CN100548880C - A kind of preparation method of beta zeolite with multilevel pore canals - Google Patents
A kind of preparation method of beta zeolite with multilevel pore canals Download PDFInfo
- Publication number
- CN100548880C CN100548880C CNB2006100013327A CN200610001332A CN100548880C CN 100548880 C CN100548880 C CN 100548880C CN B2006100013327 A CNB2006100013327 A CN B2006100013327A CN 200610001332 A CN200610001332 A CN 200610001332A CN 100548880 C CN100548880 C CN 100548880C
- Authority
- CN
- China
- Prior art keywords
- charcoal
- silica column
- hours
- monolithic silica
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a kind of preparation method of beta zeolite with multilevel pore canals, be to flood monolithic silica column with sucrose solution, drying, polymerization, charing obtain the charcoal silicon compound, after using the mixing solutions of being made up of aluminium source, mineral alkali, organic amine, water wetting the charcoal silicon compound, crystallization also reclaims product.This method raw material of wood-charcoal material in crystallization process has been protected the pore passage structure of monolithic silica column effectively, and is unlikely to be destroyed in crystallization process.There are multistage pore canals such as micron order macropore, mesoporous and micropore in the β zeolitic material of this method preparation, overcome of the restriction of zeolite molecular sieve micropore to its catalytic performance, wherein the existence of open type macropore can be shortened the distance of reaction molecular diffusion, can make the pressure drop of device reduce and then improve the unit capacity of device, can make the selectivity of product be easy to adjust and control, mesoporously provide abundant inner ratio surface area, this has very important significance to macromolecular catalyzed reaction.
Description
Technical field
The invention relates to a kind of synthetic method of zeolite, further say so about a kind of preparation method of beta zeolite with multilevel pore canals.
Background technology
International Union of Pure and Applied Chemistry(IUPAC) is defined as 3 classes according to the molecular sieve bore diameter size with them: the aperture is less than the micro porous molecular sieve that is called of 2nm, and the aperture is called mesoporous or mesoporous molecular sieve between 2～50nm, and the aperture is greater than the large pore molecular sieve that is called of 50nm.
Because the crystalline form micro porous molecular sieve is widely used in fields such as catalysis, separation and purification to the specific selectivity of guest molecule size and shape always.Have a lot of potential chemical functionals though studies show that micro-pore zeolite, the duct that it is narrow relatively and long has not only been limited the diffusion in its hole of reactant and product molecule, and has been limited its application in the bulky molecular catalysis field.
In recent years, the crude oil heaviness is on the rise both at home and abroad, and traditional micro porous molecular sieve can not satisfy the macromolecular catalysis requirement of these heavy oil.Though active component is written in the carrier can improves this situation to a certain extent, but because the aperture of support of the catalyst is still less, and can not finely link between these ducts, when the molecule of reaction passes through these apertures, just produce therein easily and be detained, make the reactant molecule that enters in the duct be difficult for diffusing out and cause unwanted drastic cracking; Simultaneously, logistics flows with layer flow mode therein, and molecule passes in and out in the hole by diffusion, so if input speed is too fast, then molecule has little time to the hole internal diffusion, reaction effect is variation obviously; These restrictions cause its heavy oil cracking performance also undesirable.
1992, the researchist of Mobil company synthesized M41S mesoporous silicate of series and aluminosilicate molecular sieves first, and the duct size is 1.5～10nm.Synthesizing of these order mesoporous materials, widened the pore diameter range of original micro porous molecular sieve greatly.But, because the hole wall of mesopore molecular sieve is in metamict, therefore, compare with the micro-pore zeolite of crystalline structure, the hydrothermal stability of mesopore molecular sieve and acid relatively low, this has limited it and has directly used as catalyzer, usually it just can directly be used as carrier or after further modifying.
(Sung Il Cho such as Sung Il Cho, Sung Dae Choi, Jong-Ho Kim, Adv.Funct.Mater, 2004,14,49～54) utilize amorphous mesopore molecular sieve Al-MCM-41, Al-MCM-48, Al-SBA-15 etc. provide silicon source and aluminium source, support in solid carbon under the situation of above-mentioned framework of molecular sieve, they are directly changed into crystalline form ZSM-5 molecular sieve, so, gained ZSM-5 molecular sieve is after charcoal is removed in burning, except characteristic, also have and Al-MCM-41 with micropore ZSM-5 molecular sieve, Al-MCM-48, the meso-hole structure that Al-SBA-15 is same, it can be made into film like, Powdered, whole column.Characterization result shows that this molecular sieve has very high heat and hydrothermal stability, and triisopropylbenzene between macromole is had very excellent catalytic cracking performance.But (1.5～3nm) is still less, still can not satisfy those bigger bulky molecular catalysis reactions in its aperture.
(EP1106575A2) such as Claus J H Jacobsen utilizes excessive zeolite gel parcel carbon granule (Carbon Black Pearls 2000, provide by Carbot company), make fully inner crystallization of gel in the carbon granules duct, simultaneously, the abundant condensing crystal of excess gel becomes big zeolite crystal and wraps up carbon granule, after carbon granule is removed in burning, just formed big zeolite beta crystal with 10～100nm aperture.But aperture branch is extremely inhomogeneous in the big zeolite crystal of synthetic in this way.
(B.T.Holland such as Holland, L.Abrams, A.Stein, J.Am.Chem.Soc, 1999,121,4308～4309) be the solid template with closelypacked polystyrene spheres, crystallization forms the method for removing the solid template after zeolite structured and has obtained multistage pore canal ZSM-5 zeolite, but this method need solve the vitreous state temperature problem of polystyrene spheres, caused the loaded down with trivial details of building-up process, and also had no idea at present to address this problem fully.
Minakuchi (Minakuchi H in 1996, Nakanishi K, Soga N, et al, Ahalchem, 1996,3498) etc. 68 (9): prepared the through hole (throughpore that has micron-sized skeleton (skeleton) and be cross-linked to each other, also claim macropore, 0.5～8 μ m) and mesoporous (mesopore, 3～30nm) monolithic silica column.An outstanding feature of this material is that " resistance to mass transfer of stagnant flow phase " greatly reduced in its hole.Because its mass transfer process is mainly by the convection current transmission in the through hole, reactant molecule can reach active surface in the hole rapidly with logistics, the mesoporous this material that exists for provides bigger surface-area and unit capacity simultaneously, is suitable for macromolecular catalyzed reaction so have the material of this structure.But, consider that this material hole wall is in metamict, so itself also is not suitable as catalytic material.
Summary of the invention
The objective of the invention is on the basis of synthesized silicon rubber integral post, a kind of method that its amorphous hole wall is converted into the crystalline form Beta zeolite structures is provided, institute's synthetic zeolite compiles the advantage in macropore, mesoporous and three grades of ducts of beta-molecular sieve micropore, and it is more suitable in macromolecular catalyzed reaction.
Therefore, the preparation method of beta zeolite with multilevel pore canals provided by the invention is characterized in that this method contains following step:
(1) floods monolithic silica column with sucrose solution, then in 3～9 hours, 150～180 ℃ polyase 13～9 of 80～120 ℃ of dryings hour, 750～1200 ℃ of charings 2～8 hours, obtain the charcoal silicon compound, wherein, the mass ratio of each component is 0.8～1.5 sucrose: 0.1～0.2H in the said sucrose solution
2SO
4: 3～7H
2O water, charcoal silicon mass ratio is in the charcoal silicon compound: 1 charcoal: 3～3.5 silicon;
(2) use the mixing solutions of forming by aluminium source, mineral alkali, organic amine, water wetting the charcoal silicon compound after, 100～150 ℃ of following crystallization 6～96 hours and reclaim product in closed reaction kettle, each reactant is in mole in the reaction system: 1～10 aluminium source: 23～29 organic amines: 4～30 mineral alkalis: 100 silicon source: 800～1200H
2O, said silicon source is from the charcoal silicon compound.
Preparation method provided by the invention, be unformed silicon skeleton with monolithic silica column through the transition of charcoal skeleton and then change into crystalline form β zeolite, prepared β zeolitic material compiles the advantage of macropore, mesoporous and micropore.
In the method provided by the invention, the process of said sucrose solution dipping monolithic silica column is preferably carried out under negative pressure, and said carbonization process preferably carries out under nitrogen protection or vacuum.
Said monolithic silica column can be with reference to Minakuchi H document (Minakuchi H, NakanishiK, Soga N, et al, Analchem, 1996,3498) 68 (9): pertinent literature such as, perhaps application number is also to mention a kind of monolithic silica column and preparation method in 200510073092.7 the Chinese patent application, and in this application, its macropore diameter of silicagel column material that relates to is 0.5～3.0 μ m, mesoporous aperture is 3～10nm, and pore volume is 2.5～3.5cm
3/ g, specific surface area is 250～710m
2/ g, this material highly for 1cm, when diameter is 0.7cm right cylinder particle shape, crush strength is 180～220N, described monolithic silica column is to be 1 in molar ratio with polyoxyethylene glycol, water, acid, silicon source: (5800～60000): (1～11): mix (300～4000), stir down at 0 ℃, form vitreosol, behind gel, with silica obtained post washing in the alcoholic solution of water successively, aging in the alcoholic solution in silicon source, in surface tension less than the liquid of water or can reduce in the capillary solution and soak, obtain through super-dry and roasting again.
Monolithic silica column among the present invention is not limited to related any one of top document.Said monolithic silica column has certain mechanical strength, good permeability, in bulky molecular catalysis, absorption with the field such as separate and obtained extensive studies and application, generally have the mesoporous of the macropore of 0.5～8.0 μ m and 3～30nm, and be penetrating between the macropore.
In the method provided by the invention, said charcoal silicon compound is the mixture of silica gel and charcoal, and wherein charcoal silicon mass ratio is: 1 charcoal: 3～3.5 silicon provide the silicon source by it in the beta zeolite with multilevel pore canals building-up process.
The preferred sodium aluminate in said aluminium source, the preferred sodium hydroxide of mineral alkali, the preferred tetraethyl ammonium hydroxide of organic amine.
In the method provided by the invention, after the process of the said recovery product of step (2) is normally used deionized water wash 3～4 times, drying is 3～8 hours under 80～150 ℃, and again 500～700 ℃ of following roastings 4～8 hours, the purpose of roasting is in order to remove organic amine and the charcoal in the product.
Method provided by the invention, operating process is simple, when charcoal solid template is removed in roasting, has also removed the organic amine template simultaneously, does not synthesize to molecular sieve and brings extra operation steps.
Method provided by the invention be will have crosslinked open type macropore and a mesoporous monolithic silica column unformed silicon skeleton through the transition of charcoal skeleton and then change into crystalline form β zeolite.The gained sample is that 7.7 °, 21.5 °, 22.4 ° three place all has diffraction peak to occur at 2 θ angles, and this three places diffraction peak is the characteristic peak of β zeolite, illustrates that the crystal formation of preparation product is β.The β zeolite is together tightly packed, after charcoal is removed in roasting, the beta zeolite with multilevel pore canals pore passage structure that obtains is clear, and multistage pore canals such as micron order macropore, mesoporous and micropore have tangible gradation sense, SEM figure explanation micron order macropore have (macropore), a N with 2～3 μ m
2Adsorption-desorption figure illustrates the existing of mesoporous and micropore (micropore with mesoporous and 0.7nm of the about 12.5nm of mean pore size) (referring to Fig. 3 and Fig. 4).
The invention provides the beta zeolite with multilevel pore canals of method preparation, huge potential using value is arranged in fields such as catalysis and separation, particularly overcome the restriction of zeolite micropore to its catalytic performance, wherein the existence of open type macropore can be shortened the distance of reaction molecular diffusion, can make the pressure drop of device reduce and then improve the unit capacity of device, can make the selectivity of product be easy to adjust and control, mesoporously provide abundant inner ratio surface area, this has very important significance to macromolecular catalyzed reaction.
Description of drawings
Fig. 1 is beta zeolite with multilevel pore canals sample A2, A7, A10, A12, the A14 of embodiment 4,9,12,14,16,19 preparation, the XRD figure of A17.
Fig. 2 is beta zeolite with multilevel pore canals sample A1, A20, A24, A28, the A32 of embodiment 3,22,26,30,34,37 preparation, the XRD figure of A35.
Fig. 3 is the SEM figure of sample A1 institute synthetic beta zeolite with multilevel pore canals among the embodiment 3.
Fig. 4 is the N of the beta zeolite with multilevel pore canals sample A1 of embodiment 3 preparations
2Adsorption-desorption figure.
Fig. 5 is the graph of pore diameter distribution of the beta zeolite with multilevel pore canals sample A1 of embodiment 3 preparations.
Fig. 6 is the SEM figure of the monolithic silica column B1 of embodiment 1 preparation.
Embodiment
The following examples will be further described method of the present invention, but therefore not limit content of the present invention.
Among the embodiment, synthetic raw materials used middle tetraethyl-oxyammonia is a technical grade, and other is SILVER REAGENT.
Among the embodiment, XRD records with day island proper Tianjin Shimadzu XRD7000 type X-ray diffractometer; SEM records with JSM-35C electronic scanning Electronic Speculum instrument; N
2How absorption obtains with the absorption instrument with TP-5000.
Embodiment 1
The 0.01mol/L acetic acid solution of tetramethoxysilance, 6g polyoxyethylene glycol and the 30ml of 30ml is stirred, after the sealing, stir 50min down at 0 ℃.In gained colloidal sol impouring tetrafluoroethylene test tube or Glass tubing, ageing is one day in 30 ℃ of water-baths, obtains wet silicagel column.Soak silicagel column with 0.01mol/L ammoniacal liquor then, with the preparation mesopore.Respectively with the ethanolic soln and the tween 80 immersion cylinder 6h of 0.1mol/L salpeter solution, distilled water, 30% ethanol/water, final drying, roasting obtain monolithic silica column B again
1
By mass ratio is 1.25 sucrose: 0.14H
2SO
4: 5 water wiring solution-formings, monolithic silica column B1 put into wherein soaks 30min, then 6 hours, 160 ℃ of 100 ℃ of dryings 6 hours, repeat to soak, dry, polymerization process once, then in 900 ℃ of charings 4 hours, obtain charcoal silicon compound sample C1.
Embodiment 3
Raw material: 0.031 gram sodium aluminate, 0.055 gram sodium hydroxide, 1.85 gram tetraethyl ammonium hydroxide solution, 0.65 gram charcoal silicon compound.
Experimentation: with sodium aluminate, sodium hydroxide, tetraethyl ammonium hydroxide solution mixing and stirring, then this solution is poured in the reactor that C1 is housed, is stirred and to make it fully wetting, with the airtight back of reactor in 150 ℃ of following crystallization 48 hours.Crystallization finishes postcooling, after filtration, washing, puts into baking oven again in 100～110 ℃ of dryings 3～4 hours, gains is burnt 5 hours in 600 ℃ of retort furnaces again, promptly gets product beta zeolite with multilevel pore canals sample, is designated as A1.
The XRD spectra of sample A1 is seen Fig. 2, as can be seen from the figure, be that 7.7 °, 21.5 °, 22.4 ° three place all has the peak to occur at 2 θ angles, and this peak, three places is the characteristic peak of β zeolite, illustrates that the crystal formation of preparation product is β.
The SEM figure of sample A1 sees Fig. 3, and as can be seen from Figure 3 A1 has the macropore of 2～3 μ m.
The N of sample A1
2Adsorption-desorption figure sees Fig. 4.
The graph of pore diameter distribution of sample A1 is seen Fig. 5, and as can be seen from Figure 5, A1 has the micropore of the mesoporous and 0.7nm of the about 12.5nm of mean pore size.
Embodiment 4～9
Be prepared experiment with the method identical with embodiment 1, change the quality of sodium hydroxide in feeding intake, be respectively: 0.015 gram, 0.027 gram, 0.043 gram, 0.066 gram, 0.09 gram, 0.097 gram, obtain the beta zeolite with multilevel pore canals sample, sample is designated as A2, A3, A4, A5, A6 and A7 respectively.
Wherein the XRD spectra of A2 and A7 is seen Fig. 1.A 3, A4, A5, A6 have the XRD spectra feature of A1.
SEM figure and the N of A2, A3, A4, A5, A6 and A7
2Adsorption-desorption figure has the feature of A1.
Be prepared experiment with the method identical with embodiment 1, change that the quality of tetraethyl ammonium hydroxide solution is 0.83 gram in feeding intake, the quality of water is 0.83 gram, obtains product beta zeolite with multilevel pore canals sample, is designated as A8.A8 has the XRD spectra feature of A1, its SEM figure and N
2Adsorption-desorption figure has the feature of A1.
Embodiment 11
Be prepared experiment with the method identical with embodiment 1, change that the quality of tetraethyl ammonium hydroxide solution is 1.1 grams in feeding intake, the quality of water is 0.62 gram, obtains product beta zeolite with multilevel pore canals sample, is designated as A9.A9 has the XRD spectra feature of A1, its SEM figure and N
2Adsorption-desorption figure has the feature of A1.
Embodiment 12
Be prepared experiment with the method identical with embodiment 1, change that the quality of tetraethyl ammonium hydroxide solution is 1.34 grams in feeding intake, the quality of water is 0.42 gram, obtains product beta zeolite with multilevel pore canals sample, is designated as A10.A10 has the XRD spectra feature of A1, its SEM figure and N
2Adsorption-desorption figure has the feature of A1.
Embodiment 13
Be prepared experiment with the method identical with embodiment 1, change that the quality of tetraethyl ammonium hydroxide solution is 1.6 grams in feeding intake, the quality of water is 0.21 gram, obtains product beta zeolite with multilevel pore canals sample, is designated as A11.A11 has XRD spectra, SEM figure and the N of A1
2The feature of adsorption-desorption figure.
The XRD spectra of A12 and A14 is seen Fig. 1.A13 and A15 have the XRD spectra feature of A1.
A12, A13, A14 and A15 have A1 SEM figure and N
2Adsorption-desorption figure feature.
Embodiment 18～21
Embodiment 18～21 usefulness and embodiment 1 identical method is prepared experiment, and difference is the difference of crystallization temperature, is respectively 100 ℃, 120 ℃, 135 ℃, 165 ℃, obtains product beta zeolite with multilevel pore canals sample, is designated as A16, A17, A18 and A19.
The XRD spectra of A17 is seen accompanying drawing 1, and A16, A18 and A19 have the XRD spectra feature of A1.
A16, A17, A18 and A19 have SEM figure and the N of A1
2The feature of adsorption-desorption figure.
Embodiment 22
Be prepared experiment with the method identical with embodiment 1, the quality of tetraethyl ammonium hydroxide solution was 1.5 grams during difference was to change and feeds intake, and obtained product beta zeolite with multilevel pore canals sample, was designated as A20.
The XRD spectra of A20 is seen Fig. 2, and A20 has SEM figure and the N of A1
2Adsorption-desorption figure feature.
Embodiment 23～26
Embodiment 23～26 usefulness and embodiment 9 identical methods are prepared experiment, to wherein adding entry 0.18 gram, 0.36 gram, 0.55 gram, 0.74 gram again, obtain product beta zeolite with multilevel pore canals sample respectively, are designated as A21, A22, A23 and A24.
The XRD spectra of A24 is seen Fig. 2, and A21, A22, A23 have the XRD spectra feature of A1.A21, A22, A23 and A24 have SEM figure and the N of A1
2Adsorption-desorption figure feature.
Embodiment 27～36
Be prepared experiment with the method identical with embodiment 1, difference is the difference of crystallization time, crystallization time was respectively 6 hours, 8 hours, 10 hours, 12 hours, 24 hours, 36 hours, 60 hours, 72 hours, 84 hours and 96 hours, obtain product multistage pore canal ZSM-5 zeolite sample, be designated as A25, A26, A27, A28, A29, A30, A31, A32, A33 and A34 respectively.
The XRD spectra of A28 and A32 is seen Fig. 2, and A25, A26, A27, A29, A30, A31, A33 have the XRD spectra feature of A1.
SEM figure and the N of A25, A26, A27, A28, A29, A30, A31, A32, A33 and A34 with A1
2Adsorption-desorption figure feature.
Embodiment 37
Be prepared experiment with the method identical with embodiment 1, difference is to change the crystallization mode, in 120 ℃ of following crystallization after 24 hours again in 150 ℃ of following crystallization 24 hours, obtain product beta zeolite with multilevel pore canals sample, be designated as A35.The XRD spectra of A35 is seen Fig. 2, and has SEM figure and the N of A1
2Adsorption-desorption figure feature.
Claims (6)
1, a kind of preparation method of beta zeolite with multilevel pore canals, this method comprises the steps:
(1) floods monolithic silica column with sucrose solution, then in 3～9 hours, 150～180 ℃ polyase 13～9 of 80～120 ℃ of dryings hour, 750～1200 ℃ of charings 2～8 hours, obtain the charcoal silicon compound, wherein, the mass ratio of each component is 0.8～1.5 sucrose: 0.1～0.2H in the said sucrose solution
2SO
4: 3～7H
2O water, charcoal silicon mass ratio is in the charcoal silicon compound: 1 charcoal: 3～3.5 silicon, said monolithic silica column is to be the silicon source with tetramethoxy-silicane, tetraethoxysilane or water glass, polyoxyethylene glycol is a template, with second acid for adjusting pH value to 10～12,, washing mesoporous through preparing, drying and roasting obtain, and it is to soak 5～7h with 0.01mol/L ammoniacal liquor at 110～130 ℃ that said monolithic silica column prepares mesoporous process;
(2) use the mixing solutions of forming by aluminium source, mineral alkali, tetraethyl ammonium hydroxide, water wetting the charcoal silicon compound after, 100～150 ℃ of following crystallization 6～96 hours and reclaim product in closed reaction kettle, each reactant is in mole in the reaction system: 1～10 aluminium source: 23～29 tetraethyl ammonium hydroxides: 4～30 mineral alkalis: 100 silicon source: 800～1200H
2O, said silicon source is from the charcoal silicon compound.
2, according to the method for claim 1, it is characterized in that said sucrose solution dipping monolithic silica column carries out in the step (1) under negative pressure, said charing is carried out under nitrogen protection or vacuum.
3, according to the method for claim 1, it is characterized in that the said monolithic silica column of step (1), its macropore diameter is 0.5～8.0 μ m, mesoporous aperture is 3～30nm, and is penetrating between the macropore.
4,, it is characterized in that the said aluminium of step (2) source is that sodium aluminate, mineral alkali are sodium hydroxide according to the method for claim 1.
5, according to the method for claim 1, it is characterized in that the said recovery product of step (2) be with crystallization product with deionized water wash after, drying is 3～8 hours under 80～150 ℃, removes tetraethyl ammonium hydroxide and charcoal in 4～8 hours 500～700 ℃ of following roastings again.
6, the beta zeolite with multilevel pore canals of one of claim 1～5 method preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100013327A CN100548880C (en) | 2006-01-19 | 2006-01-19 | A kind of preparation method of beta zeolite with multilevel pore canals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100013327A CN100548880C (en) | 2006-01-19 | 2006-01-19 | A kind of preparation method of beta zeolite with multilevel pore canals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101003378A CN101003378A (en) | 2007-07-25 |
| CN100548880C true CN100548880C (en) | 2009-10-14 |
Family
ID=38702815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100013327A Active CN100548880C (en) | 2006-01-19 | 2006-01-19 | A kind of preparation method of beta zeolite with multilevel pore canals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100548880C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1882676A3 (en) * | 2006-07-12 | 2009-07-01 | Haldor Topsoe A/S | Fabrication of hierarchical zeolite |
| CN101830480B (en) * | 2009-03-11 | 2012-01-25 | 中国石油化工股份有限公司 | Preparation method of zeolite molecular sieve monolith with composite pore structure |
| CN102874830B (en) * | 2011-07-11 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing mesopore-micropore zeolite molecular sieve material |
| CN103964458B (en) * | 2013-01-29 | 2015-09-16 | 中国石油大学(北京) | Beta zeolite of a kind of high silica alumina ratio multistage pore canal and preparation method thereof |
| CN103708488B (en) * | 2013-12-27 | 2015-04-22 | 复旦大学 | Method for preparing multilevel porous zeolite through microwave assisted decomposition of hydrogen peroxide |
| CN103979570B (en) * | 2014-05-14 | 2016-01-06 | 武汉理工大学 | The synthetic method of a kind of novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve |
| CN106391102B (en) * | 2015-07-28 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of multi-stage porous hydrocracking catalyst of the molecular sieve of type containing Beta and its application |
| CN106391103B (en) * | 2015-07-28 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of multi-stage porous hydrocracking catalyst of silicon-aluminum containing and its application |
| WO2019010700A1 (en) * | 2017-07-14 | 2019-01-17 | 北京大学深圳研究生院 | Multi-pore zeolite having layered structure and preparation method therefor |
| CN109647501B (en) * | 2019-01-18 | 2021-12-28 | 中国科学院城市环境研究所 | Hierarchical porous Fe-beta molecular sieve catalyst and preparation method and application thereof |
| CN114835136B (en) * | 2022-05-24 | 2023-12-26 | 天津大学 | Hierarchical pore beta molecular sieve with ordered mesoporous structure, preparation method and application |
-
2006
- 2006-01-19 CN CNB2006100013327A patent/CN100548880C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101003378A (en) | 2007-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100548880C (en) | A kind of preparation method of beta zeolite with multilevel pore canals | |
| CN101003380B (en) | Method for synthesizing ZSM-5 zeolite with multilevel pore canals | |
| CN101885493B (en) | Synthesis method of ZSM-5/beta nuclear shell-shaped molecular sieve | |
| CN102515195B (en) | Method for synthesizing integral multi-stage pore canal molecular sieve in one step | |
| CN101362598A (en) | Synthetic process of ordered mesoporous carbon material | |
| CN105692644A (en) | Hierarchical-porous zeolite preparation method | |
| CN105271299B (en) | A kind of preparation method of the zeolites of mesoporous ZSM 5 | |
| CN101830480B (en) | Preparation method of zeolite molecular sieve monolith with composite pore structure | |
| CN108069437B (en) | Beta molecular sieve and synthetic method and application thereof | |
| CN106219569B (en) | A method of no one step of secondary template prepares porous zeotile | |
| CN108658087B (en) | Hierarchical pore TS-1 zeolite material and preparation method thereof | |
| CN108069436B (en) | Beta molecular sieve and synthetic method thereof | |
| CN108069435B (en) | Beta molecular sieve with multistage pore canals and synthesis method thereof | |
| US11434140B2 (en) | Hierarchical zeolites and preparation method therefor | |
| CN107020145B (en) | Mesoporous IM-5 molecular sieve and preparation method thereof | |
| CN1338427A (en) | Silicon molecular sieve and its synthesizing process | |
| CN105664860A (en) | MOF type hierarchical porous material IPD-mesonMOF-12 | |
| CN113830787B (en) | Hierarchical pore MFI type nano zeolite molecular sieve and preparation method and application thereof | |
| CN102500408B (en) | Micropore-mesopore catalyst material and preparation method thereof | |
| CN112744831A (en) | Method for preparing titanium-containing molecular sieve, titanium-containing molecular sieve produced by method and cyclohexanone oximation reaction method | |
| CN111484038A (en) | Hierarchical porous aluminum-rich Beta molecular sieve and preparation method thereof | |
| CN101177281A (en) | Method for preparing nano NaY molecular sieve | |
| CN101112995A (en) | Method for preparing organic-inorganic hybrid integral material | |
| CN115140746B (en) | ZSM-5 molecular sieve with cascade hole distribution and preparation method thereof | |
| CN111099602A (en) | Iron-containing composite porous molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |