CN107792864A - A kind of preparation method of the molecular sieves of size tunable P ZSM 5 - Google Patents
A kind of preparation method of the molecular sieves of size tunable P ZSM 5 Download PDFInfo
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- CN107792864A CN107792864A CN201711038405.4A CN201711038405A CN107792864A CN 107792864 A CN107792864 A CN 107792864A CN 201711038405 A CN201711038405 A CN 201711038405A CN 107792864 A CN107792864 A CN 107792864A
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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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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
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Abstract
The invention discloses a kind of molecular sieve preparation methods of P ZSM 5 of size tunable.This method uses phosphorus source, silicon source, silicon source, alkali source, inorganic acid, template, alkali metal salt, anion surfactant, the crystal seeds of ZSM 5 as raw material, the hydrothermal crystallizing in reactor, filtered, washing, dry, roasting, obtain the molecular sieves of P ZSM 5 that particle diameter is 100nm~10 μm.The present invention controls particle size by adding alkali metal salt or anion surfactant, the molecular sieves of gained P ZSM 5 have high hydrothermal stability, and it disclosure satisfy that requirement of the differential responses to different-grain diameter, the application of the molecular sieves of P ZSM 5 is increased, is reacted suitable for methanol-to-olefins, preparing gasoline by methanol, alkylation of toluene methanol etc..
Description
Technical field
The invention belongs to Zeolite synthesis field, and in particular to a kind of P-ZSM-5 points of the high hydrothermal stability of controllable crystal
The preparation method of son sieve.
Background technology
ZSM-5 molecular sieve is as template, in 1972 first by Mobil companies of the U.S. using TPAOH
A kind of micropore Si-Al molecular sieve of synthesis, its structure is mainly alumino-silicate anion frame, by [SiO2] tetrahedron and
[Al2O3] tetrahedron composition.The main aperture road of ZSM-5 molecular sieve is a kind of containing two kinds of cross one another pore canal systems into ten-ring
The sinusoidal duct in (100) face is parallel to, pore size is 0.55nm × 0.51nm；Another kind is parallel to (010) face
Straight hole road, size are 0.56nm × 0.53nm.ZSM-5 main structure body is aluminosilicate framework, has acid resistance, good heat
Stability and hydrothermal stability, while there is good Shape-selective, it is widely used in catalytic reaction, including catalytic pyrolysis,
Isomerization, aromatisation, disproportionation, alkylation etc. are reacted.
ZSM-5 molecular sieve grain size is to control the important indicator of its Shape-selective and catalytic performance, small-grain ZSM-5 point
Son sieve external surface area is big, and diffusion duct is short, and aperture is more, and catalytic activity is high, and carbon accumulation resisting ability is strong, less demanding to shape selectivity
Excellent catalytic performance is shown in catalytic reaction；Big crystal grain ZSM-5 molecular sieve activated centre is predominantly located inside duct, although
Catalytic activity is relatively low, but has higher shape selectivity, is usually used in shape selective catalytic reaction.Except grain size, ZSM-5 molecular sieve hydro-thermal
Stability is also that the catalytic reaction that ZSM-5 molecular sieve participates in is in thermal and hydric environment mostly an important factor for influenceing its catalytic performance
Lower progress, such as preparing gasoline by methanol, methanol-to-olefins, alkylation of toluene methanol, toluene disproportionation, FCC propylene enhancings etc., in high temperature
Framework dealumination and permanent inactivation are easily caused under hydrothermal condition, it is steady to improving its catalysis to improve ZSM-5 molecular sieve hydrothermal stability
It is qualitative significant.
About patent and document report, by phosphorous modified ZSM-5 molecular sieve, its hydrothermal stability can be improved.Patent
CN104108724 discloses a kind of method of one-step synthesis method little crystal grain P-ZSM-5 molecular sieves, and crystallite dimension is 1~2 μm, is carried
High hydrothermal stability of molecular sieve, available for improving productivity of propylene in catalyst for heavy oil catalytic cracking or improve octane number.
Patent CN1915821 discloses a kind of method being deposited in phosphorous oxides by chemical vapor infiltration on ZSM-5 molecular sieve,
Phosphorous oxides is uniformly dispersed over a molecular sieve, improves the hydrothermal stability of molecular sieve.Patent USP5171921 discloses one kind
The ZSM-5 molecular sieve for being 20~60 with phosphoric acid or phosphate dipping silica alumina ratio, is then activated in high-temperature vapor, available for general
Alkene or aliphatic hydrocarbon are converted into the catalytic active component of C2~C5 alkene.Patent CN101184710 discloses a kind of phosphorus compound
The method of modified high silica alumina ratio ZSM-5 molecular sieve hydro-thermal process, after P Modification, calcining, hydro-thermal process, available for aromatics
Alkylated reaction.Patent CN101759199 discloses ZSM-5 molecular sieve of a kind of silicon, P Modification and preparation method thereof, and phosphorus is dividing
The top layer of son sieve and central core uneven distribution, excellent pair is shown in alkylation of toluene methanol prepares paraxylene reaction
Dimethylbenzene selective and preferable catalytic stability.
It is basic to be prepared using by the method for the ZSM-5 molecular sieve post-modification synthesized in published result of study
P-ZSM-5 molecular sieves, also needing just obtain product by last handling processes such as drying, roastings, preparation flow length, technique is cumbersome,
Virtually add production cost；And the P-ZSM-5 molecular sieves of direct synthesis are used, particle diameter distribution is single, can not meet not
With the reaction requirement different to grain size.
The content of the invention
The technical problems to be solved by the invention are to overcome technical problem existing for prior art, there is provided a kind of grain size
Controllable, high hydrothermal stability P-ZSM-5 Zeolite synthesis methods.
The technical solution of the present invention is a kind of preparation method of controllable crystal P-ZSM-5 molecular sieves, its specific preparation
Step is as follows：
(1) by silicon source deionized water dissolving, add mineral acid acidified, until completely dissolved, addition water dissolves
Alkali metal salt or surfactant, the phosphorus source dissolved with water is eventually adding, stir to obtain solution A at room temperature；
(2) silicon source, sodium hydroxide, template, deionized water are mixed, after stirring, it is brilliant adds ZSM-5 molecular sieve
Kind, stir down to obtain solution B at room temperature；The addition of wherein described ZSM-5 molecular sieve crystal seed is SiO in silicon source2Quality point
Several 0~10%；
(3) under agitation, solution A is slowly added in solution B so that mixture total composition mol ratio is Na2O:
Al2O3:SiO2:P2O3:Q:H2O:M or LAS=(3~40)：1：(20~150)：(0.2~1.5)：(5~40)：(1000~
6000)：(5~60) or (3~30), wherein Na2O represents basicity, M represents the alkali metal salt added, LAS represents anionic surface
Activating agent, Q represent template；
(4) above-mentioned silicon-aluminum mixture is fitted into reactor and carries out hydro-thermal reaction, 70 DEG C~120 DEG C 6~48h of aging, risen
Temperature is to 120 DEG C~190 DEG C 6~72h of crystallization.Reaction is terminated into rear product to filter, wash, dry to obtain P-ZSM-5 molecular sieves.
In above-mentioned technical proposal, source of aluminium preferably is selected from least one of aluminum sulfate, aluminum nitrate, aluminium chloride, aluminium isopropoxide.
In above-mentioned technical proposal, the inorganic acid preferably is selected from sulfuric acid, hydrochloric acid or nitric acid.
In above-mentioned technical proposal, the alkali metal salt preferably be selected from sodium chloride, sodium nitrate, sodium sulphate, potassium chloride, potassium nitrate or
Potassium sulfate.
In above-mentioned technical proposal, the anion surfactant preferably is selected from lauryl sodium sulfate, hexadecyl hydrosulfate
Sodium or sodium stearyl sulfate.
In above-mentioned technical proposal, described ZSM-5 molecular sieve crystal seed be silica alumina ratio be 20~60, particle diameter be 150~300nm
ZSM-5 molecular sieve with small crystal grains, addition is preferably SiO in silicon source2The 0.5%~5% of mass fraction.
In above-mentioned technical proposal, phosphorus source preferably is selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or AlPO4。
In above-mentioned technical proposal, the silicon source preferably is selected from waterglass, Ludox, Silica hydrogel, white carbon or tetraethyl orthosilicate
At least one of.
In above-mentioned technical proposal, the template preferably is selected from n-butylamine, ethylenediamine, tripropyl amine (TPA), hexamethylene diamine or triethanolamine.
In above-mentioned technical proposal, mixture total composition mol ratio is preferably Na2O:Al2O3:SiO2:P2O3:Q:H2O:M or
LAS=(5~20):1:(30~100):(0.5~1):(10~25):(1000~3000):(10~30) or (5~20).Its
Middle Na2O represents basicity, M represents the alkali metal salt added, LAS represents anion surfactant, Q represents template.
In above-mentioned technical proposal, step (4) is preferably 80 DEG C~100 DEG C 12~24h of aging, 150 DEG C~180 DEG C crystallization 18
~48h, filtering, washing, dry, calcine routinely condition.
By adding alkali metal salt or anion surfactant, P-ZSM-5 particle diameters can be controlled, size controlling scope is
100nm~10 μm, within this range, P-ZSM-5 molecular sieve particle diameter distributions are uniform.
The beneficial effect that is reached of the present invention is：
1) the inventive method introduces phosphorus into framework of molecular sieve, direct hydrothermal synthesis P-ZSM-5 molecular sieves, work by one-step method
Skill is simple, avoids post-modification step.
2) the inventive method can accurately control P-ZSM- by adding alkali metal or surfactant into synthetic system
5 zeolite crystal sizes, and alkali metal salt and anion surfactant are cheap, and production cost is low.
3) it is high by P-ZSM-5 hydrothermal stability of molecular sieve made from the inventive method, the size tunable (μ of 100nm~10
M), requirement of the differential responses to P-ZSM-5 different-grain diameters can be met, methanol-to-olefins suitable for the requirement to different-grain diameter,
Preparing gasoline by methanol, alkylation of toluene methanol etc. react, so as to expand P-ZSM-5 applications.
Brief description of the drawings
Fig. 1 is the SEM figures of P-ZSM-5 sieve samples prepared by embodiment 1,2,3,4.
Fig. 2 is the SEM figures of P-ZSM-5 sieve samples prepared by embodiment 5,6,8,9.
Fig. 3 is the XRD before and after P-ZSM-5 molecular sieve water heats prepared by embodiment 3.
Embodiment
Technical solution of the present invention is described further with reference to embodiment and accompanying drawing.
Embodiment 1
2.62g aluminium isopropoxides are weighed, add 78.5g deionized waters thereto, stirring makes it fully dissolve, and then adds successively
Enter 9.13g sodium chloride, 1.01g diammonium hydrogen phosphates, being stirred continuously is completely dissolved it, forms solution A.
56.3g Ludox is weighed with 53.2g deionized waters, then sequentially adding 4.64g sodium hydroxides, 7.23g second two
Amine, 0.7g ZSM-5 molecular sieve crystal seeds, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 90 DEG C of aging 18h, 150 DEG C of crystallization 48h are warming up to, products therefrom is filtered, washs, dries, being obtained after calcining
To P-ZSM-5 molecular sieves, PZ-1 is designated as.
Embodiment 2
4.74g aluminum nitrates are weighed, add 85.5g deionized waters thereto, stirring makes it fully dissolve, then sequentially added
14.6g sodium nitrate, 0.8g phosphoric acid, being stirred continuously is completely dissolved it, forms solution A.
13.5g white carbons are weighed with 90.6g deionized waters, then sequentially adding the positive fourth of 4.06g sodium hydroxides, 5.62g
Amine, 0.61g ZSM-5 molecular sieve crystal seeds, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 90 DEG C of aging 18h, 160 DEG C of crystallization 42h are warming up to, products therefrom is filtered, washs, dries, being obtained after calcining
To P-ZSM-5 molecular sieves, PZ-2 is designated as.
Embodiment 3
2.09g aluminum sulfate is weighed, adds 48.6g deionized waters thereto, stirring makes it fully dissolve, then sequentially added
The 2.13g concentrated sulfuric acids, 4.62g sodium sulphate, 1.57g diammonium hydrogen phosphates, being stirred continuously is completely dissolved it, forms solution A.
67.2g waterglass is weighed with 51.3g deionized waters, then sequentially adding 4.56g n-butylamines, 0.84g ZSM-5
Molecular sieve seed, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 100 DEG C of aging 12h, 180 DEG C of crystallization 24h are warming up to, products therefrom is filtered, washs, dries, after calcining
P-ZSM-5 molecular sieves are obtained, are designated as PZ-3.
Embodiment 4
2.47g aluminum sulfate is weighed, adds 60.5g deionized waters thereto, stirring makes it fully dissolve, then sequentially added
7.1g sodium sulphate, 1.55g phosphoric acid, being stirred continuously is completely dissolved it, forms solution A.
55.52g Ludox is weighed in 39.63g deionized waters, then sequentially adds 5.26g sodium hydroxides, 3.1g second two
Amine, 0.32g ZSM-5 molecular sieve crystal seeds, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 80 DEG C of aging 24h, 180 DEG C of crystallization 18h are warming up to, products therefrom is filtered, washs, dries, being obtained after calcining
To P-ZSM-5 molecular sieves, PZ-4 is designated as.
Embodiment 5
2.62g aluminium isopropoxides are weighed, add 71.5g deionized waters thereto, stirring makes it fully dissolve, and then adds successively
Enter 8.74g potassium chloride, 1.46g ammonium dihydrogen phosphates, being stirred continuously is completely dissolved it, forms solution A.
43.9g tetraethyl orthosilicates are weighed with 55.8g deionized waters, then sequentially adding 5.45g sodium hydroxides, 7.6g second
Diamines, 0.33g ZSM-5 molecular sieve crystal seeds, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 100 DEG C of aging 12h, 160 DEG C of crystallization 42h are warming up to, products therefrom is filtered, washs, dries, after calcining
P-ZSM-5 molecular sieves are obtained, are designated as PZ-5.
Embodiment 6
3.4g aluminum sulfate is weighed, adds 68.8g deionized waters thereto, stirring makes it fully dissolve, then sequentially added
The 0.78g concentrated sulfuric acids, 6.27g potassium sulfates, 2.09g diammonium hydrogen phosphates, being stirred continuously is completely dissolved it, forms solution A.
52.1g waterglass is weighed with 58.6g deionized waters, then sequentially adding 4.13g n-butylamines, 0.36g ZSM-5
Molecular sieve seed, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 100 DEG C of aging 12h, 150 DEG C of crystallization 48h are warming up to, products therefrom is filtered, washs, dries, after calcining
P-ZSM-5 molecular sieves are obtained, are designated as PZ-6.
Embodiment 7
2.18g aluminium isopropoxides are weighed, add 71.4g deionized waters thereto, stirring makes it fully dissolve, and then adds successively
Enter 9.8g potassium chloride, 1.17g ammonium dihydrogen phosphates, being stirred continuously is completely dissolved it, forms solution A.
64.2g tetraethyl orthosilicates are weighed with 55.7g deionized waters, then sequentially adding 3.79g sodium hydroxides, 4.42g
Ethylenediamine, 0.13g ZSM-5 molecular sieve crystal seeds, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 100 DEG C of aging 12h, 160 DEG C of crystallization 36h are warming up to, products therefrom is filtered, washs, dries, after calcining
P-ZSM-5 molecular sieves are obtained, are designated as PZ-7.
Embodiment 8
2.2g aluminium isopropoxides are weighed, add 80.8g deionized waters thereto, stirring makes it fully dissolve, and then adds successively
Enter 10.9g lauryl sodium sulfate, 2.66gAlPO4.Being stirred continuously is completely dissolved it, forms solution A.
56.3g Ludox is weighed with 67.5g deionized waters, then sequentially adding 6.52g sodium hydroxides, 5.63g second two
Amine, 0.25g ZSM-5 molecular sieve crystal seeds, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 80 DEG C of aging 24h, 170 DEG C of crystallization 36h are warming up to, products therefrom is filtered, washs, dries, being obtained after calcining
To P-ZSM-5 molecular sieves, PZ-8 is designated as.
Embodiment 9
0.75g aluminum nitrates are weighed, add 89.3g deionized waters thereto, stirring makes it fully dissolve, then sequentially added
15.1g sodium hexadecyl sulfates, 3.42g AlPO4, being stirred continuously is completely dissolved it, forms solution A.
18.9g white carbons are weighed with 95.5g deionized waters, then sequentially adding the positive fourth of 5.32g sodium hydroxides, 6.15g
Amine, 0.66g ZSM-5 molecular sieve crystal seeds, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 90 DEG C of aging 24h, 180 DEG C of crystallization 24h are warming up to, products therefrom is filtered, washs, dries, being obtained after calcining
To P-ZSM-5 molecular sieves, PZ-9 is designated as.
Embodiment 10
2.63g aluminum nitrates are weighed, add 89.7g deionized waters thereto, stirring makes it fully dissolve, then sequentially added
18.2g lauryl sodium sulfate, 2.06g AlPO4, being stirred continuously is completely dissolved it, forms solution A.
10.9g white carbons are weighed with 95.2g deionized waters, then sequentially adding the positive fourth of 4.76g sodium hydroxides, 4.22g
Amine, 0.17g ZSM-5 molecular sieve crystal seeds, stir at room temperature, form B solution.
Solution A is slowly added into B solution under agitation, after being sufficiently mixed uniformly, is transferred to liner polytetrafluoro
In ethylene reaction kettle, 90 DEG C of aging 24h, 170 DEG C of crystallization 30h are warming up to, products therefrom is filtered, washs, dries, being obtained after calcining
To P-ZSM-5 molecular sieves, PZ-10 is designated as.
Comparative example 1
In embodiment 3, diammonium hydrogen phosphate addition is changed to 0.69g, and other conditions are constant, is designated as C-1
Comparative example 2
In embodiment 3, diammonium hydrogen phosphate is not added, other conditions are constant, are designated as C-2.
Comparative example 3
In embodiment 3, diammonium hydrogen phosphate is not added, other conditions are constant, and gained molecular sieve ZSM-5 is born by infusion process
P is carried, is designated as C-3.
Hydrothermal stability is tested
The P-ZSM-5 molecular sieves or the hydrothermally stable of ZSM-5 molecular sieve that 1-10 of the embodiment of the present invention and comparative example 1-3 are obtained
Property test be to be carried out in 600 DEG C of hydro-thermal process 36h, crystallinity change and mesopore retain situation before and after analysis, and test result is listed in
Table 1.
Molecular sieve particle size and hydrothermal stability prepared by table 1
Claims (10)
1. the preparation method of the P-ZSM-5 molecular sieves of a kind of size tunable, it is characterised in that comprise the following steps：
(1) by silicon source deionized water dissolving, add it is mineral acid acidified, until completely dissolved, the alkali gold that addition water dissolves
Belong to salt or surfactant, be eventually adding the phosphorus source dissolved with water, stir to obtain solution A at room temperature；
(2) silicon source, sodium hydroxide, template, deionized water are mixed, after stirring, adds ZSM-5 molecular sieve crystal seed, room
Stir to obtain solution B under temperature；The addition of wherein described ZSM-5 crystal seeds is SiO in silicon source2The 0~10% of mass fraction；
(3) under agitation, solution A is slowly added in solution B so that mixture total composition mol ratio is Na2O:Al2O3:
SiO2:P2O5:Q:H2O:M or LAS=(3~40)：1：(20~150)：(0.2~1.5):(5~40)：(1000~6000)：(5
~60) or (3~30), wherein Na2O represents basicity, M represents the alkali metal salt added, LAS represents anion surfactant, Q
Represent template；
(4) above-mentioned silicon-aluminum mixture is fitted into reactor and carries out hydro-thermal reaction, 70 DEG C~120 DEG C 6~48h of aging, be warming up to
120 DEG C~190 DEG C 6~72h of crystallization；Reaction is terminated into rear product to filter, wash, dry, calcine to obtain P-ZSM-5 molecular sieves.
2. preparation method according to claim 1, it is characterised in that described silicon source be aluminum sulfate, aluminum nitrate, aluminium chloride,
At least one of aluminium isopropoxide.
3. preparation method according to claim 1, it is characterised in that described inorganic acid is sulfuric acid, hydrochloric acid or nitric acid.
4. preparation method according to claim 1, it is characterised in that described alkali metal salt is sodium chloride, sodium nitrate, sulphur
Sour sodium, potassium chloride, potassium nitrate or potassium sulfate.
5. preparation method according to claim 1, the anion surfactant described in it is lauryl sodium sulfate, ten
Six sodium alkyl sulfates or sodium stearyl sulfate.
6. preparation method according to claim 1, it is characterised in that described phosphorus source is phosphoric acid, diammonium hydrogen phosphate, phosphoric acid
Ammonium dihydrogen or AlPO4。
7. preparation method according to claim 1, it is characterised in that described silicon source be waterglass, Ludox, Silica hydrogel,
At least one of white carbon or tetraethyl orthosilicate.
8. preparation method according to claim 1, it is characterised in that described organic formwork agent be n-butylamine, ethylenediamine,
Tripropyl amine (TPA), hexamethylene diamine or triethanolamine.
9. preparation method according to claim 1, it is characterised in that the molecular sieve seed of described ZSM~5 is that silica alumina ratio is
20~60, the molecular sieve of fine grain ZSM-5~5 that particle diameter is 150~300nm, addition are SiO in silicon source2The 0.5 of mass fraction~
5%.
10. preparation method according to claim 1, it is characterised in that the particle size of described P-ZSM-5 molecular sieves is equal
It is even and controllable in the μ m of 100nm~10.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112473726A (en) * | 2019-09-11 | 2021-03-12 | 国家能源投资集团有限责任公司 | Composite ZSM-5 molecular sieve, preparation method thereof, catalyst and application thereof |
| CN113351158A (en) * | 2021-06-28 | 2021-09-07 | 上海中船临港船舶装备有限公司 | Zeolite molecular sieve adsorbing material for concentrating VOCs (volatile organic compounds), and preparation method and application thereof |
| CN114933315A (en) * | 2022-06-06 | 2022-08-23 | 中海油天津化工研究设计院有限公司 | High hydrothermal stability UZM-8 molecular sieve and preparation method thereof |
| CN115043413A (en) * | 2022-07-06 | 2022-09-13 | 安阳工学院 | Cross coffin-shaped twin crystal ZSM-5 molecular sieve and controllable preparation method of crystal face exposure size thereof |
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| CN112473726A (en) * | 2019-09-11 | 2021-03-12 | 国家能源投资集团有限责任公司 | Composite ZSM-5 molecular sieve, preparation method thereof, catalyst and application thereof |
| CN112473726B (en) * | 2019-09-11 | 2022-01-28 | 国家能源投资集团有限责任公司 | Composite ZSM-5 molecular sieve, preparation method thereof, catalyst and application thereof |
| CN113351158A (en) * | 2021-06-28 | 2021-09-07 | 上海中船临港船舶装备有限公司 | Zeolite molecular sieve adsorbing material for concentrating VOCs (volatile organic compounds), and preparation method and application thereof |
| CN114933315A (en) * | 2022-06-06 | 2022-08-23 | 中海油天津化工研究设计院有限公司 | High hydrothermal stability UZM-8 molecular sieve and preparation method thereof |
| CN115043413A (en) * | 2022-07-06 | 2022-09-13 | 安阳工学院 | Cross coffin-shaped twin crystal ZSM-5 molecular sieve and controllable preparation method of crystal face exposure size thereof |
| CN115043413B (en) * | 2022-07-06 | 2023-10-20 | 安阳工学院 | Cross coffin twin crystal ZSM-5 molecular sieve and controllable preparation method of crystal face exposure size thereof |
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