CN101723402B - Method for synthesizing core-shell type zeolite molecular sieve - Google Patents
Method for synthesizing core-shell type zeolite molecular sieve Download PDFInfo
- Publication number
- CN101723402B CN101723402B CN2008100438769A CN200810043876A CN101723402B CN 101723402 B CN101723402 B CN 101723402B CN 2008100438769 A CN2008100438769 A CN 2008100438769A CN 200810043876 A CN200810043876 A CN 200810043876A CN 101723402 B CN101723402 B CN 101723402B
- Authority
- CN
- China
- Prior art keywords
- zsm
- molecular sieve
- core
- sio
- shell type
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing ZSM-5/ZSM-5 core-shell type zeolite molecular sieve, mainly solving the technical problems of expensive used raw materials, great environment pollution of template agent, high difficulty of industrial amplification and synthesis, difficult industrial production and the like of the core-shell type zeolite molecular sieve in the prior art. The invention adopts the following technical scheme: the core-shell zeolite molecular sieve is prepared by adopting ZSM-5 core phase molecular sieve with a relatively low silica alumina ratio as a seed crystal, using at least one of soluble glass, silica solution, sodium silicate, white carbon black or atlapulgite which are cheap and easily obtained as a silicon source, and taking at least one organic amine from ethylamine, ethanediamine, propylamine and butylamine or the mixture of the organic amine and inorganic amine as a template agent so as to better solve the above technical problems. The invention can be used in industrialized synthetic production of core-shell type molecular sieve.
Description
Technical field
The present invention relates to a kind of synthetic method of ZSM-5/ZSM-5 core-shell type zeolite molecular sieve.
Background technology
Zeolite molecular sieve is the crystalline microporous material that a class has skeleton structure, pore passage structure with specific dimensions, shape, bigger specific surface and stronger adjustable acid matter, be widely used in the process of refining of petroleum and processing, as catalyzed reactions such as catalytic cracking, alkane isomerization, catalytic reforming and toluene disproportionations.
Along with the petrochemical complex industrial expansion, round the output that how to improve the purpose product, suppress side reaction, improve the problems such as selectivity of reaction, people have carried out increasing research.Generally speaking, improve catalyzer in reaction process optionally simultaneously, tend to cause the decline significantly of catalyst activity.Therefore, in order to improve the selecting property performance of molecular sieve catalyst, reduce the activity of such catalysts loss simultaneously, the investigator has carried out big quantity research to the modification of zeolite molecular sieve.Usually the method for modifying that adopts comprises: high-temperature vapor is handled, organic acid dealuminzation, chemical modification, outside surface organosilicon passivation etc.Wherein industrial more use is, outside surface repeated multiple times at the ZSM-5 molecular sieve catalyst is carried out the organosilicon Passivation Treatment, buried in oblivion the acidic site of catalyzer outside surface, thereby make catalyzer have selectivity of product, yet the shortcoming of this method is that preparation process is various, industrial operation repeatability is relatively poor, when molecular sieve outer surface carries out organosilicon Passivation Treatment modification raising catalyst selectivity, also tend to blocking portion aperture or duct, thereby catalytic activity is descended significantly.
As a kind of new zeolite molecular sieve material, the ZSM-5/ZSM-5 core-shell type zeolite molecular sieve is meant that with ZSM-5 zeolite molecular sieve crystal grain be nuclear phase, at its outside surface parcel growth one deck molecular sieve shell, this layer molecular sieve shell can be Different Silicon aluminum ratio ZSM-5, it also can be the Silicate-I molecular sieve shell of pure silicon, this ZSM-5 or total silicon Silicate-I shell can be under the prerequisites of duct diffusion that does not influence nuclear phase ZSM-5 zeolite and acid matter, the modulation outer surface properties, pure silicon shell the even also outside surface of highly active nuclear phase ZSM-5 molecular sieve can be tuned as the inertia structure.The hud typed structure of this uniqueness helps suppressing to occur in the side reaction of outside surface, reduces the disadvantageous effect to the nuclear phase molecular sieve catalytic active.In addition, because the nuclear phase of core-shell type molecular sieve is identical with the crystalline structure of shell phase, growth to each other is in conjunction with tight, and the duct communicates, thereby diffusion is good, then can have been overcome " back setting effect " of organic-silicon-modified back generation preferably by the catalyzer of this molecular sieve preparation.
Document U.S. Pat 4067920, US4011276 among US5367099 and the US5607888, has proposed institute's synthetic ZSM-5 molecular sieve is carried out the modification of pore structure, promptly reduces port size and shielding outer surface acidity active sites, the preparation shape-selective catalyst; Need in the above-mentioned patent catalyzer is carried out repeatedly modification, and modification rear catalyst para-selectivity is when rising, its transformation efficiency descends more, promptly exists so-called " back setting effect ".
Introduced a kind of outside surface inert silicate zeolite molecular sieve among the US4868146, this zeolite is the core phase with the ZSM-5 or the ZSM-23 of central hole structure, under the situation that fluorion exists, forms outer persilicic shell.This zeolite molecular sieve needs earlier that the nuclear phase zeolite molecular sieve and the water thorough mixing of sodium hydroxide, 4-propyl bromide, silicon sol, little crystal grain is even in building-up process, again mixed slurry is moved into crystallizing kettle, 99 ℃ of crystallization are after 3 hours, add ammonium fluoride solution again, continued crystallization 16 hours, the gained solid product makes core-shell type molecular sieve through washing, drying.In this synthetic method, must use 4-propyl bromide to be template, also need introduce fluorion simultaneously, could form the total silicon shell of better quality, and use 4-propyl bromide and fluorochemical to be raw material, have synthetic cost height, environmental pollution is big, shortcomings such as water treatment difficulty height.
Disclosing among the US4503164 that a kind of what have geminus is nucleus with the borosilicate crystal, is the zeolite molecular sieve of shell with the silica crystal, in the nucleus of borosilicate, and SiO
2/ B
2O
3At least be higher than 12, the weight ratio of shell and nuclear is from 0.1/1～5/1, and this zeolite catalyst has good para-selectivity in toluene and methyl alcohol reaction, and p-X concentration in Mixed XYLENE is much higher than thermodynamic(al)equilibrium in its product.But it is template that this patent needs 4-propyl bromide, is the silicon source with positive tetraethyl orthosilicate, the uniform silicon oxide shell that in building-up process, will make it to form, and operation easier is big in industrial production, poor repeatability.
Generally speaking, the research of core-shell type molecular sieve report is mainly based on total silicon shell layer at present, in building-up process, need be the silicon source with positive tetraethyl orthosilicate often, be template with the 4-propyl bromide, thereby in the industrial building-up process, exist the raw materials for production costliness, the template environmental pollution is big, and the industrial operation difficulty is big, and poor repeatability is difficult to technical barriers such as industry's enlarging production.
Summary of the invention
Technical problem to be solved by this invention is the core-shell molecular sieve that the shell of the core-shell type molecular sieve of prior art report mostly is the total silicon type mutually, it is the silicon source that this molecular sieve analog often needs with positive tetraethyl orthosilicate, with the 4-propyl bromide is template, exist the raw material costliness, the template environmental pollution is big, the problem that is difficult to industry's enlarging production provides a kind of synthetic method of new core-shell type zeolite molecular sieve.This method is the silicon source with water glass cheap and easy to get, is template with ammoniacal liquor or hypotoxic small molecules organic amine, and it is inexpensive to have a raw material, and production cost is low, the advantage that environmental pollution is little.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of synthetic method of ZSM-5/ZSM-5 core-shell type zeolite molecular sieve may further comprise the steps:
A) silicon source, aluminium source and organic amine template R are mixed obtain PH 9 basoid solution, the mole proportioning of synthetic liquid is: R/SiO
2=0.02～2, H
2O/SiO
2=10～5000, OH
-/ SiO
2=0.02～10, SiO
2/ Al
2O
3=60～400, M
2O/SiO
2=0～2, M is Na or K;
B) in the synthetic liquid of above-mentioned alkalescence, add SiO
2/ Al
2O
3Mol ratio be 15～100 ZSM-5 zeolite as nuclear Jingjing kind, stir; Wherein to examine the mass ratio of contained silicon-dioxide in brilliant add-on and the synthetic mixed solution be 0.01～50 to ZSM-5;
C) with the mixed solution in above-mentioned (b) step in 70～180 ℃ of following crystallization 0.5～480 hour;
D) crystallization finishes postcooling, filtration, washing, ammonium exchange, drying, gets the ZSM-5/ZSM-5 core-shell type zeolite molecular sieve;
Wherein the silicon source is selected from least a in water glass, silicon sol, water glass, white carbon black or the atlapulgite in (a) step; The aluminium source is selected from Tai-Ace S 150, sodium aluminate, aluminum isopropylate, aluminum chloride or γ-Al
2O
3In at least a; The organic amine template is selected from least a or inorganic ammonia in the organic amine of ethamine, quadrol, propylamine, butylamine and composition thereof.
In the technique scheme, the PH of the alkaline aqueous solution of organic amine template in the building-up process of ZSM-5/ZSM-5 core-shell type zeolite molecular sieve〉9; The preferable range of the mole proportioning of synthetic mixed solution is: R/SiO
2=0.05～1, H
2O/SiO
2=200～2000, OH
-/ SiO
2=1～8, SiO
2/ Al
2O
3=100～300, M
2O/SiO
2=0～2, M=Na or K; (b) to examine the quality of contained silicon-dioxide in brilliant add-on and the synthetic mixed solution be 0.2～40 than preferable range to the ZSM-5 in the step; (c) the crystallization temperature preferable range is 100～150 ℃ in the step, and the crystallization time preferable range is 2.5～240 hours.
Adopt technique scheme, with SiO
2/ Al
2O
3Mol ratio be 15～100 ZSM-5 molecular sieve as the nuclear phase crystal seed, join in the above-mentioned synthesis reaction mixture, can obtain through hydrothermal crystallizing, can synthesize a kind of ZSM-5/ZSM-5 core-shell type zeolite molecular sieve material, the nuclear phase SiO of this molecular sieve
2/ Al
2O
3Mol ratio is 15～100, shell phase SiO
2/ Al
2O
3Mol ratio is 50～350 core-shell type zeolite molecular sieve, and the periphery of the nuclear phase ZSM-5 of this molecular sieve is wrapped in the ZSM-5 shell, and shell thickness is 20～800nm, and nuclear phase and the shell weight ratio between mutually is 10/90～98/2.
The present invention is in the building-up process of zeolite, and as crystal seed, the shell that joins high silica alumina ratio becomes in the sizing material with the ZSM-5 zeolite molecular sieve of a large amount of relatively low silica alumina ratios, on the one hand, in building-up process, promotes the formation of MFI structure, and is unfavorable for α-SiO
2Generation Deng stray crystal; On the other hand, in the zeolite shell crystallisation process stage, the existence of the zeolite molecular sieve of a large amount of low silica-alumina ratios, the more nucleus that become in the glue homodisperse, can be by regulating the grain size of the shell phase zeolite molecular sieve that crystallizing kettle offset plate rotating speed speed, shell become the basicity of glue to control to generate on the final nuclear phase zeolite molecular sieve, help that synthetic shell high silica alumina ratio and crystal grain are thin, the low bigger core-shell type zeolite molecular sieve of crystal grain of nuclear phase silica alumina ratio.
In addition, the present invention has adopted silicon source cheap and easy to get, and the mixture that pollutes little small molecules organic amine or itself and inorganic ammonia with low toxicity is a template, has synthesized nuclear phase SiO
2/ Al
2O
3Mol ratio is 15～100, shell phase SiO
2/ Al
2O
3Mol ratio is 50～350 ZSM-5/ZSM-5 core-shell type zeolite molecular sieve, and nuclear phase is the different of aluminum content with the key distinction of shell phase, and biphase crystal topological framework is identical, and two-phase is grown closely each other and the duct communicates.Therefore, can think that the catalytic activity of this core-shell molecular sieve will be suitable with the catalytic activity of low silica-alumina ratio nuclear phase, on the other hand, because the SiO of shell phase
2/ Al
2O
3Mol ratio is 50～350, and the sour density of its outside surface has obtained suitably reducing, and has reduced the generation of outside surface side reaction, thereby when keeping than high reaction activity, improves the selectivity and the stability of reaction effectively.The inventive method synthetic material is particularly useful for the reaction of methylbenzene methanol selective methylation, its stability has obtained improving significantly, and through 300 hours stability reaction, its average toluene conversion was 25%, the p-Xylol selectivity is 80%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
Comparative example 1 is used for illustrating nuclear phase SiO
2/ Al
2O
3Be 25, shell is the synthetic and Preparation of catalysts of the hud typed ZSM-5/ZSM-5 zeolite molecular sieve of total silicon Silicate-I mutually
[comparative example 1]
The 10 gram 25%TPAOH aqueous solution, 4 gram tetraethoxys, 200 gram water are mixed, stirred 4 hours, add 20 gram SiO then
2/ Al
2O
3Be 25 ZSM-5 nuclear phase molecular sieve, put into the 1 liter stainless steel crystallizing kettle that band stirs, airtight, be warming up to 180 ℃, thermostatic crystallization 1 day, stirring velocity is 100rpm.When crystallization finished, chilling filtered solid product, wash to washings PH=7, and 110 ℃ of oven dry of spending the night, 550 ℃ of roastings made core-shell molecular sieve CS1 in 4 hours in retort furnace then.Shell SiO wherein
2/ Al
2O
3The analysis showed that to be 510, nuclear phase is 95/5 with shell weight ratio mutually, and its XRD analysis is the result conform to data in literature.
Core-shell molecular sieve CS1 was joined in the 10 weight % amine nitrate solutions under 95 ℃ of stirrings ion-exchange 3～4 hours.Repeated exchanged 2～3 times, filtration, washing after filtering, oven dry.
Get core-shell molecular sieve CS1 10 grams after the ion-exchange, add 40% silica sol binder, 6.3 grams, and 0.3 gram methylcellulose gum (or sesbania powder), stir and mediate, and extrusion is shaped, and dries back 550 ℃ of roastings 4 hours in retort furnace, obtains core-shell molecular sieve catalyzer CS-Cat.1.Wherein, core-shell molecular sieve accounts for 80% in catalyzer, SiO
2Binding agent accounts for 20%.
[embodiment 1]
15 milliliters of ethamine, 210 gram water glass (are contained SiO
225.8 weight %, Na
2O7.3 weight %), 9.7 gram Tai-Ace S 150 and 650 gram water mix, and stir 1 hour, add 25 then and restrain SiO
2/ Al
2O
3Be 25 ZSM-5 nuclear phase molecular sieve, synthetic liquid PH is 9.2, and powerful the stirring 3 hours put into 1000 milliliters stainless steel crystallizing kettle, and be airtight, is warming up to 150 ℃, thermostatic crystallization 3 days.When crystallization finished, chilling filtered solid product, washing, and 110 ℃ of oven dry of spending the night make core-shell molecular sieve CS2, shell SiO
2/ Al
2O
3The analysis showed that to be 80, the nucleocapsid ratio is 95/5, and its XRD analysis is the result conform to data in literature.
Core-shell molecular sieve CS2 is pressed described in the comparative example 1 after the method ion-exchange, in molecular sieve account for 80%, binding agent accounts for 20% ratio, with core-shell molecular sieve CS2 and SiO
2Binding agent mixes, and stir and mediate, and extrusion is shaped, dry back 550 ℃ of roastings 4 hours in retort furnace, cut grain, again saccharoid is immersed in 25% the silicon oil solution 10 hours, natural air drying, 538 ℃ of roastings 4 hours obtain core-shell molecular sieve catalyzer CS-Cat.2.
[embodiment 2～10]
Embodiment 2～10th, with the synthetic ratio and the synthesis condition of table 1, by implementing the synthetic core-shell molecular sieve CS3～12# that obtains of 1 similar approach and step, and be prepared into nuclear brilliant catalyzer Cat.0 and core-shell molecular sieve catalyzer CS-Cat1～4# according to embodiment 1 similar method, see table 2 for details.
Table 1 core-shell molecular sieve preparation condition
Table 2 nucleocapsid catalyst preparation condition
[embodiment 11]
Estimate methylbenzene methanol selective alkylation reaction performance with 2 gram catalyzer on the continuous micro-reaction equipment of fixed bed: reaction raw materials is methylbenzene methanol mixing solutions (the methylbenzene methanol mol ratio is 2), under the gas phase hydro condition, reaction pressure is that 0.5 MPa, 420 ℃ of temperature of reaction, feed liquid volume space velocity are 4 hours
-1, hydrogen-hydrocarbon ratio is that sampling analysis records toluene conversion and p-Xylol selectivity in the process, and is as shown in table 3 under 3 the condition.The response data of having listed silica alumina ratio in the table and be 25 the brilliant catalyzer of making of ZSM-5 nuclear as a comparative example, the result shows, examining brilliant catalyzer with ZSM-5 compares with total silicon shell phase catalyst (comparative example 1), the core-shell molecular sieve catalyzer has higher p-Xylol selectivity, catalyst deactivation speed is all slowed down to some extent, at the catalytic performance of catalyzer simultaneously preferably, stability is improved significantly.
Table 3 core-shell molecular sieve catalyzer toluene methylation reactivity worth
Claims (4)
1. the synthetic method of a ZSM-5/ZSM-5 core-shell type zeolite molecular sieve may further comprise the steps:
A) silicon source, aluminium source and organic amine template R are mixed the synthetic mixed solution that obtains pH＞9, the mole proportioning of synthetic mixed solution is: R/SiO
2=0.02～2, H
2O/SiO
2=10～5000, OH
-/ SiO
2=0.02～10, SiO
2/ Al
2O
3=60～400, M
2O/SiO
2=0～2, M is Na or K;
B) in above-mentioned synthetic mixed solution, add SiO
2/ Al
2O
3Mol ratio be 15～100 ZSM-5 zeolite as nuclear Jingjing kind, stir; Wherein to examine the mass ratio of contained silicon-dioxide in brilliant add-on and the synthetic mixed solution be 0.01～50 to ZSM-5;
C) with the mixed solution in above-mentioned (b) step in 70～180 ℃ of following crystallization 0.5～480 hour;
D) crystallization finishes postcooling, filtration, washing, ammonium exchange, drying, gets the ZSM-5/ZSM-5 core-shell type zeolite molecular sieve;
Wherein the silicon source is selected from least a in water glass, silicon sol, water glass, white carbon black or the atlapulgite in (a) step; The aluminium source is selected from Tai-Ace S 150, sodium aluminate, aluminum isopropylate, aluminum chloride or γ-Al
2O
3In at least a; The organic amine template is selected from least a in the organic amine of ethamine, quadrol, propylamine, butylamine.
2. according to the synthetic method of the described ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of claim 1, it is characterized in that pH＞9 of the alkaline aqueous solution of organic amine template; The mole proportioning of synthetic mixed solution is: R/SiO
2=0.05～1, H
2O/SiO
2=200～2000, OH
-/ SiO
2=1～8, SiO
2/ Al
2O
3=100～300, M
2O/SiO
2=0～2, M=Na or K.
3. the synthetic method of ZSM-5/ZSM-5 core-shell type zeolite molecular sieve according to claim 1 is characterized in that the mass ratio that ZSM-5 in (b) step examines contained silicon-dioxide in brilliant add-on and the synthetic mixed solution is 0.2～40.
4. the synthetic method of ZSM-5/ZSM-5 core-shell type zeolite molecular sieve according to claim 1 is characterized in that crystallization temperature is 100～150 ℃ in (c) step, and crystallization time is 2.5～240 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100438769A CN101723402B (en) | 2008-10-28 | 2008-10-28 | Method for synthesizing core-shell type zeolite molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100438769A CN101723402B (en) | 2008-10-28 | 2008-10-28 | Method for synthesizing core-shell type zeolite molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101723402A CN101723402A (en) | 2010-06-09 |
| CN101723402B true CN101723402B (en) | 2011-07-20 |
Family
ID=42445059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100438769A Active CN101723402B (en) | 2008-10-28 | 2008-10-28 | Method for synthesizing core-shell type zeolite molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101723402B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102463136B (en) * | 2010-11-05 | 2014-01-01 | 中国石油化工股份有限公司 | Core-shell structure MFI molecular sieve and its preparation method |
| CN102951656B (en) * | 2012-10-16 | 2014-06-04 | 大连瑞克科技有限公司 | Method for synthesizing even-grained ZSM-5 molecular sieves |
| CN103803579B (en) * | 2012-11-07 | 2015-07-22 | 中国石油化工股份有限公司 | Core-shell structured ZSM-5 composite molecular sieve and preparation method thereof |
| CN103803580B (en) * | 2012-11-07 | 2015-12-02 | 中国石油化工股份有限公司 | Isomorphous ZSM-5 composite molecular screen of a kind of nucleocapsid structure and preparation method thereof |
| CN104211085B (en) * | 2013-06-05 | 2017-01-25 | 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 |
| CN105621434B (en) * | 2014-11-20 | 2018-11-20 | 中国石油化工股份有限公司 | Molecular sieve and its direct synthesis method with Shape-selective |
| CN107226474A (en) * | 2016-03-23 | 2017-10-03 | 中国石化扬子石油化工有限公司 | Mend aluminium method of modifying in a kind of ZSM-5 original positions |
| CN108383136B (en) * | 2018-05-07 | 2021-04-06 | 太原理工大学 | Preparation method of SSZ-13@ Nano SSZ-13 molecular sieve with core-shell structure |
| CN109516471B (en) * | 2018-12-24 | 2021-11-05 | 大连理工大学 | Synthesis method of ZSM-23 molecular sieve with aluminum-rich surface |
| CN112705248B (en) * | 2019-10-24 | 2023-07-04 | 中国石油化工股份有限公司 | Core-shell type MFI/MFI molecular sieve and preparation method thereof |
| CN111054430B (en) * | 2020-01-17 | 2022-11-25 | 太原理工大学 | Core-shell structure HZSM-5 molecular sieve for reaction of preparing aromatic hydrocarbon from methanol and preparation method thereof |
| CN111530494B (en) * | 2020-05-15 | 2023-11-10 | 洛阳市科创石化科技开发有限公司 | Composite carrier with inner core of molecular sieve and preparation method thereof |
| CN114425406B (en) * | 2020-10-10 | 2024-01-30 | 中国石油化工股份有限公司 | SiO for shape selective catalytic zeolite molecular sieve catalysts 2 Directional modification method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788374A (en) * | 1987-12-23 | 1988-11-29 | Mobil Oil Corporation | Zeolite catalysis |
| CN1699173A (en) * | 2005-06-14 | 2005-11-23 | 大连理工大学 | Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio |
| CN1982215A (en) * | 2005-12-16 | 2007-06-20 | 中国石油化工股份有限公司 | Core-shell structured molecular sieve, its production and use |
-
2008
- 2008-10-28 CN CN2008100438769A patent/CN101723402B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788374A (en) * | 1987-12-23 | 1988-11-29 | Mobil Oil Corporation | Zeolite catalysis |
| CN1699173A (en) * | 2005-06-14 | 2005-11-23 | 大连理工大学 | Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio |
| CN1982215A (en) * | 2005-12-16 | 2007-06-20 | 中国石油化工股份有限公司 | Core-shell structured molecular sieve, its production and use |
Non-Patent Citations (2)
| Title |
|---|
| Younes Bouizi et al..Factors Controlling the Formation of Core-Shell Zeolite-Zeolite Composites.《Chem. Mater.》.2006,第18卷(第20期),4959-4966. * |
| 张哲等.ZSM25(核)/AlPO4-5(壳)双结构分子筛的合成与催化裂化性能.《催化学报》.2003,第24卷(第11期),856-860. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101723402A (en) | 2010-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101723402B (en) | Method for synthesizing core-shell type zeolite molecular sieve | |
| CN101723401B (en) | ZSM-5/ZSM-5 core-shell type zeolite molecular sieve | |
| CN101885493B (en) | Synthesis method of ZSM-5/beta nuclear shell-shaped molecular sieve | |
| CN101332995B (en) | Method for preparing kaolin in-situ crystallization ZSM-5 molecular sieve | |
| CN101249968B (en) | Method for synthesizing Beta molecular sieve by organic-free template | |
| CN101722033A (en) | Core-shell type aromatic conversion catalyst, preparation method and application thereof | |
| CN101884935B (en) | Catalyst material and preparation method thereof | |
| CN101885662B (en) | Toluene methanol alkylation method | |
| CN101722034A (en) | Preparation method of mordenite/ZSM-5 core-shell type molecular sieve material | |
| CN103539152B (en) | Core-shell molecular sieve of Si modification and preparation method thereof | |
| CN102745714A (en) | Preparation method of small crystal grain ZSM-5 molecular sieve | |
| CN101618333B (en) | Y/silicate compound molecular sieve and method for preparing same | |
| CN104556094A (en) | Y/Silicalite-1 composite molecular sieve and preparation method thereof | |
| CN102557066A (en) | Tetraethoxysilane modified datolite molecular sieve and preparation method and application thereof | |
| CN101121526A (en) | Method for preparing nano Fe-ZSM-5 zeolite molecular sieve | |
| CN101885663B (en) | Method for converting heavy aromatics to light aromatics and transferring alkyl radical | |
| CN104556130A (en) | Method for synthesizing ZSM-5/Silicalite core-shell molecular sieve by using vapor phase process | |
| CN105621449A (en) | NaY type molecular sieve and preparation method thereof | |
| CN108529645B (en) | Preparation method of prismatic microporous small-grain mordenite molecular sieve | |
| CN102533316A (en) | Method for selective hydrocracking of light oil | |
| CN102050466B (en) | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material | |
| CN101514004B (en) | Coexisting molecular sieve and synthesis method thereof | |
| CN100408180C (en) | Method for preparing catalyst of para xylene through methylation of toluene | |
| CN103058209B (en) | Method for synthesizing small-grain PZSM-5 molecular sieve catalyst through two-step hydrothermal method | |
| CN103693654A (en) | Method for synthesis of IM-5 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 |