CN106542545A - A kind of step hole ZSM-5 zeolite and preparation method thereof - Google Patents
A kind of step hole ZSM-5 zeolite and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of step hole ZSM-5 zeolite and preparation method thereof.The preparation method includes：Template and water are mixed to get into solution；Sodium hydroxide, silicon source, short chain alcohol, silicon source are added in solution, gel mixture is mixed to form, wherein, silicon source is with SiO2Meter, silicon source is with Al2O3Meter, sodium hydroxide, silicon source, silicon source, template, the mol ratio of short chain alcohol and water are (5-15):1:(30-100):(0.5-3):(70-500):(1000-8000)；Crystallization is carried out to gel mixture, solid product is separated, wash, be dried, obtain ZSM-5 zeolite original powder；Roasting is carried out to ZSM-5 zeolite original powder, step hole ZSM-5 zeolite is obtained.Present invention also offers one kind step hole ZSM-5 zeolite by obtained in above-mentioned preparation method.The step hole ZSM-5 zeolite that the present invention is provided has orderly big mesoporous, is conducive to effective diffusion and reaction of macromolecular compound.
Description
Technical field
The present invention relates to a kind of zeolite and preparation method thereof, more particularly to a kind of step hole of orderly mesoporous-micropore
ZSM-5 zeolite and preparation method thereof, belongs to zeolite preparing technical field.
Background technology
Micro-pore zeolite is due to the hole wall with regularly arranged micropore canals and height crystallization and a large amount of equally distributed
Active sites, are widely used in petroleum refining and petrochemical industry.20 century 70s, Mobil companies profit
ZSM type zeolites are developed first with organic additive synthesized gel rubber.HZSM-5 zeolites have acid centre, load
There is after active metal Hydrogenation, therefore be widely used in the petrochemical industries such as catalytic cracking, catalytic hydrogenation.
But universal less, the mass transfer of the molecule that kinetic diameter can be prevented larger, it is impossible to table in the ZSM zeolite aperture of routine
Reveal good catalytic performance.
Ordered mesoporous material (2nm<Diameter<Appearance 50nm), obtains the great attention of material educational circles.For one
Do not need strongly active center and reactant and the larger-size catalytic reaction of product molecule, its catalysis activity apparently higher than
Micro-pore zeolite.But it is unformed due to mesoporous material hole wall so as to which that hydrothermal stability is poor with catalysis activity so as to
Extensively application is restricted.
In order to make up the deficiencies such as the little hydrothermal stability and poor catalytic activity with ordered mesoporous molecular sieve in micro-pore zeolite aperture,
Recently, scientist is prepared by a number of procedures step hole zeolite, wherein having by the method for desiliconization or dealuminzation in zeolite
Middle generation is mesoporous, and using adding mesoporous template to prepare containing mesopore zeolite after pre- crystallization, also hard template method synthesis is containing Jie
The zeolite in hole, resulting containing mesopore zeolite show higher catalysis activity and selectivity compared with Conventional zeolites,
Longer catalytic life and higher anti-carbon deposition ability.
It is how golden that Chinese patent application 201010010136.2 supports structure with Keggin on Nano grade ZSM-5 molecular sieve
Category oxygen hydrochlorate (POM), and the catalytic performance that nickel nitrate improves catalyst is introduced, the gasoline Jing after the catalyst treatment,
The sulfur content in gasoline can be greatly reduced.But the molecular sieve of Nano grade is easily reunited, the life-span of catalyst is made to contract
It is short.
Lizama et al. (Applied Catalusis B:Environmental.82.2008.135) report using mesoporous
SBA-15 is carrier loaded phosphorus tungsten and phosphorus molybdenum, is divided with probe of 4, the 6- dimethyl Dibenzothiophenes for hydrodesulfurization reaction
Son.Result of study shows：The larger aperture of the ordered mesoporous material can allow for larger 4,6- dimethyl dibenzo thiophenes
Fen molecule is reacted into inside duct, reaches deep hydrodesulfurizationof, but, its hole wall is impalpable structure, surely
Qualitative difference, acidity are weak.
(20) petroleum journal, PETROLEUM PROCESSING, 22,2006 report modified Nano ZSM-5 boilings to Zhao Xiaobo et al.
Application of the stone in FCC gasoline modification.Their result of study shows that hydrothermal treatment consists and oxide-metal combinations change
Property nanoparticle HZSM-5 catalyst have a good desulfurization performance, but its stability still needs to improve.
In sum, there is provided the ZSM-5 zeolite of a kind of catalysis activity height and good stability is that this area is urgently to be resolved hurrily
Problem.
The content of the invention
In order to solve the above problems, it is an object of the invention to provide a kind of step hole ZSM-5 zeolite and its preparation side
Method, the ZSM-5 zeolite that the preparation method is obtained have the micropore hole wall of crystallization, and abundant is order mesoporous, and has
There are larger specific surface area and pore volume, be conducive to effective diffusion and reaction of macromolecular compound.
In order to achieve the above object, the invention provides a kind of preparation method of step hole ZSM-5 zeolite, the preparation
Method is comprised the following steps：
Step one：Template and water are mixed to get into solution；
Step 2：Sodium hydroxide, silicon source, short chain alcohol, silicon source are added in solution, gel mixture is mixed to form,
Wherein, sodium hydroxide, silicon source, silicon source, template, the mol ratio of short chain alcohol and water are
(5-15):1:(30-100):(0.5-3):(70-500):(1000-8000), the silicon source is with SiO2Meter, silicon source is with Al2O3Meter；
Step 3：Crystallization is carried out to gel mixture, solid product is separated, wash, be dried, obtain ZSM-5
Zeolite powder；
Step 4：Roasting is carried out to ZSM-5 zeolite original powder, step hole ZSM-5 zeolite is obtained.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that in step 2, in solution
Add sodium hydroxide to stir, add silicon source and stir, be eventually adding the mixture of short chain alcohol and silicon source, stir
Mix to form gel mixture, wherein, the Si in silicon source is 1 with the mol ratio of short chain alcohol:(1-50).
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that in step one and step 2
Mixing temperature is 20 DEG C -60 DEG C.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that the crystallization temperature in step 3
For 120 DEG C -250 DEG C, crystallization time is 12h-240h.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that the sintering temperature in step 4
For 500 DEG C -650 DEG C, roasting time is 4h-12h.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that also include in the preparation method
The step of ammonium is exchanged, carries out, after roasting, carrying out ammonium exchange to ZSM-5 zeolite original powder in step 4, then through taking out
Filter, washing, dry and roasting, obtain step hole ZSM-5 zeolite.
Specific embodiment of the invention, carries out ammonium exchange, and Na type steps hole ZSM-5 zeolite is converted into H
Type step hole ZSM-5 zeolite, wherein, baking temperature is 120 DEG C, and drying time is 6h；Sintering temperature is 500
DEG C -650 DEG C, roasting time is 4h-12h.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that the template of employing includes double
Subtype polyquaternary ammonium salt surfactant；The double type polyquaternary ammonium salt surfactant is by double end cationic polyquaternary amine
Salt is formed with bull cationic polyquaternary ammonium salt.Wherein, double type polyquaternary ammonium salt surfactant can arbitrarily be compared
The double end cationic polyquaternary ammonium salt of example is formed with bull cationic polyquaternary ammonium salt.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that the bull cationic of employing
Polyquaternary ammonium salt be selected from three polyquaternary ammonium salt, four polyquaternary ammonium salt and many polyquaternary ammonium salt, bull cationic polyquaternary ammonium salt it is hydrophobic
Chain is C8-C22Alkyl chain, the connecting group of polyquaternary ammonium salt is C2-C10Alkyl chain.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that the double type polyquaternary amine of employing
Salt surfactant is CH3(CH2)15N(CH3)2(CH2)6N(CH3)2(CH2)15CH3Br2With
CH3(CH2)15[N(CH3)2(CH2)6]n-1N(CH3)2(CH2)15CH3Brn, integers of the n for 3-5.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that the silicon source of employing includes inorganic
The combination of one or more in silicon source and organic silicon source；It is highly preferred that the inorganic silicon source for adopting includes aluminum sulfate, aluminum
Sour sodium, organic silicon source include C2-C5Three secondary aluminum alkoxides；Most preferably, organic silicon source of employing includes different
Aluminum tripropoxide, isobutanol aluminum.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that the silicon source of employing includes inorganic
The combination of one or more in silicon source and organic silicon source；It is highly preferred that the inorganic silicon source for adopting includes waterglass, silicon
Colloidal sol, sodium silicate, organic silicon source are C2-C5Alkyl silicate；Most preferably, organic silicon source bag of employing
Include tetraethyl orthosilicate, positive silicic acid propyl ester.
In the preparation method of the step hole ZSM-5 zeolite that the present invention is provided, it is preferable that the short chain alcohol of employing includes second
Alcohol and C3-C5Secondary alcohol in the combination of one or more.
Present invention also offers a kind of step hole ZSM-5 zeolite, which is prepared by above-mentioned preparation method.
Double type polyquaternary ammonium salt surfactant is adopted for template in the preparation method of the present invention.Double type polyquaternary ammonium salt
Surfactant is had an effect with silicon source, silicon source, is oriented to the formation of ZSM-5 structures, while double type polyquaternary ammonium salt
Long alkyl chain in surfactant plays a part of to prevent silicon-oxy tetrahedron and aluminum-oxygen tetrahedron growth, reaction from completing it
Afterwards, template is removed by roasting and forms micropore and mesopore orbit.
In the present invention, the formation of the meso-hole structure of step hole ZSM-5 zeolite is by following two modes：One is by height
The little crystal grain of crystallization is piled up and is formed, and two is to remove hydrophobic alkyl chain by roasting to produce.
Preparation method provided by the present invention goes out step as templated synthesis with novel gemini type polyquaternary ammonium salt surfactant
Hole ZSM-5 zeolite.The zeolite has step pore structure, and object macromole can be made to react in duct,
And have more acid activity positions and higher acid strength.
Description of the drawings
Fig. 1 is the little angle XRD figure of comparative example 1 and Different Pore Structures ZSM-5 zeolite obtained in embodiment 1-4；
Fig. 2 is the big angle XRD figure of comparative example 1 and Different Pore Structures ZSM-5 zeolite obtained in embodiment 1-4；
Fig. 3 is the N of comparative example 1 and Different Pore Structures ZSM-5 zeolite obtained in embodiment 1-42Adsorption-desorption isothermal
Curve chart；
Fig. 4 is that the ammonia temperature programming of comparative example 1 and Different Pore Structures ZSM-5 zeolite obtained in embodiment 1-4 takes off
Attached curve.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Comparative example 1
This comparative example provides a kind of ZSM-5 zeolite, and which is through the following steps that prepare：
By 70.0g deionized waters, 0.5g sodium hydroxide, 0.3g Patent alums, 2.7g 4-propyl bromides
Mix homogeneously, is added dropwise over 6.6g tetraethyl orthosilicates 4-6h is stirred at 60 DEG C obtaining gel；
Gel is proceeded in teflon-lined stainless steel cauldron, in 150 DEG C of hydrothermal crystallizings 4 days, by water
Product sucking filtration after thermal crystallisation, is washed with deionized to pH<9, then 12h is dried at 120 DEG C, then in horse
Not in stove, 550 DEG C of roastings remove template, obtain Na types routine ZSM-5 zeolite；
Ammonium exchange is carried out to above-mentioned Na types routine ZSM-5 zeolite, then sucking filtration, washing, 120 DEG C be dried 6h, 500
H types routine ZSM-5 zeolite is obtained after DEG C roasting 4h, Z-0 is designated as.
The powder X-ray RD test result of the ZSM-5 zeolite Z-0 that this comparative example is obtained as depicted in figs. 1 and 2, N2
Adsorption-desorption isothermal curve is as shown in figure 3, ammonia temperature programmed desorption curve is as shown in Figure 4.
Embodiment 1
Present embodiments provide a kind of step hole ZSM-5 zeolite, which is through the following steps that prepare：
By 50g deionized waters, tri- polyquaternary ammonium salt C of 1.45g16C6C6C16Br3With 0.38g double end polyquaternary ammonium salt
C16C6C16Br2Mix homogeneously, obtains solution；
0.7g sodium hydroxide is added in solution, is stirred, added 0.6g Patent alums, be subsequently adding
The mixture of 12.4g ethanol and 8.2g tetraethyl orthosilicates, at 40-60 DEG C stirs 4-6h and obtains gel mixture；
Gel mixture is proceeded in teflon-lined stainless steel cauldron, in 150 DEG C of hydrothermal crystallizings 4 days；
The product obtained to hydrothermal crystallizing carries out sucking filtration, is washed with deionized to pH<9, then in 120 DEG C of dryings
Dried sample is put into 550 DEG C of roasting 4h in Muffle furnace by 12h, obtains Na type ZSM-5 zeolites；
Ammonium exchange is carried out to above-mentioned Na types ZSM-5 zeolite, then sucking filtration, washing, 120 DEG C be dried 6h and 500 DEG C
The step hole ZSM-5 zeolite of H types is obtained after roasting 4h, Z-1 is designated as.
The powder X-ray RD test result of the step hole ZSM-5 zeolite Z-1 that the present embodiment is obtained as depicted in figs. 1 and 2,
N2Adsorption-desorption isothermal is as shown in figure 3, ammonia temperature programmed desorption curve is as shown in Figure 4.
Embodiment 2
Present embodiments provide a kind of step hole ZSM-5 zeolite, which is through the following steps that prepare：
Preparation method is general with embodiment 1 same, and difference is that template is changed to 1.77g four-head cationic polyquaternary ammonium salt
Surfactant and 0.38g double end cationic surface active agents, other conditions are constant, the H types for preparing
Step hole ZSM-5 zeolite is designated as Z-2.
The powder X-ray RD test result of the step hole ZSM-5 zeolite Z-2 that the present embodiment is obtained as depicted in figs. 1 and 2,
N2Adsorption-desorption isothermal is as shown in figure 3, ammonia temperature programmed desorption curve is as shown in Figure 4.
Embodiment 3
Present embodiments provide a kind of step hole ZSM-5 zeolite, which is through the following steps that prepare：
Preparation method is general with embodiment 1 same, and difference is that template is changed to tri- cation polyquaternary ammonium salt of 1.94g,
Other conditions are constant, and the step hole ZSM-5 zeolite of the H types for preparing is designated as Z-3.
The powder X-ray RD test result of the step hole ZSM-5 zeolite Z-3 that the present embodiment is obtained as depicted in figs. 1 and 2,
N2Adsorption-desorption isothermal is as shown in figure 3, ammonia temperature programmed desorption curve is as shown in Figure 4.
Embodiment 4
Present embodiments provide a kind of step hole ZSM-5 zeolite, which is through the following steps that prepare：
Preparation method is general with embodiment 1 same, and difference is that template adopts 1.54g double end cation polyquaternary ammonium salt, its
His condition is constant, and the step hole ZSM-5 zeolite of the H types for preparing is designated as Z-4.
The powder X-ray RD test result of the step hole ZSM-5 zeolite Z-4 that the present embodiment is obtained as depicted in figs. 1 and 2,
N2Adsorption-desorption isothermal is as shown in figure 3, ammonia temperature programmed desorption curve is as shown in Figure 4.
Embodiment 5
The ZSM-5 zeolite of the different structure that the present embodiment is obtained to embodiment 1-4 and comparative example 1 has carried out structure point
Analysis, as shown in table 1, table 1 is the hole knot of the ZSM-5 zeolite that embodiment 1-4 and comparative example 1 are obtained to analysis result
Structure parameter.
Table 1
From table 1 it follows that in step hole ZSM-5 zeolite obtained in the preparation method that the present invention is provided, plus
Enter double type polyquaternary ammonium salt surfactant can guide step hole ZSM-5 zeolite formation, using bull quaternary ammonium salt
The step hole ZSM-5 zeolite of synthesis can increase substantially its specific surface area, hole compared with conventional ZSM-5 zeolite,
Hold and pore size, especially external surface area are dramatically increased, and bull cationic polyquaternary ammonium salt and double end sun
Ion polyquaternary ammonium salt surfactant structure is similar, with good compound property, can be increased by two kinds of mixing
Mesoporous quantity, to adjust the ratio of step hole ZSM-5 zeolite intermediary hole and micropore.
In addition, from figure 3, it can be seen that adding ZSM-5 zeolite obtained in double type polyquaternary ammonium salt surfactant
With obvious hysteresis loop, showing can be while be oriented to ZSM-5 zeolite structure and mesoporous knot with novel multi-bit polyquaternary ammonium salt
Structure, and knowable in Fig. 1 and Fig. 2, the mesoporous of ZSM-5 zeolite prepared by the present invention tends to ordering.
As seen in Figure 4, add the ammonia of ZSM-5 zeolite obtained in double type polyquaternary ammonium salt surfactant
Corresponding to the low temperature desorption peaks (150 DEG C -225 DEG C) at weak acid center and corresponding to strong in gas temperature programmed desorption curve
The elevated temperature desorption peak (300 DEG C -450 DEG C) in acid site is obviously higher than conventional ZSM-5 zeolite；And behind its weak acid position
Move, illustrate to add ZSM-5 zeolite obtained in double type polyquaternary ammonium salt surfactant to have higher acid amount and acid strong
Degree.
By above-described embodiment, by ZSM-5 zeolite tool in step hole obtained in the preparation method that the present invention is provided
Orderly meso-hole structure, it is allowed to which object macromole reacts in duct, belongs to good mesoporous material.
Claims (10)
1. the preparation method of a kind of step hole ZSM-5 zeolite, the preparation method are comprised the following steps：
Step one：Template and water are mixed to get into solution；
Step 2：Sodium hydroxide, silicon source, short chain alcohol, silicon source are added in solution, gel mixture is mixed to form,
Wherein, sodium hydroxide, silicon source, silicon source, template, the mol ratio of short chain alcohol and water are
(5-15):1:(30-100):(0.5-3):(70-500):(1000-8000), the silicon source is with SiO2Meter, silicon source is with Al2O3Meter；
Step 3：Crystallization is carried out to gel mixture, solid product is separated, wash, be dried, obtain ZSM-5
Zeolite powder；
Step 4：Roasting is carried out to ZSM-5 zeolite original powder, step hole ZSM-5 zeolite is obtained.
2. preparation method according to claim 1, wherein, in step 2, sodium hydroxide is added in solution
After stirring, add silicon source and stir, be eventually adding the mixture of short chain alcohol and silicon source, stirring forms gel
Mixture, the Si in silicon source are 1 with the mol ratio of short chain alcohol:(1-50).
3. preparation method according to claim 1, wherein, the mixing temperature in step one and step 2 is 20
℃-60℃；Crystallization temperature in step 3 is 120 DEG C -250 DEG C, and crystallization time is 12h-240h；In step 4
Sintering temperature be 500 DEG C -650 DEG C, roasting time is 4h-12h.
4. preparation method according to claim 1, wherein, the step of also exchange including ammonium in the preparation method,
ZSM-5 zeolite original powder is carried out, after roasting, carrying out ammonium exchange in step 4, through sucking filtration, washing, be dried and roasting
Burn, obtain step hole ZSM-5 zeolite.
5. preparation method according to claim 1, wherein, the template includes double type polyquaternary ammonium salt table
Face activating agent；The double type polyquaternary ammonium salt surfactant is by double end cationic polyquaternary ammonium salt and bull cation
What type polyquaternary ammonium salt was formed.
6. preparation method according to claim 5, wherein, the bull cationic polyquaternary ammonium salt is selected from three
Polyquaternary ammonium salt, four polyquaternary ammonium salt and many polyquaternary ammonium salt, the hydrophobic chain of the bull cationic polyquaternary ammonium salt is C8-C22
Alkyl chain, the connecting group of the polyquaternary ammonium salt is C2-C10Alkyl chain；Live on the double type polyquaternary ammonium salt surface
Property agent be CH3(CH2)15N(CH3)2(CH2)6N(CH3)2(CH2)15CH3Br2With
CH3(CH2)15[N(CH3)2(CH2)6]n-1N(CH3)2(CH2)15CH3Brn, integers of the n for 3-5.
7. preparation method according to claim 1, wherein, source of aluminium includes inorganic silicon source and organic silicon source
In the combination of one or more；Preferably, the inorganic silicon source includes aluminum sulfate, sodium aluminate, organic silicon source
Including C2-C5Three secondary aluminum alkoxides；It is highly preferred that organic silicon source includes aluminum isopropylate., isobutanol aluminum.
8. preparation method according to claim 1, wherein, the silicon source includes inorganic silicon source and organic silicon source
In the combination of one or more；Preferably, the inorganic silicon source includes waterglass, Ludox, sodium silicate, described
Organic silicon source is C2-C5Alkyl silicate；It is highly preferred that organic silicon source includes tetraethyl orthosilicate, positive silicic acid
Propyl ester.
9. preparation method according to claim 1 and 2, wherein, the short chain alcohol includes ethanol and C3-C5
Secondary alcohol in the combination of one or more.
10. a kind of step hole ZSM-5 zeolite, which is prepared by the preparation method by described in any one of claim 1-9
Obtain.
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| 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 |
| CN109665542A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method thereof |
| CN112707411A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Binder-free hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof |
| CN115385357A (en) * | 2022-08-25 | 2022-11-25 | 山东京博石油化工有限公司 | HZSM-5 molecular sieve, preparation method thereof and application thereof in light hydrocarbon catalytic cracking |
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| CN102416344A (en) * | 2011-10-20 | 2012-04-18 | 中国石油天然气集团公司 | Preparation method of step hole ZSM-5 zeolite composite material-based low-temperature sulfur transfer catalyst for FCC (Fluid Catalytic Cracking) petroleum |
| CN102895991A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Method for preparing fluid catalytic cracking (FCC) gasoline small-molecule sulfur densification catalyst |
| CN103007983A (en) * | 2012-10-08 | 2013-04-03 | 太原理工大学 | HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof |
| CN104211085A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Core-shell type ZSM-5 molecular sieve and preparation and application thereof |
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| CN102416344A (en) * | 2011-10-20 | 2012-04-18 | 中国石油天然气集团公司 | Preparation method of step hole ZSM-5 zeolite composite material-based low-temperature sulfur transfer catalyst for FCC (Fluid Catalytic Cracking) petroleum |
| CN103007983A (en) * | 2012-10-08 | 2013-04-03 | 太原理工大学 | HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109665542A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method thereof |
| CN109665542B (en) * | 2017-10-17 | 2022-07-12 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
| CN112707411A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Binder-free hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof |
| CN115385357A (en) * | 2022-08-25 | 2022-11-25 | 山东京博石油化工有限公司 | HZSM-5 molecular sieve, preparation method thereof and application thereof in light hydrocarbon catalytic cracking |
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