CN104445259A - Multilayered structure ZSM-5 molecular sieve and preparation method thereof - Google Patents
Multilayered structure ZSM-5 molecular sieve and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to a multilayered structure ZSM-5 molecular sieve and a preparation method thereof, and the preparation method is mainly used for solving the technical problem in the prior art that the multilayered structure ZSM-5 molecular sieve cannot be obtained. In order to better solve the problem, the technical scheme adopted by the invention is as follows: the multilayered structure ZSM-5 molecular sieve comprises a core phase and a shell layer cladding the core phase; the core phase and the shell layer have MFI structures; the silicon-aluminum atomic ratio Si/Al of the core phase is greater than or equal to 8; the silicon-aluminum atomic ratio of the shell layer is greater than or equal to 8; the thickness of the shell layer is 0.5-3,000nm; the preparation method of the molecular sieve comprises the following steps: evenly mixing the ZSM-5 molecular sieve core with a silicon source, an aluminum source, a templating agent R and a water raw material; and synthesizing for at least twice under the hydrothermal condition, so as to prepare the required multilayered structure ZSM-5 molecular sieve. The preparation method can be applied to industrial production of the multilayered structure ZSM-5 molecular sieve.
Description
Technical field
The present invention relates to a kind of multilayered structure ZSM-5 molecular sieve and preparation method thereof.
Background technology
Zeolite molecular sieve is the crystalline microporous material that a class has skeleton structure, because it has the controlled advantage of specific pore size, constitutional features, larger specific surface area, suitable physical strength, the suitability to chemical reaction and the selectivity to catalyzed reaction, often be applied in many catalyzed reactions, especially in refining of petroleum and processing, Coal Chemical Industry, gas chemical industry, biomass industry and polymer precursor the aspect such as to be prepared and are had a wide range of applications.
Along with the development of human society, the product demand kind of people to petrochemical complex, Coal Chemical Industry, biomass conversion, gas chemical industry and carbon one chemical industry gets more and more, and demand is increasing, and thus the requirement of relevant industries to catalyzer is also more and more higher.This just proposes requirement to the molecular sieve catalysts performance that raising chemical industry is most widely used.The difficult point of molecular sieve catalysts is the selectivity how improving its catalysis while improving its catalytic activity.
The molecular sieve that current catalytic field is conventional is generally sieve and silica-sesquioxide, and also have some to contain a small amount of phosphorus, arsenic, germanium, the elements such as iron, in general, the aluminium in molecular sieve, iron and phosphorus equipotential are set to the active sites of catalyzed reaction, and silicon is the inertia position of catalyzed reaction.Improving the catalytic reaction activity of molecular sieve, generally by reducing the way of Si/Al ratio, as increased aluminium content or removing a part of silicon, can increase the catalytic active site of molecular sieve.In addition, the methods such as dipping, grinding, chemical vapour deposition or physical vapor deposition also can be adopted in molecular sieve surface or duct, to increase some elements (as: iron, platinum, palladium and gold etc.) content to increase the way of active sites.
But too high reactive behavior may cause generation and the carbon distribution of a lot of side reaction, and causes catalyst deactivation.Especially the active sites of molecular sieve outer surface contacts with reactant fully, is easy to cause side reaction and cause carbon distribution in catalytic process, to such an extent as to blocks duct, causes the thorough inactivation of molecular sieve.Therefore, how under the prerequisite keeping molecular sieve high catalytic activity, molecular sieve is modified, reduce the reaction active site of its outside surface, reach and improve the Important Problems that its selectivity and life-span are current catalytic fields.
Once had US Patent No. 4067920, modification that US4011276, US5367099 and US5607888 proposed to carry out ZSM-5 molecular sieve pore structure, namely reduce port size and shield outer surface acidity active sites to prepare shape-selective catalyst, but it needs to carry out repeatedly modification to catalyzer, and after the rising of modified catalysts selectivity, transformation efficiency declines more.
In 99 oC crystallization after 3 hours after US4868146 introduced and was fully mixed with water by the nuclear phase molecular sieve of sodium hydroxide, 4-propyl bromide, silicon sol, little crystal grain, add Neutral ammonium fluoride again, continue crystallization 16 hours, products therefrom can obtain a kind of molecular sieve of outside surface inertia through washing, drying and roasting, and this kind of method can be prepared into the molecular sieve that ZSM-5 and ZSM-23 is nuclear phase.US4503164 describes with borosilicate crystal for core, and silica crystal is the zeolite molecular sieve of shell, SiO in its borosilicate nucleus
2/ B
2o
3be greater than 12, the proportion of shell and core is 0.1 ~ 5.
CN101279288B and CN100469695C describes respectively and adopts located growth method after ZSM-5 molecular sieve area load phosphorus aluminium or silicon phosphorus aluminium, to prepare core-shell molecular sieve in advance, with be core with aluminium silicophosphate molecular sieve, take Pentasil as the synthetic method of the core-shell molecular sieve of shell.The preparation method of the binary zeolite that it be karyophan light is shell that CN101177276B describes with Beta, this catalyzer can catalysis methanol preparing dimethy ether.It is silicon source that CN100595146C also introduced with water glass, using alumel as aluminium source, ethamine is auxiliary agent, then by synthesis liquid under normal conditions crystallization prepare the method for core-shell molecular sieve, and by the nanocrystalline pattern in regulation and control crystallization temperature, time, the thickness of regulation and control shell and inside.
CN101723401B, CN101723402B and document (D.J. Kong, J.L. Zheng, X.H. Yuan, Y.D. Wang, D.Y. Fang, Fabrication of Core/shell Structure via Overgrowth of ZSM-5 Layers on Mordenite Crystals, Microporous and Mesoporous Materials 119 (2009) 91-96.) describe the method adopting epitaxial growth method directly to synthesize ZSM-5/ZSM-5 type nucleocapsid structure molecular sieve.
The molecular sieve of the nucleocapsid structure of current bibliographical information generally passes through the parameter such as pore passage structure, silica alumina ratio, shell thickness of modulation nuclear phase molecular sieve and shell, adjust the activity of molecular sieve surface, reduce carbon distribution, the object in extending catalyst life-span to reach in catalyzed reaction.
The molecular sieve of multilayered structure can make the privileged site of reactant molecule in molecular sieve pore passage that specific chemical reaction occurs, and also can be come catalysis and the absorption property of modulation molecular sieve by the composition and structure controlling every layer.But still there is no ZSM-5 molecular sieve and the synthetic method thereof of bibliographical information multilayered structure at present.
Summary of the invention
One of technical problem to be solved by this invention is the problem that prior art cannot prepare the ZSM-5 molecular sieve of multilayered structure, provides a kind of new multilayered structure ZSM-5 molecular sieve.Multilayered structure ZSM-5 molecular sieve every layer of the present invention all has MFI structure, has under the prerequisite of not blocking molecular sieve pipeline, modifies ZSM-5 molecular sieve surface, improves the advantage of the performance of catalyzer.
Two of technical problem to be solved by this invention is to provide a kind of synthetic method of the multilayered structure ZSM-5 molecular sieve corresponding with one of technical solution problem.
Three of technical problem to be solved by this invention is that the low problem of p-Xylol reaction preference is prepared in catalysis, provides a kind of method preparing dimethylbenzene newly.When the method is used for the mixing raw materials such as benzene, toluene, methyl alcohol to be converted into dimethylbenzene, have the advantages that selectivity of product is high.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ZSM-5 molecular sieve of multilayered structure, comprise nuclear phase ZSM-5 molecular sieve and the shell ZSM-5 molecular sieve being wrapped in nuclear phase outside, nuclear phase and shell all have MTW structure, described nuclear phase sial atomic ratio Si/Al=8 ~ ∞, described shell sial atomic ratio is 8 ~ ∞, and shell thickness is 0.5 ~ 3000 nm.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of described multilayered structure ZSM-5 molecular sieve, comprises following several step:
A () is by silicon source Si, aluminium source Al, with M
xthe alkali source that O counts, water and template R mixing and stirring according to a certain percentage, obtain mixture I, the mol ratio of the various materials in gained mixture I is: R:SiO
2=0.02 ~ 2, H
2o:SiO
2=5 ~ 5000, Si:Al > 20, M
xo:Si=0.06 ~ 0.6, x=1,2;
B the ZSM-5 molecular sieve of any silica alumina ratio is put into said mixture I by (), and continue to stir, and obtains mixture II;
C mixture II obtained above is put into reactor by (); Crystallization temperature is 70 ~ 180 oC, and constant temperature keeps 0.5 h to 480 h;
D above-mentioned product cools by (), and after filtration, dry after washing, after 400 ~ 700 oC roasting 1 ~ 10 hour;
E () repeats above-mentioned (a)-(d) step at least one times, namely obtain the ZSM-5 molecular sieve of multilayered structure;
Wherein, silicon source is at least one in silica gel, white carbon black, water glass, tetraethoxy etc.; Aluminium source is at least one in sodium metaaluminate, aluminum chloride, Tai-Ace S 150, aluminum nitrate, aluminium hydroxide, AlOOH etc.; Alkali metal source is containing the material of at least one element in sodium, potassium, elemental lithium; Template is at least one in Neutral ammonium fluoride, ammoniacal liquor, TPAOH, 4-propyl bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetraethyl ammonium hydroxide.
In technique scheme, the mol ratio of the various materials in gained mixture I is: R:SiO
2=0.02 ~ 2, H
2o:SiO
2=5 ~ 5000, Si:Al > 20, M
xo:Si=0.06 ~ 0.6, x=1,2.
Described crystallization time is 0.5 h to 480 h, and crystallization temperature is 70 ~ 180 oC, repeats a-d step at least twice, namely obtains the ZSM-5 molecular sieve of multilayered structure.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method of producing dimethylbenzene, when the mixing raw materials such as benzene, toluene, methyl alcohol are converted into dimethylbenzene, has the advantages that selectivity of product is high.Be 250 ~ 480 DEG C in temperature of reaction, reaction pressure 0.1 ~ 3.5MPa, weight space velocity is 1.0 ~ 4.5h
-1, reaction generates the product comprising dimethylbenzene.
The present invention is owing to adopting Si-Al molecular sieve to be nuclear phase, and the shell prepared can, only containing silica, also can be the mixture containing silica or aluminum oxide.The innovative point of this technology is that the molecular sieve synthesized is multilayered structure, can the silica alumina ratio of each layer of modulation and thickness flexibly.Multilayered structure ZSM-5 molecular sieve can be used for the production field of dimethylbenzene, and improve selectivity and the Selectivity for paraxylene of xylene products, the selectivity of p-Xylol reaches more than 76%.
Accompanying drawing explanation
Fig. 1: the XRD characterization result of the ZSM-5 molecular sieve after growth shell
Fig. 2: the SEM characterization result of the ZSM-5 molecular sieve after growth shell
Below by specific examples, the present invention is further elaborated.
Embodiment
[embodiment 1]
1, by tetraethyl silane, TPABr, NaOH, Al (NO
3)
3, H
2o prepares burden with the ratio of mol ratio 1.44:0.45:0.53:0.04:118, and wherein the amount of water is 150 grams; First by water-soluble to aluminum nitrate, sodium hydroxide and TPABr, slowly drip tetraethoxy afterwards, stir.
2, the ZSM-5 molecular sieve 10 g core of sodium form Si/Al=70 is poured in above-mentioned solution, and continue to stir.
3, sample is poured into in the little vexed tank of teflon-lined, sealing, and be heated to 180 oC constant temperature and keep 24 h.
4, above-mentioned product is adopted water coolant chilling, and after filtration, washing, at 120 oC baking oven inner drying 12 h.
5,550oC roasting 4 hours after taking out, namely Product samples is obtained.These product core Si/Al=70, outer Si/Al=104, shell thickness about 1000 nm.
Product X RD and SEM the results are shown in Figure of description: as can be seen from XRD result, and nuclear phase ZSM-5 and the sample after growing shell are MFI structure.
[embodiment 2]
1, the TEAOH aqueous solution of 40% is mixed with 0.685 g sodium metaaluminate and 37g water and stirs, be added dropwise to 40% silicon sol and at room temperature mixing and stirring.
2, product 10 g in embodiment 1 is poured in above-mentioned solution, and continue to stir.
3, sample is poured into in the little vexed tank of teflon-lined, sealing, and heat, make temperature remain on 160 oC and keep 120 h.
4, above-mentioned product is adopted water coolant chilling, and after filtration, washing, at 120 oC baking oven inner drying 12 h.
5,550oC roasting 4 hours after taking out, the MFI structure product of three layers is obtained, core kernel Si/Al=70 of product; Si/Al=104, middle layer, thickness 1000 nm; Outer Si/Al=190, thick 50 nm.
[embodiment 3]
1,3 g dehydrated alcohols are added after the TPAOH aqueous solution 9 g of 25% and tetraethoxy 8 g and water 40 g fully being stirred 5 h.
2, product 10 g in embodiment 1 is poured in above-mentioned solution, and continue to stir.
3, sample is poured into in the little vexed tank of teflon-lined, sealing, and heat, make temperature remain on 180 oC and keep 24 h.
4, above-mentioned product is adopted water coolant chilling, and after filtration, washing, at 120 oC baking oven inner drying 12 h.
5,550oC roasting 4 hours after taking out, MFI structure product is obtained, core kernel Si/Al=70 of product; Si/Al=104, middle layer, thickness 1000 nm; Skin is pure silicon, thick 400 nm.
[embodiment 4-11]
By the ZSM-5 molecular sieve of any silica alumina ratio of 10 g, according to material proportion and the synthesis condition of table 1, operate according to the step in embodiment 1, the MFI structure molecular sieve shell meeting silica alumina ratio in table can be obtained.
Table 1
[embodiment 12-10]
The multilayered structure ZSM-5 molecular sieve of embodiment 1 is used for the production of dimethylbenzene, with benzene, toluene, methyl alcohol, water etc. for raw material, be 250 ~ 480 DEG C in temperature of reaction, reaction pressure 0.1 ~ 3.5MPa, weight space velocity is 1.0 ~ 4.5h
-1, reaction generates the product comprising dimethylbenzene.Refer to table 2.
Table 2
| Embodiment | Raw material | Feed molar proportioning | Reaction pressure (MPa) | Time heavy air speed (h -1） | Temperature of reaction (DEG C) | Hydrogen-hydrocarbon ratio | Dimethylbenzene selective | P-Xylol/dimethylbenzene |
| 12 | Benzene: toluene: methyl alcohol: water | 2:1:9:1 | 2.5 | 2.5 | 420 | 0 | 63% | 89.14% |
| 13 | Benzene: toluene: methyl alcohol: water | 1:2:6:0 | 0.1 | 4.0 | 310 | 1 | 52% | 90.32% |
| 14 | Toluene: methyl alcohol: water | 2:7:1 | 2.0 | 1.0 | 350 | 0 | 76% | 92.64% |
| 15 | Toluene: methyl alcohol: water | 4:2:1 | 0.5 | 2.3 | 480 | 0.5 | 75% | 91.44% |
| 16 | Toluene: methyl alcohol: water | 4:2.5:1 | 0.2 | 3.5 | 370 | 0 | 35% | 89.93% |
| 17 | Benzene: methyl alcohol: water | 4:8:1 | 0.2 | 2.8 | 450 | 0 | 63% | 90.07% |
| 18 | Benzene: methyl alcohol: water | 4:3:1 | 0.1 | 4.0 | 440 | 0.1 | 20% | 90.35% |
| 19 | Toluene | 3.5 | 2.5 | 460 | 1.5 | 45% | 93.65% | |
| 20 | Toluene | 2.0 | 3.3 | 360 | 2.3 | 42 | 92.80% | |
| 21 | Toluene | 3.0 | 4.5 | 280 | 4.3 | 41% | 92.41% |
Claims (10)
1. the ZSM-5 molecular sieve of a multilayered structure, comprise nuclear phase ZSM-5 molecular sieve and the shell ZSM-5 molecular sieve being wrapped in nuclear phase outside, nuclear phase and shell all have MFI structure, described nuclear phase sial atomic ratio Si/Al=8 ~ ∞, described shell sial atomic ratio is 8 ~ ∞, and shell thickness is 0.5 ~ 3000 nm.
2. multilayered structure ZSM-5 molecular sieve according to claim 1, is characterized in that described nuclear phase sial atomic ratio Si/Al=10 ~ 1000, and described shell sial atomic ratio is 10 ~ 1000, and shell thickness is 1 ~ 500 nm.
3. the preparation method of multilayered structure ZSM-5 molecular sieve according to claim 1, comprises following several step:
A) by silicon source Si, aluminium source Al, with M
xthe alkali source that O counts, water and template R mixing and stirring according to a certain percentage, obtain mixture I, the mol ratio of the various materials in gained mixture I is: R:SiO
2=0.02 ~ 2, H
2o:SiO
2=5 ~ 5000, Si:Al > 20, M
xo:Si=0.06 ~ 0.6, x=1,2;
B) ZSM-5 molecular sieve is mixed with said mixture I, obtain mixture II;
C) mixture II obtained above is put into reactor; Crystallization temperature is 70 ~ 180 oC, and constant temperature keeps 0.5 h to 480 h;
D) above-mentioned product is cooled, and after filtration, dry after washing, after 350 ~ 700 oC roasting 1 ~ 10 hour;
E) repeat above-mentioned a) ~ d) step at least one times, namely obtain the ZSM-5 molecular sieve of multilayered structure.
4. multilayered structure ZSM-5 molecular sieve according to claim 3, is characterized in that: silicon source is at least one in silica gel, white carbon black, water glass, tetraethoxy etc.; Aluminium source is at least one in sodium metaaluminate, aluminum chloride, Tai-Ace S 150, aluminum nitrate, aluminium hydroxide, AlOOH etc.; Alkali metal source is containing the material of at least one element in sodium, potassium, elemental lithium; Template is at least one in Neutral ammonium fluoride, ammoniacal liquor, TPAOH, 4-propyl bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetraethyl ammonium hydroxide.
5. multilayered structure ZSM-5 molecular sieve according to claim 3, is characterized in that: the mol ratio of the various materials in gained mixture I is: R:SiO
2=0.03 ~ 2, H
2o:SiO
2=5 ~ 3500, Si:Al > 25, M
xo:Si=0.07 ~ 0.5, x=1,2.
6. multilayered structure ZSM-5 molecular sieve according to claim 3, is characterized in that: mixed with said mixture I by ZSM-5 molecular sieve, and stir.
7. multilayered structure ZSM-5 molecular sieve according to claim 3, is characterized in that: crystallization temperature is 90 ~ 175 oC, and constant temperature keeps 5 h to 240 h.
8. multilayered structure ZSM-5 molecular sieve according to claim 3, is characterized in that: 380 ~ 650 oC roastings 1 ~ 5 hour.
9. multilayered structure ZSM-5 molecular sieve according to claim 3, is characterized in that: repeat a) ~ d) step at least twice.
10. produce a method for dimethylbenzene, with benzene, toluene, methyl alcohol, water etc. for raw material, be 250 ~ 480 DEG C in temperature of reaction, reaction pressure 0.1 ~ 3.5MPa, weight space velocity is 1.0 ~ 4.5h
-1, raw material is contacted with any one molecular sieve catalyst in claim 1 or 2 by beds, and reaction generates the product comprising dimethylbenzene.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082257A (en) * | 2016-06-08 | 2016-11-09 | 清华大学 | A kind of hollow molecular sieve, preparation method and applications |
| CN108726534A (en) * | 2018-06-07 | 2018-11-02 | 西安工程大学 | A kind of preparation method of micro- mesoporous ZSM-5 molecular sieve |
| CN109133084A (en) * | 2018-09-12 | 2019-01-04 | 中国科学院山西煤炭化学研究所 | A kind of method that catalytic gasification coal ash prepares molecular sieve |
| CN109775722A (en) * | 2019-03-26 | 2019-05-21 | 大连理工大学 | A kind of preparation method of multi-stage porous ZSM-5 nanometers of aggregates |
| CN111054430A (en) * | 2020-01-17 | 2020-04-24 | 太原理工大学 | Core-shell structure HZSM-5 molecular sieve for reaction of preparing aromatic hydrocarbon from methanol and preparation method thereof |
| CN111744542A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Xylene isomerization catalyst and preparation method thereof |
| WO2023201810A1 (en) * | 2022-04-18 | 2023-10-26 | 瑞声声学科技(深圳)有限公司 | Core-shell molecular sieve and preparation method therefor, sound-absorbing material, and loudspeaker |
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| CN101884935A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Catalyst material and preparation method thereof |
| CN102463136A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Core-shell structure MFI molecular sieve and its preparation method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082257A (en) * | 2016-06-08 | 2016-11-09 | 清华大学 | A kind of hollow molecular sieve, preparation method and applications |
| CN108726534A (en) * | 2018-06-07 | 2018-11-02 | 西安工程大学 | A kind of preparation method of micro- mesoporous ZSM-5 molecular sieve |
| CN108726534B (en) * | 2018-06-07 | 2021-08-10 | 西安工程大学 | Preparation method of micro-mesoporous ZSM-5 molecular sieve |
| CN109133084A (en) * | 2018-09-12 | 2019-01-04 | 中国科学院山西煤炭化学研究所 | A kind of method that catalytic gasification coal ash prepares molecular sieve |
| CN109775722A (en) * | 2019-03-26 | 2019-05-21 | 大连理工大学 | A kind of preparation method of multi-stage porous ZSM-5 nanometers of aggregates |
| CN109775722B (en) * | 2019-03-26 | 2020-08-21 | 大连理工大学 | Preparation method of hierarchical pore ZSM-5 nano aggregate |
| CN111744542A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Xylene isomerization catalyst and preparation method thereof |
| CN111054430A (en) * | 2020-01-17 | 2020-04-24 | 太原理工大学 | Core-shell structure HZSM-5 molecular sieve for reaction of preparing aromatic hydrocarbon from methanol and preparation method thereof |
| WO2023201810A1 (en) * | 2022-04-18 | 2023-10-26 | 瑞声声学科技(深圳)有限公司 | Core-shell molecular sieve and preparation method therefor, sound-absorbing material, and loudspeaker |
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