore, mesoporous, macroporous structure of centimetre-sized size.The ZSM-5 molecular sieve adopting the method for the invention to prepare is the laminated structure that the phenyl ring sheet being about 4.0nm by thickness of high-crystallinity is piled up, and its specific surface area is 387.26m
2/ g, mesopore volume is 0.112cm
3/ g, mesoporous main integrated distribution is between 3.0nm-4.5nm.Preparation method provided by the invention, simplifies the step of existing preparation monoblock type multi-stage porous catalyst technology, does not need the subsidiary material such as expensive structure directing agent and special monolithic substrate, reduce preparation cost.This preparation method has that degree of crystallinity is high, productive rate is high, the simple advantage with being easy to be separated of operation steps.
In addition, this molecular sieve is the congeries with lamella and multi-stage artery structure of the interaction self-assembly between cats product and crystal seed gel, inorganic species, there is larger specific surface area, shorter the evolving path and good stability, between the multistage hole of ZSM-5 molecular sieve, series connection is through mutually, their diffusion feature each other can be given full play to, for catalyzed reaction.
Accompanying drawing explanation
Fig. 1 is X-ray powder diffraction spectrum (XRD) figure of the nano-lamellar structure monoblock type multi-stage porous ZSM-5 molecular sieve that embodiment 1 is synthesized.
Fig. 2 is the optical photograph of the nano-lamellar structure monoblock type multi-stage porous ZSM-5 molecular sieve that embodiment 1 is synthesized.
Fig. 3 is stereoscan photograph (SEM) figure of the nano-lamellar structure monoblock type multi-stage porous ZSM-5 molecular sieve that embodiment 1 is synthesized.
Fig. 4 is the N of the nano-lamellar structure monoblock type multi-stage porous ZSM-5 molecular sieve that embodiment 1,5,6 is synthesized
2-adsorption/desorption isotherms and graph of pore diameter distribution.
Fig. 5 is transmission electron microscope photo (TEM) figure of the monoblock type multi-stage porous ZSM-5 molecular sieve that embodiment 1 is synthesized.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
First it should be noted that, in following all embodiments: agents useful for same, except special instruction, all adopts analytical reagent; The XRD analysis of sample adopts Rigaku company D/MAX2200 type X-ray powder diffractometer.Test condition is: Cu target, K α radiation, Ni filtering, tube voltage 40Kv, and tube current 30mA, sweep limit 5 °-50 ° (2 θ), sweep velocity are 4 °/min, step-length 0.02 °; The SEM of sample measures and adopts the test of Jeol Ltd. (JEOL) JSM-7500F type field emission scanning electron microscope, and all samples is before testing through metal spraying process; The specific surface of sample and pore structure adopt JW-BK132F specific surface and Porosimetry to measure; Before surveying, sample is degassed 2 hours at 300 DEG C, and under liquid nitrogen temperature, (-197 DEG C) adsorb, N
2for adsorbate.By BrunauerEmmettTeller (BET) Equation for Calculating sample specific surface, pore distribution adopts BJ hour method to calculate; The TEM of sample measures and adopts Czech FEI Co. TecnaiG20 type transmission electron microscope, and operating voltage is 200KV.
The present invention is described further for the following examples, but do not limit the present invention.
As Fig. 1 ~ Fig. 5 jointly shown in, the nano-lamellar structure monoblock type multi-stage porous ZSM-5 molecular sieve that each embodiment obtains carries out XRD, SEM, N
2-physical adsorption and tem analysis, be described further method of the present invention by reference to the accompanying drawings, specific as follows:
Embodiment 1
(1) with tetraethoxy, TPAOH (20%), deionized water for starting raw material, preparation mol ratio be 9TPAOH: 25SiO
2: 480H
2the synthesis liquid of O: 100EtOH, in 80 DEG C of hydrothermal crystallizings 6 hours, takes out crystallization thing after cooling, for subsequent use as crystal seed gel;
(2) potassium hydroxide is dissolved in deionization H
2wiring solution-forming A in O, adds load weighted TPAOH and aluminum isopropylate respectively in the solution A of 30% and stirs 2 hours formation solution B, load weighted tetraethoxy is slowly added rapid stirring in the solution A of 30% and forms solution C in 2 hours;
(3) B is joined rapid stirring in C and form solution D in 5 hours;
(4) 0.483g cetyl trimethylammonium bromide (CTA) is added in the solution A of 40%, after 1 hour in 50 DEG C of heating, join in solution D and continue stirring 1 hour forming reactions mixture;
(5) the crystal seed gel prepared is joined in reaction mixture, to stir after 1 hour at 175 DEG C hydrothermal crystallizing 48 hours;
(6), after reaction terminates, sample is taken out, in 120 DEG C of oven dry of spending the night after large water gaging rinses, then 550 DEG C of roastings 6 hours under oxygen atmosphere in tube furnace.
Embodiment 2
In the step (2) of the present embodiment, potassium hydroxide is dissolved in deionization H
2wiring solution-forming A in O, respectively load weighted 4-propyl bromide and aluminum isopropylate are added in the solution A of 20% to stir and form solution B in 2 hours, load weighted tetraethoxy is slowly added rapid stirring in the solution A of 20% and form solution C in 2 hours, other step is with embodiment 1.
Embodiment 3
In the step (2) of the present embodiment, potassium hydroxide is dissolved in deionization H
2wiring solution-forming A in O, respectively load weighted benzyl triethyl ammonium bromide and aluminum isopropylate are added in the solution A of 25% to stir and form solution B in 2 hours, load weighted tetraethoxy is slowly added rapid stirring in the solution A of 25% and form solution C in 2 hours, other step is with embodiment 1.
Embodiment 4
In the step (2) of the present embodiment, potassium hydroxide is dissolved in deionization H
2wiring solution-forming A in O, respectively load weighted benzyl tributyl brometo de amonio and aluminum isopropylate are added in the solution A of 40% to stir and form solution B in 2 hours, load weighted tetraethoxy is slowly added rapid stirring in the solution A of 40% and form solution C in 2 hours, other step is with embodiment 1.
Embodiment 5
Add 0.325gCTAB in the step (4) of the present embodiment, other step is with embodiment 1.
Embodiment 6
The step (4) of the present embodiment adds 0.975gCTAB, and other step is with embodiment 1.
As shown in table 1 is the contrast of embodiment 1, embodiment 5 and embodiment 6
Table 1
Specific embodiment described in the present invention is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment.Although made a detailed description the present invention and quoted some specific embodiments as proof, to those skilled in the art, only otherwise it is obvious for leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (9)
1. a multi-stage porous ZSM-5 molecular sieve, it is characterized in that, described molecular sieve has nanoscale twins and is one-piece construction, described nanoscale twins to be piled up in order along b direction of principal axis by typical nano thickness benzene cyclic crystalline to form, and described one-piece construction is the diameter piled up by laminated structure is centimetre-sized congeries;
Above-mentioned a kind of multi-stage porous ZSM-5 molecular sieve is synthesized by following steps:
(1) with tetraethoxy, 20% TPAOH, deionized water for starting raw material, in 80 DEG C of hydrothermal crystallizings 2 ~ 24 hours, cool centrifugal rear taking-up crystallization thing, for subsequent use as crystal seed gel;
(2) potassium hydroxide is dissolved in deionization H
2wiring solution-forming A in O, adds load weighted quaternary ammonium salt structure directed agents and aluminum isopropylate in the solution A of 20-40% and stirs 2 ~ 4 hours formation solution B;
(3) appropriate tetraethoxy is slowly added rapid stirring in the solution A of 20-40% and form solution C in 2 ~ 4 hours;
(4) B is joined in C rapid stirring 2-5 hour and form solution D;
(5) by appropriate cats product, add in the solution A of 20-40%, after 1-3 hour in 50 DEG C of heating, join in solution D and continue stirring 1 hour forming reactions mixture;
(6) the crystal seed gel prepared is joined in reaction mixture, to stir after 1-3 hour at 175 DEG C hydrothermal crystallizing 48 hours;
(7), after reaction terminates, take out sample, in 120 DEG C of oven dry of spending the night after large water gaging rinses, then in tube furnace 500 ~ 650 DEG C of roastings 4 ~ 8 hours.
2. a kind of multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, it is characterized in that, crystal seed gel described in step (1) is Silicalite-1 molecular sieve crystal seed gel, and synthesis liquid mol ratio is: (3-9) TPAOH: (25-100) SiO
2: (480-1000) H
2o: (100-400) EtOH.
3. a kind of multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, it is characterized in that, any one that to be quaternary ammonium salt be in TPAOH, 4-propyl bromide, benzyl triethyl ammonium bromide and benzyl tributyl brometo de amonio of the structure directing agent described in step (2).
4. a kind of multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, is characterized in that, quaternary ammonium salt structure directed agents and aluminum isopropylate described in step (2) add in the alkaline solution of 20-40% stir 2 ~ 4 hours.
5. a kind of multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, is characterized in that, tetraethoxy described in step (3) slowly to add in the alkaline solution of 20-40% rapid stirring 2 ~ 4 hours.
6. a kind of multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, is characterized in that, described in step (5), the mol ratio of reaction mixture is: (20-100) SiO
2: (0.25-3) Al
2o
3: (10-30) SDA: (10-50) KOH: (1000-3000) H
2o: (1-10) CSF.
7. a kind of multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, it is characterized in that, cats product described in step (5), be preferably cetyl trimethylammonium bromide (CTAB), addition is: n (TEOS): n (CTAB)=30 ~ 10.
8. a kind of multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, is characterized in that, the content of crystal seed gel described in step (6) is 10 % by weight to 20 % by weight of described reaction mixture, and described crystallization adopts conventional hydrothermal reactor crystallization.
9. a kind of multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, is characterized in that, roasting condition described in step (7) is in 500 ~ 650 DEG C of roastings 4 ~ 8 hours in tube furnace.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310201578.9A CN103288100B (en) | 2013-05-21 | 2013-05-21 | A kind of multi-stage porous ZSM-5 molecular sieve and synthetic method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310201578.9A CN103288100B (en) | 2013-05-21 | 2013-05-21 | A kind of multi-stage porous ZSM-5 molecular sieve and synthetic method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103288100A CN103288100A (en) | 2013-09-11 |
CN103288100B true CN103288100B (en) | 2015-11-25 |
Family
ID=49089715
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310201578.9A Expired - Fee Related CN103288100B (en) | 2013-05-21 | 2013-05-21 | A kind of multi-stage porous ZSM-5 molecular sieve and synthetic method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103288100B (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103896304B (en) * | 2014-04-01 | 2015-12-09 | 汕头大学 | A kind of preparation method and application of HZSM-5 molecular sieve |
CN105712379B (en) * | 2014-12-02 | 2018-07-13 | 中国科学院大连化学物理研究所 | A kind of synthetic method of multi-stage porous ZSM-5 molecular sieve |
CN104591205B (en) * | 2015-02-06 | 2016-08-17 | 厦门大学 | A kind of preparation method with compound duct catalysis material |
CN104671253B (en) * | 2015-02-16 | 2017-01-04 | 黑龙江大学 | A kind of preparation method of ZSM-22 molecular sieve nanometer sheet |
CN105195226B (en) * | 2015-10-10 | 2019-06-25 | 苏州智烃新材料科技有限公司 | The polymeric the preparation method of MFI zeolite and its application |
CN106629768A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Synthetic method for uniform nanosized ZSM-5 molecular sieve |
CN106006667B (en) * | 2016-04-22 | 2019-01-29 | 宁夏大学 | A kind of nano-lamellar structure ZSM-5 molecular sieve and its synthetic method |
CN106006669B (en) * | 2016-04-22 | 2018-12-07 | 宁夏大学 | A kind of super-paramagnetism nano lamellar structure ZSM-5 molecular sieve and its synthetic method |
CN106006666B (en) * | 2016-04-22 | 2019-02-05 | 宁夏大学 | Nano-lamellar structure multi-stage porous ZSM-5 molecular sieve and its synthetic method |
CN106185978B (en) * | 2016-07-06 | 2018-02-23 | 华东师范大学 | A kind of synthetic method of the high silicon b orientations nanometer sheets of ZSM 5 |
CN107128947A (en) * | 2017-06-30 | 2017-09-05 | 华南理工大学 | A kind of preparation method of the middle zeolite molecular sieves of micro-diplopore ZSM 5 |
CN108059170A (en) * | 2017-12-20 | 2018-05-22 | 广东工业大学 | A kind of controllable method for preparing of the ZSM-5 molecular sieve grown along c-axis |
EP3844103B1 (en) * | 2018-08-27 | 2022-04-06 | Chevron U.S.A. Inc. | Synthesis of molecular sieve ssz-56 |
KR101994765B1 (en) * | 2018-09-21 | 2019-07-01 | 에스케이이노베이션 주식회사 | Hierarchical zeolite and method of preparing the same |
CN109384245A (en) * | 2018-11-30 | 2019-02-26 | 中国科学院大连化学物理研究所 | A kind of macropore-micropore composite S ilicalite-1 molecule sieve and its synthetic method |
CN109911913A (en) * | 2019-04-18 | 2019-06-21 | 南开大学 | Prepare the method and BEA type molecular sieve of BEA type molecular sieve |
CN114057213B (en) * | 2020-07-27 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina material |
CN112279268A (en) * | 2020-08-06 | 2021-01-29 | 中国石油大学胜利学院 | Preparation method and application of hierarchical pore ZSM-5 nano lamellar zeolite |
CN112408419A (en) * | 2020-12-17 | 2021-02-26 | 河南科技大学 | Preparation method of hierarchical porous ZSM-5 nano zeolite |
CN114804143A (en) * | 2022-05-17 | 2022-07-29 | 宁夏大学 | Nano-lamella ZSM-5 molecular sieve and preparation method thereof |
CN116119681A (en) * | 2023-01-11 | 2023-05-16 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101983921A (en) * | 2010-12-01 | 2011-03-09 | 复旦大学 | Method for synthesizing ZSM-5 zeolite orderly accumulated by nanometer crystallite |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0132550A1 (en) * | 1983-06-27 | 1985-02-13 | Norton Company | Novel zeolite and process for preparation |
-
2013
- 2013-05-21 CN CN201310201578.9A patent/CN103288100B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101983921A (en) * | 2010-12-01 | 2011-03-09 | 复旦大学 | Method for synthesizing ZSM-5 zeolite orderly accumulated by nanometer crystallite |
Non-Patent Citations (1)
Title |
---|
ZSM_5型分子筛的微波合成与表征;王燕等;《承德医学院学报》;20121231;第29卷(第4期);第407页3.2合成方法的影响,图3 * |
Also Published As
Publication number | Publication date |
---|---|
CN103288100A (en) | 2013-09-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103288100B (en) | A kind of multi-stage porous ZSM-5 molecular sieve and synthetic method thereof | |
CN108910910B (en) | ZSM-35 molecular sieve and preparation method thereof | |
CN104030314B (en) | A kind of ZSM-5 Quito level porous molecular sieve material and preparation method thereof | |
CN103803581B (en) | A kind of nucleocapsid structure ZSM-5 composite molecular screen and its preparation method and application | |
US8709963B2 (en) | Molecular sieve | |
CN107777701B (en) | SCM-12 molecular sieve and preparation method thereof | |
CN110668458B (en) | Al-SBA-15 mesoporous molecular sieve, denitration catalyst, preparation methods of Al-SBA-15 mesoporous molecular sieve and denitration catalyst, and application of Al-SBA-15 mesoporous molecular sieve and denitration catalyst | |
CN101314135A (en) | Method for preparing double-catalysis center molecular sieve nucleocapsid material with hydrothermal/solvent-thermal system | |
CN106673011A (en) | Production method of SFE-structured molecular sieve, SFE-structured molecular sieve and application of SFE-structured molecular sieve | |
CN104117384B (en) | Toluene methylation catalyst and method for producing p-xylene in presence of same | |
CN106745055A (en) | A kind of synthetic method of the molecular sieves of monoblock type multi-stage porous ZSM 5 | |
CN102838131A (en) | Sapo-34 molecular sieve and preparation method thereof | |
CN114014334A (en) | Medium silicon-aluminum ratio ZSM-5 heterozygous nanosheet molecular sieve and preparation method thereof | |
CN102910644A (en) | Multistage pore ZSM-5 molecular sieve and preparation method thereof | |
CN102627297A (en) | Synthetic method for SAPO (Silicoaluminophosphate)-34 molecular sieve | |
KR101451902B1 (en) | Zeolite with MRE structure and their analogue materials possessing mesopore, and synthesis method thereof | |
Koike et al. | Increasing the ion-exchange capacity of MFI zeolites by introducing Zn to aluminosilicate frameworks | |
CN105731484A (en) | Synthetic method of meso-microporous SAPO-34 molecular sieve | |
CN103058208A (en) | Preparation method of SAPO-56 molecular sieve | |
CN109607563A (en) | Zinc modification multi-stage porous ZSM-5 nano zeolite and preparation method thereof | |
CN106809859A (en) | The synthetic method and ZSM-5 molecular sieve of a kind of ZSM-5 molecular sieve | |
CN103043681A (en) | Preparation method of nano layered ZSM (Zeolite Molecular Sieve)-5 zeolite molecular sieve | |
CN112694100B (en) | Fe-ZSM-5 molecular sieve, preparation method and application thereof | |
CN101205171B (en) | Method for preparing dimethyl ether by dehydration of methanol | |
KR20050019530A (en) | Metal-incorporated nanoporous materials, Metal-VSB-5 molecular sieve and their preparation methods |
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 | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151125 Termination date: 20160521 |
|
CF01 | Termination of patent right due to non-payment of annual fee |