CN101993091A - Method for synthesizing ZSM-5 zeolite - Google Patents
Method for synthesizing ZSM-5 zeolite Download PDFInfo
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- CN101993091A CN101993091A CN2009101696160A CN200910169616A CN101993091A CN 101993091 A CN101993091 A CN 101993091A CN 2009101696160 A CN2009101696160 A CN 2009101696160A CN 200910169616 A CN200910169616 A CN 200910169616A CN 101993091 A CN101993091 A CN 101993091A
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Abstract
The invention discloses a method for synthesizing zeolite Socony Mobil (ZSM)-5 zeolite. The method comprises the following steps of: mixing a composite silicon source, an aluminum source and water, adding or not adding inorganic alkali, and crystallizing an obtained reaction mixture at the temperature of between 100 and 200 DEG C for 8 to 16 hours, wherein in the reaction mixture, the molar ratio of Na2O to SiO2 is 0.05-0.2:1, the molar ratio of SiO2 to Al2O3 is 20-100:1 and the molar ratio of H2O to SiO2 is 5-15:1, and the composite silicon source consists of an active silicon source in an amount which is 13 to 99 weight percent based on the SiO2 and an inert silicon source in an amount which is 1 to 87 weight percent based on the SiO2. The method for synthesizing the ZSM-5 zeolite has low water consumption, high yield in a single kettle, short crystallization time and low cost; and the synthesized ZSM-5 zeolite has high crystallinity and uniform particle size.
Description
Technical field
The present invention relates to a kind of method of synthetic ZSM-5 zeolite.
Background technology
The ZSM-5 zeolite in 1972 by U.S. Mobil company reported first (USP3702886), because of its silica alumina ratio height, thermostability and good hydrothermal stability, characteristic and unique three-dimensional open-framework and shape selective catalysis effect with oleophilic drainage, to alkylation, isomerization, disproportionation, select reactions such as shaped reaction, catalytic pyrolysis, preparing gasoline by methanol, methanol-to-olefins and have unique catalytic performance, be widely used in petrochemical industry.
The synthetic method of ZSM-5 zeolite can be divided into organic method and inorganic method.So-called organic method is used organic formwork agent exactly in reaction system, inorganic rule is without organic formwork agent in reaction system.Organic formwork agent costs an arm and a leg, contaminate environment, and uses organic formwork agent synthetic ZSM-5 zeolite to need high-temperature roasting, and removing organic formwork agent contained in the zeolite cavity, and there are not the problems referred to above in the synthetic ZSM-5 of inorganic method.
CN85100463, CN97100145, US5240892 be disclosed not to be used in the method for the synthetic ZSM-5 of organic formwork agent, uses water glass to be the silicon source, and H still feeds intake
2O/SiO
2(mol ratio) is higher, and single-autoclave yield rate is lower.
CN200710156479 discloses a kind of ZSM-5 zeolite synthesis method, mixture with soft silica solid or itself and solid state si hydrochlorate is the silicon source, with aluminate or aluminium salt is the aluminium source, by a certain percentage with deionized water, mineral alkali (if the two silicon sources of employing, mineral alkali can) mix, then mixture is placed in the stainless steel cauldron of teflon lined, under certain condition hydrothermal crystallizing.But this method easily produces mordenite stray crystal and quartzy stray crystal, and synthetic ZSM-5 zeolite crystallinity is lower, and the zeolite particle diameter is inhomogeneous.
CN1318302C discloses is not a kind ofly having under the organic formwork agent condition to adopt variable temp to prepare the method for ZSM-5, and its characteristics are that reaction mixture has following mole and forms: M
2O/SiO
2(M: be 0.07～0.14 alkalimetal ion), H
2O/SiO
2Be 15～42, SiO
2/ Al
2O
3Be 20～100; This reaction mixture is in relatively-high temperature degree (180～210 ℃) nucleation, crystallization under relative low temperature (130～170 ℃) then down.It is the silicon source that this method adopts single silicon sol, and heating up during actually operating is easy to, but cooling needs the long time, and therefore low temperature has certain difficulty behind the first high temperature in actually operating.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method of not using the synthetic ZSM-5 zeolite of organic formwork agent, and this zeolite has more uniform particle diameter.
The invention provides a kind of method of synthetic ZSM-5 zeolite, comprising: comprehensive silicon source, aluminium source, water are mixed, add or do not add mineral alkali, then with the reaction mixture that obtains in 100～200 ℃ of crystallizations 8～16 hours, obtain the ZSM-5 zeolite; Wherein the mol ratio of each component is in the reaction mixture: Na
2O/SiO
2=0.05～0.2: 1, SiO
2/ Al
2O
3=20～100: 1, H
2O/SiO
2=5～15: 1, described comprehensive silicon source is by with SiO
2The activated silica source of meter 13～99 weight % and the inertia silicon source of 1～87 weight % are formed, and the activated silica source is water glass and/or silicon sol, and inertia silicon source is silica gel and/or silicon sol.
Zeolite preparation method provided by the invention is used the silicon source of different activities, does not use organic formwork agent, at lower water silicon than (H
2O/SiO
2Mol ratio is lower than 15) down synthetic ZSM-5 zeolite, water consumption is low, single-autoclave yield rate height, but mother liquor reuse, crystallization time is short, and technology is simple, and running cost and synthetic cost are low, and the synthetic ZSM-5 of institute zeolite crystallinity height, particle diameter are more even.
Description of drawings
Fig. 1 is the XRD spectra of embodiment 2 synthetic ZSM-5 zeolites.
Fig. 2 is the XRD spectra of Comparative Examples 1 synthetic ZSM-5 zeolite.
Fig. 3 is the SEM figure of embodiment 2 synthetic ZSM-5 zeolites.
Fig. 4 is the SEM figure of embodiment 5 synthetic ZSM-5 zeolites.
Fig. 5 is the SEM figure of Comparative Examples 2 synthetic ZSM-5 zeolites.
Embodiment
In the method for synthetic ZSM-5 zeolite provided by the invention, (perhaps also adding mineral alkali) mixed in comprehensive silicon source, aluminium source, deionized water obtain reaction mixture, wherein, described comprehensive silicon source is preferably by with SiO
2The activated silica source of meter 15～85 weight % and the inertia silicon source of 15～85 weight % are formed, and more preferably the activated silica source is 17～45 weight %, and inertia silicon source is 55～83 weight %.Described comprehensive silicon source is two or three in water glass, silicon sol, the silica gel, is preferably water glass and silicon sol, water glass and silica gel or silicon sol and silica gel.Described silica gel is for example: one or more in silochrom, chromatographic silica gel, the silica gel of being fuming (white carbon black) and the Kiselgel A.Described silicon sol can be acidic silicasol, alkaline silica sol or ammonium type silicon sol, is preferably alkaline silica sol.SiO in silicon sol
2When the median size of particle is no more than 10nm, use as the activated silica source; SiO in silicon sol
2The median size of particle is used as inertia silicon source during greater than 10nm.When comprising water glass and silicon sol in the comprehensive silicon source, silicon sol is inertia silicon source, selects SiO for use
2Average particle size is greater than the silicon sol of 10nm; When the comprehensive silicon source was silicon sol and silica gel, silicon sol was the activated silica source, selects SiO for use
2Average particle size is less than the silicon sol of 10nm.
In the method for synthetic ZSM-5 zeolite provided by the invention, described aluminium source is the hydrate of aluminate or aluminum oxide, and for example: sodium aluminate, potassium aluminate, boehmite, pseudo-boehmite or gibbsite are preferably sodium aluminate or pseudo-boehmite.Described mineral alkali is sodium hydroxide or potassium hydroxide.Described water is deionized water.
In the method for synthetic ZSM-5 zeolite provided by the invention, will can also introduce crystal seed, crystal seed/SiO in comprehensive silicon source, aluminium source, the deionized water blended process
2(weight ratio)=0.03～0.15: 1.Described crystal seed comprises isomorphous crystal seed and xenocryst crystal seed, and isomorphous crystal seed is organic method or inorganic method synthetic ZSM-5 zeolite, comprises Na type or H type, the roasting or the ZSM-5 zeolite of roasting not; The xenocryst crystal seed is non-ZSM-5 zeolite, and preferred X, y-type zeolite comprise the non-ZSM-5 zeolite of Na type, H type, ion-exchange and hydrothermal treatment consists, for example REX, NaY or USY zeolite.Introduce crystal seed and can improve crystallization velocity, shorten crystallization time.
In the method for synthetic ZSM-5 zeolite provided by the invention, the method of described crystallization can adopt and well known to a person skilled in the art the whole bag of tricks, for example can adopt thermostatic crystallization or multistage variable temperature crystallization, in adopting above-mentioned two kinds of crystallization methods, specifically can adopt static crystallization, dynamic crystallization or intermittent type dynamic crystallization.Preferred crystallization temperature is 150～190 ℃, and crystallization time is 8～16 hours.
In the method for synthetic ZSM-5 zeolite provided by the invention, obtain the ZSM-5 crystallization of zeolites after the reaction mixture crystallization, reclaim then and obtain ZSM-5 zeolite product, the described prior art that is recovered as, comprise filtration, washing, exsiccant step, the present invention does not have particular requirement.
With embodiment the present invention is described further below.
Table 1 is raw materials used source and a composition in embodiment and the Comparative Examples, and institute's water is a deionized water.
Table 1
Embodiment 1
Get 200 gram water glass,, add 133 gram silica gel and 35.5 and restrain the NaY zeolites, stirred 30 minutes, obtain even gel to wherein adding 442 gram water and 76.5 grams are low stirred 30 minutes partially.Gel is transferred in 2 liters of stainless steel crystallizing kettles, airtight, then in 170 ℃ of dynamic crystallizations 14 hours, dynamic crystallization mixing speed 100rpm, after suction filtration, washing, drying solid product.Solid product is a pure phase ZSM-5 zeolite through X-ray diffraction analysis, and relative crystallinity is 103%.In the present embodiment, the mol ratio between each component of reaction mixture is as follows: Na
2O/SiO
2=0.13: 1, SiO
2/ Al
2O
3=25: 1, H
2O/SiO
2=12.Crystal seed/SiO
2(weight ratio)=0.15: 1.Wherein to account for the ratio in total silicon source be 24% in the activated silica source.The size-grade distribution of resulting ZSM-5 zeolite sees Table 2.
Embodiment 2
Get 372 gram water glass,, add 282 gram silica gel and 17 and restrain the ZSM-5 zeolites, stirred 30 minutes, obtain even gel to wherein adding 396 gram water and 178 grams are low stirred 30 minutes partially.Gel is transferred in 2 liters of stainless steel crystallizing kettles, airtight, in 180 ℃ of dynamic crystallizations 12 hours, dynamic crystallization mixing speed 100rpm, after suction filtration, washing, drying solid product.Solid product is a pure phase ZSM-5 zeolite through X-ray diffraction analysis, and relative crystallinity is 105%.In the present embodiment, the mol ratio between each component of reaction mixture is as follows: Na
2O/SiO
2=0.15: 1, SiO
2/ Al
2O
3=40: 1, H
2O/SiO
2=8.Crystal seed/SiO
2(weight ratio)=0.05: 1.Wherein to account for the ratio in total silicon source be 22% in the activated silica source.
Embodiment 3
Get 255 gram silicon sol A, to wherein adding 417 gram water and 11.7 gram NaOH, stirred 30 minutes, adding 45 grams are partially low, stir 30 minutes, add 133 and restrain silica gel and 20.7 gram NaY zeolites, stir 30 minutes, obtain even gel.Gel is transferred in 2 liters of stainless steel crystallizing kettles, and airtight back is in 160 ℃ of dynamic crystallizations 16 hours, rotating speed 100rpm, after suction filtration, washing, the drying solid product.Solid-liquid separation was collected mother liquor 360 gram (SiO in the mother liquor after crystallization was finished
2Content is 4.68 weight %, Na
2O content is 1.30 weight %).Collecting solid product is pure phase ZSM-5 zeolite through X-ray diffraction analysis, and relative crystallinity is 100%.In the present embodiment, the mol ratio between each component of reaction mixture is as follows: Na
2O/SiO
2=0.07: 1, SiO
2/ Al
2O
3=50: 1, H
2O/SiO
2=10.Crystal seed/SiO
2(weight ratio)=0.07: 1.Wherein to account for the ratio in total silicon source be 38% in the activated silica source.
Embodiment 4
Get 326 gram silicon sol A, to wherein adding 342 gram water and 56 gram NaOH, stirred 30 minutes, adding 45 grams are partially low, stir 30 minutes, add 155 and restrain silica gel and 20.7 gram NaY zeolites, stir 30 minutes, obtain even gel.Gel is transferred in 2 liters of stainless steel crystallizing kettles, airtight, in 190 ℃ of dynamic crystallizations 8 hours, the mixing speed 100rpm during dynamic crystallization, after suction filtration, washing, drying solid product.Solid product is a pure phase ZSM-5 zeolite through X-ray diffraction analysis, and relative crystallinity is 101%.In the present embodiment, the mol ratio between each component of reaction mixture is as follows: Na
2O/SiO
2=0.18: 1, SiO
2/ Al
2O
3=60: 1, H
2O/SiO
2=8.Crystal seed/SiO
2(weight ratio)=0.06: 1.Wherein to account for the ratio in total silicon source be 40% in the activated silica source.
Embodiment 5
Get 408 gram water glass,, stirred 30 minutes, add the partially low and 18 gram NaY zeolites of 38 grams, stirred 30 minutes, obtain even gel to wherein adding 242 gram water and 662 gram silicon sol B.Gel is transferred in 2 liters of stainless steel crystallizing kettles, and 110 ℃ of crystallization 4 hours were warming up to 180 ℃ of crystallization 10 hours, crystallization mixing speed 100rpm, after suction filtration, washing, drying solid product.Solid product is a pure phase ZSM-5 zeolite through X-ray diffraction analysis, and relative crystallinity is 97%.In the present embodiment, the mol ratio between each component of reaction mixture is as follows: Na
2O/SiO
2=0.1: 1, SiO
2/ Al
2O
3=80: 1, H
2O/SiO
2=12.Crystal seed/SiO
2(weight ratio)=0.05: 1.Wherein to account for the ratio (butt) in total silicon source be 29% in the activated silica source.
Get 381 gram water glass,, add 370 gram silica gel and 21 and restrain the ZSM-5 zeolites, stirred 30 minutes, obtain even gel to wherein adding 658 gram water and 89 grams are low stirred 30 minutes partially.Gel is transferred in 2 liters of stainless steel crystallizing kettles, and 200 ℃ of crystallization 8 hours, mixing speed was 100rpm during crystallization, after suction filtration, washing, drying solid product.Solid product is a pure phase ZSM-5 zeolite through X-ray diffraction analysis, and relative crystallinity is 95%.In the present embodiment, the mol ratio between each component of reaction mixture is as follows: Na
2O/SiO
2=0.08: 1, SiO
2/ Al
2O
3=100: 1, H
2O/SiO
2=8.Crystal seed/SiO
2(weight ratio)=0.05: 1.Wherein to account for the ratio in total silicon source be 17% in the activated silica source.
Embodiment 7
Get 336 gram water glass,, after stirring, add 109 gram silica gel, 9.5 gram pseudo-boehmites and 5 gram ZSM-5 zeolites, stirred 90 minutes, obtain even gel to wherein adding 504 gram water.Gel is transferred in 2 liters of stainless steel crystallizing kettles, and airtight back is in 180 ℃ of dynamic crystallizations 12 hours, dynamic crystallization mixing speed 100rpm, after suction filtration, washing, drying solid product.Solid product is a pure phase ZSM-5 zeolite through X-ray diffraction analysis, and relative crystallinity is 104%.In the present embodiment, the mol ratio between each component of reaction mixture is as follows: Na
2O/SiO
2=0.12: 1, SiO
2/ Al
2O
3=40: 1, H
2O/SiO
2=15.Crystal seed/SiO
2(weight ratio)=0.03: 1.Wherein the activated silica source accounts for 40% of total silicon source.
Zeolite and ammonium sulfate, Secondary ammonium phosphate and the deionized water of embodiment 2 preparations were pressed 1: 0.06: 0.04: 10 (weight) were in 75 ℃ of exchanges 30 minutes, and exchange twice has exchanged filtration drying and obtained zeolite A.
Comparative Examples 1
Prepare the ZSM-5 zeolite by CN200710156479.
4.608 gram dissolution of sodium hydroxide in 71.46 gram water, after stirring to clarify, are added 1.592 gram sodium aluminate (Al successively
2O
341.0 weight %, Na
2O 24.9 weight %, H
2O 34.1 weight %) and 19.23 gram solid silicones (100～200 order), stirred 1 hour, must an even gel.Gel is transferred in the stainless steel crystallizing kettle of 100mL teflon lined, crystallization were stirred 24 hours in 190 ℃ in airtight back, after suction filtration, washing, drying solid product.Its XRD figure as shown in Figure 2.In this Comparative Examples, the mol ratio between each component of reaction mixture is as follows: Na
2O: SiO
2=0.2: 1, SiO
2: Al
2O
3=50: 1, H
2O: SiO
2=12.5: 1.
Comparative Examples 2
Press CN200710156479 embodiment 2 these Comparative Examples of preparation
5.457 gram water glass (are contained SiO
221.15 weight %, Na
2O 21.82 weight %, H
2O57.03 weight %) is dissolved in the 34.30 gram water, stirs to clarify, get solution A; In another beaker, 0.796 gram sodium aluminate (is contained Al
2O
341 41.0 weight %, Na
2O 24.9 weight %, H
2O34.1 weight %) is dissolved in the 34.30 gram water, stirs to clarify, get solution B.Under the room temperature solution B is added in the solution A fast, adds 8.462 gram solid silicones (100～200 order) then while stirring, add the back and stirred 1 hour, get even gel.Gel is transferred in the stainless steel crystallizing kettle of 100mL teflon lined, crystallization were stirred 72 hours in 180 ℃ in airtight back, after suction filtration, washing, drying solid product.In this Comparative Examples, the mol ratio between each component of reaction mixture is as follows: SiO
2/ Al
2O
3=50: 1, Na
2O/SiO
2=0.14: 1, H
2O/SiO
2=25: 1.Wherein to account for the ratio in total silicon source be 12% in the activated silica source.
Comparative Examples 3
Method according to embodiment 8 exchanges, and the zeolite that different is is adopted is the prepared zeolite of Comparative Examples 1, makes zeolite DB.
Performance test
The zeolite relative crystallinity
Adopt Philips Analytical type X-ray diffractometer, the thing phase of test sample.Experiment condition: Cu target, K alpha-ray, Ni filter plate, solid-state detector, tube voltage 30kV, tube current 20mA, step-scan, 0.01669 ° of stride, 5 °～50 ° of sweep limits.
The relative crystallinity of ZSM-5 zeolite is represented with percentage ratio with the ratio of the peak intensity sum of five characteristic diffraction peaks of 2 θ between 20.00 °～25.00 ° in the XRD spectra of the peak area sum of five characteristic diffraction peaks of 2 θ in the XRD spectra of preparation-obtained product between 20.00 °～25.00 ° and ZSM-5 zeolite standard specimen.The qualified ZSM-5 zeolite Industrial products that standard specimen adopts commercially available Sinopec catalyst Co. Shandong branch office to produce are set at 100% with the degree of crystallinity of this product.
The XRD spectra of embodiment 2 and Comparative Examples 1 product is seen Fig. 1 and Fig. 2.
Size-grade distribution
Adopt the HORIBA LB-500 of company dynamic light scattering particle size distribution instrument, dispersion medium is a water.Particle size distribution test the results are shown in Table 2.
Sem analysis
Adopt the Quanta 3D FEG of FEI Co. scanning electron microscope, acceleration voltage is 20kV, environmental scanning.
Little the living of zeolite estimated (MA)
Zeolite A and zeolite DB compressing tablet are sized to 20～40 orders, and 800 ℃ of 100% aging 17h of water vapour carries out little test of living.Little test condition alive is: temperature of reaction is 460 ℃, 70 seconds reaction times, and agent-oil ratio 3.2, oil inlet quantity 1.56 grams, reaction raw materials is a huge port straight-run diesel oil.Evaluation result sees Table 3.
By Fig. 1 and Fig. 2 as seen, the zeolite of the inventive method preparation has higher degree of crystallinity.
Can scheme as seen with SEM by table 2, the inventive method synthetic ZSM-5 zeolite, granularity is more even, and size-grade distribution is more concentrated.
By table 3 as seen, the ZSM-5 zeolite of the present invention's preparation has higher micro-activity, low-carbon alkene (C
2 =, C
3 =And C
4 =) productive rate higher.
Table 2
Table 3
| Sample number into spectrum | Zeolite A | Zeolite DB |
| ?MA | 37 | 33 |
| Material balance, m% | ||
| Dry gas | 1.05 | 0.75 |
| Liquefied gas | 18.93 | 16.31 |
| Gasoline | 16.37 | 15.26 |
| Diesel oil | 63.51 | 67.54 |
| Coke | 0.14 | 0.14 |
| Transformation efficiency, m% | 36.49 | 32.46 |
| The productive rate of main thing in the reacted gas, m% | ||
| Hydrogen | 0.03 | 0.03 |
| Methane | 0.01 | 0.01 |
| Ethane | 0.03 | 0.03 |
| Ethene | 0.98 | 0.68 |
| Propane | 2.87 | 2.38 |
| Propylene | 5.49 | 4.73 |
| Total butane | 3.95 | 3.04 |
| Total butylene | 6.62 | 6.15 |
| Trimethylmethane | 1.75 | 1.28 |
| Iso-butylene | 3.02 | 2.88 |
Claims (10)
1. the method for a synthetic ZSM-5 zeolite comprises: comprehensive silicon source, aluminium source, water are mixed, add or do not add mineral alkali, then with the reaction mixture that obtains in 100～200 ℃ of crystallization 8～16 hours; Wherein the mol ratio of each component is in the reaction mixture: Na
2O/SiO
2=0.05～0.2: 1, SiO
2/ Al
2O
3=20～100: 1, H
2O/SiO
2=5～15: 1, described comprehensive silicon source is by with SiO
2The inertia silicon source of the meter activated silica source of 13～99 weight % and 1～87 weight % is formed, and the activated silica source is that water glass and/or silicon sol, inertia silicon source are silica gel and/or silicon sol.
2. in accordance with the method for claim 1, it is characterized in that described comprehensive silicon source is by with SiO
2The activated silica source of meter 15～85 weight % and the inertia silicon source of 15～85 weight % are formed.
3. in accordance with the method for claim 2, it is characterized in that described comprehensive silicon source is by with SiO
2The activated silica source of meter 17～45 weight % and the inertia silicon source of 55～81 weight % are formed.
4. according to claim 1,2 or 3 described methods, it is characterized in that described comprehensive silicon source is water glass and silicon sol, water glass and silica gel or silicon sol and silica gel.
5. in accordance with the method for claim 1, it is characterized in that the median size of described activated silica source silicon sol is no more than 10nm, the median size of inertia silicon source silicon sol is greater than 10nm.
6. in accordance with the method for claim 1, it is characterized in that described aluminium source is sodium aluminate, potassium aluminate, boehmite, pseudo-boehmite or gibbsite.
7. in accordance with the method for claim 1, it is characterized in that, will also introduce crystal seed, crystal seed and SiO in comprehensive silicon source, aluminium source, the deionized water blended process
2Weight ratio be 0.03～0.15: 1.
8. in accordance with the method for claim 1, it is characterized in that described crystal seed is ZSM-5 zeolite, X type zeolite or y-type zeolite.
9. in accordance with the method for claim 1, it is characterized in that crystallization temperature is 150～190 ℃
10. a ZSM-5 zeolite is characterized in that, described ZSM-5 zeolite is by each described method preparation of claim 1～9.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848437A (en) * | 2012-12-03 | 2014-06-11 | 中国石油大学(华东) | Preparation method of ZSM-5 molecular sieve |
| CN104549436A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogen type ZSM-5 molecular sieve catalyst as well as preparation method and application thereof |
| CN106745052A (en) * | 2016-12-06 | 2017-05-31 | 神华集团有限责任公司 | A kind of synthetic method of the molecular sieves of HZSM 5 of use double template |
| CN107934986A (en) * | 2017-11-23 | 2018-04-20 | 武汉凯迪工程技术研究总院有限公司 | Biomass ash resource utilization method |
| CN107954445A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Even ZSM-5 molecular sieve synthetic method |
| CN109437232A (en) * | 2018-12-13 | 2019-03-08 | 东莞理工学院 | A kind of preparation method of the ZSM-5 molecular sieve of multilevel structure |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100463B (en) * | 1985-04-03 | 1988-06-01 | 南开大学 | Direct synthesis of zsm-5 zeolite |
| US5240892A (en) * | 1987-09-02 | 1993-08-31 | Mobil Oil Corporation | Small crystal ZSM-5, as a catalyst |
| CN1056818C (en) * | 1997-01-10 | 2000-09-27 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN101177282A (en) * | 2007-11-01 | 2008-05-14 | 浙江大学 | Method for synthesizing high-crystallinity ZSM-5 molecular sieve without organic template |
-
2009
- 2009-08-27 CN CN2009101696160A patent/CN101993091B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848437A (en) * | 2012-12-03 | 2014-06-11 | 中国石油大学(华东) | Preparation method of ZSM-5 molecular sieve |
| CN103848437B (en) * | 2012-12-03 | 2016-02-17 | 中国石油大学(华东) | A kind of preparation method of ZSM-5 molecular sieve |
| CN104549436A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogen type ZSM-5 molecular sieve catalyst as well as preparation method and application thereof |
| CN107954445A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Even ZSM-5 molecular sieve synthetic method |
| CN106745052A (en) * | 2016-12-06 | 2017-05-31 | 神华集团有限责任公司 | A kind of synthetic method of the molecular sieves of HZSM 5 of use double template |
| CN106745052B (en) * | 2016-12-06 | 2021-03-30 | 神华集团有限责任公司 | Method for synthesizing HZSM-5 molecular sieve by using double templates |
| CN107934986A (en) * | 2017-11-23 | 2018-04-20 | 武汉凯迪工程技术研究总院有限公司 | Biomass ash resource utilization method |
| CN107934986B (en) * | 2017-11-23 | 2020-09-01 | 武汉凯迪工程技术研究总院有限公司 | Resource utilization method of biomass ash |
| CN109437232A (en) * | 2018-12-13 | 2019-03-08 | 东莞理工学院 | A kind of preparation method of the ZSM-5 molecular sieve of multilevel structure |
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|---|---|
| CN101993091B (en) | 2012-07-18 |
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