CN101723401A - ZSM-5/ZSM-5 core-shell type zeolite molecular sieve - Google Patents
ZSM-5/ZSM-5 core-shell type zeolite molecular sieve Download PDFInfo
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Abstract
The invention relates to a ZSM-5/ZSM-5 core-shell type zeolite molecular sieve which mainly solves the problem of a synthetic core-shell molecular sieve with the mol ratio of shell phase SiO2/Al2O3 larger than 100 or a total silicon type core-shell molecular sieve existing in the prior art. The invention better solves the problem by adopting the following technical scheme for forming the ZSM-5/ZSM-5 core-shell type zeolite molecular sieve: a ZSM-5 with the mol ratio of SiO2/Al2O3 as 15-100 is used as a core phase molecular sieve, a ZSM-5 with the mol ratio of SiO2/Al2O3 as 60-100 is used as a shell phase molecular sieve, a ZSM-5 shell layer is wrapped at the periphery of the core phase ZSM-5, the thickness of the shell layer is 20-800nm, and the proportion by weight of the core phase and the shell phase is 10/90-98/2; the ZSM-5/ZSM-5 core-shell type zeolite molecular sieve can be used in the industrial production of core-shell type molecular sieves.
Description
Technical field
The present invention relates to a kind 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 relatively low silica alumina ratio ZSM-5, it also can be the molecular sieve shell of the higher relatively or pure silicon ZSM-5 of silica alumina ratio, this ZSM-5 or total silicon Silicate-I shell mutually 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, diffusion is good, thereby then can overcome " back setting effect " that organic-silicon-modified back produces 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.
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 the silicon oxide shell that forms in this patent, operation easier is big in industrial production, poor repeatability.
Generally speaking, the applied research of core-shell type molecular sieve report is that shell is combined to hud typed ZSM-5/ZSM-5 zeolite molecular sieve with total silicon type Silicate-I mainly at present.In amplifying building-up process, poor repeatability, operation easier is big, 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 shell phase SiO of the core-shell type molecular sieve of existing application report
2/ Al
2O
3Mol ratio is greater than 100 or the problem of the core-shell molecular sieve of total silicon type, and a kind of new ZSM-5/ZSM-5 core-shell type zeolite molecular sieve is provided.This molecular application in aromatic hydrocarbons conversion catalyst processes such as toluene methylation, toluene ethylization, ethylbenzene alkylation, has the advantage that can reduce coking deactivation speed, prolongation catalyst life, improve product selectivity in the aromatic hydrocarbons conversion reaction.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ZSM-5/ZSM-5 core-shell type zeolite molecular sieve material, and with SiO
2/ Al
2O
3Mol ratio is that 15～100 ZSM-5 is the nuclear phase molecular sieve, with SiO
2/ Al
2O
3Mol ratio is that 60～≤ 100 ZSM-5 is a shell phase molecule sieve, and the periphery of nuclear phase ZSM-5 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.
In the technique scheme, the SiO of the nuclear phase of ZSM-5/ZSM-5 core-shell type zeolite molecular sieve
2/ Al
2O
3The preferable range of mol ratio is 15～70, and preferred scope is 15～50; The preferable range of the thickness of shell is 20～500nm, and preferred scope is 100～200nm; Nuclear phase and shell mutually between the preferable range of weight ratio be 50/50～98/2, more preferably scope is 80/20～90/10.
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.
ZSM-5/ZSM-5 core-shell type zeolite Preparation of catalysts method may further comprise the steps:
(a) mixing such as silicon source, aluminium source and organic amine template R are obtained the basoid solution of PH＞9, 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=60～100, 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) mixed solution in (b) is packed in the crystallizing kettle, in 70～180 ℃ of following crystallization 0.5～480 hour;
(d) crystallization finishes postcooling, filtration, washing, drying, gets the nucleocapsid zeolite molecular sieve;
(e) in required ratio the nucleocapsid zeolite molecular sieve is mixed with binding agent, get catalyst prod through kneading, extruded moulding, drying, roasting.
In the technique scheme, (a) a kind of or its mixture in silicon source employing tetraethoxysilance, water glass, silicon sol, water glass, white carbon black, the atlapulgite in the step; Sodium aluminate, Tai-Ace S 150, aluminum chloride, γ-Al are adopted in the aluminium source
2O
3, a kind of or its mixture in the aluminum isopropylate; The organic amine template adopts a kind of or its mixture in the organic or inorganic amine such as tetrapropyl oxyammonia, tetrapropyl amine bromide, methylamine, ethamine, propylamine, butylamine, hexahydroaniline, triethylene tetramine, diethylenetriamine, ammoniacal liquor; The PH of the alkaline aqueous solution of organic amine template＞9; The mole proportioning of synthetic mixed solution is: R/SiO
2=0.02～2, H
2O/SiO
2=5～500, OH
-/ SiO
2=0.02～10, SiO
2/ Al
2O
3=60～100, M
2O/SiO
2=0～2, M=Na or K.(b) to examine the mass ratio of contained silicon-dioxide in brilliant add-on and the synthetic mixed solution be 0.2～40 to the ZSM-5 in the step.(c) crystallization temperature is 80～130 ℃ in the step, 0～1000 rev/min of stirring velocity; Crystallization time is 0.5～480 hour.
The present invention is owing to adopted SiO
2/ Al
2O
3Mol ratio is that 15～100 ZSM-5 crystal grain is nuclear phase, SiO
2/ Al
2O
3Mol ratio is that 60～≤ 100 ZSM-5 molecular sieve is the core-shell type zeolite molecular sieve that shell is combined to, and nuclear phase is the different of aluminum content with the key distinction of shell phase, and biphase crystal topological framework is identical, two-phase each other growth closely and the duct communicate.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 60～≤ 100, 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.Material of the present invention is used for the reaction of methylbenzene methanol selective methylation, and its stability has obtained improving significantly, and through the stability reaction of 300hr, its average toluene conversion is 25%, and 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 2 is used for illustrating nuclear phase SiO
2/ Al
2O
3Be 25, shell is or SiO mutually
2/ Al
2O
3Synthetic and the Preparation of catalysts of＞100 hud typed ZSM-5/ZSM-5 zeolite molecular sieve.
[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 10wt% (wt the is a weight) amine nitrate solution 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, Si0
2Binding agent accounts for 20%.
[comparative example 2]
30 gram ethamine, 150 gram water glass (are contained SiO
225.8wt%, Na
2O 7.3wt%), 0.05 gram Tai-Ace S 150 and 700 gram water mix, and stir 1 hour, add 25 then and restrain SiO
2/ Al
2O
3Be 25 ZSM-5 nuclear phase molecular sieve, put into 1000 milliliters stainless steel crystallizing kettle, airtight, be 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 250, the nucleocapsid ratio is 95/5, and its XRD analysis is the result conform to data in literature.
With core-shell molecular sieve CS2 by method ion-exchange described in the Comparative Examples 1 after, 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, and dries back 550 ℃ of roastings 4 hours in retort furnace, cuts grain, saccharoid is immersed in 10hr in 25% the silicon oil solution again, natural air drying, and 538 ℃ of roastings 4 hours obtain core-shell molecular sieve catalyzer CS-Cat.2.
[embodiment 1]
15 milliliters of ethamine, 210 gram water glass (are contained SiO
225.8wt%, Na
2O 7.3wt%), 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, the powerful 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 CS3, 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.
With core-shell molecular sieve CS3 by method ion-exchange described in the Comparative Examples 1 after, in molecular sieve account for 80%, binding agent accounts for 20% ratio, with core-shell molecular sieve CS3 and SiO
2Binding agent mixes, and stir and mediate, and extrusion is shaped, and dries back 550 ℃ of roastings 4 hours in retort furnace, cuts grain, saccharoid is immersed in 10hr in 25% the silicon oil solution again, natural air drying, and 538 ℃ of roastings 4 hours obtain core-shell molecular sieve catalyzer CS-Cat.3.
[embodiment 2～10]
Embodiment 2～10th, and with the synthetic ratio and the synthesis condition of table 1,1 similar approach and step are synthetic to obtain core-shell molecular sieve CS4～12# by implementing, and is prepared into core-shell molecular sieve catalyzer CS-Cat4～12# according to embodiment 1 similar method, sees 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 that with ZSM-5 nuclear crystalline phase ratio, the core-shell molecular sieve catalyzer has higher p-Xylol selectivity, catalyst deactivation speed is all slowed down to some extent; With the pure silicon shell mutually (comparative example 1) or high silicon shell phase (comparative example 2) compare, the core-shell molecular sieve of low silicon shell phase at the catalytic performance of catalyzer simultaneously preferably, stability is improved significantly.
Table 3 core-shell molecular sieve catalyzer toluene disproportionation process performance
Claims (8)
1. ZSM-5/ZSM-5 core-shell type zeolite molecular sieve is with SiO
2/ Al
2O
3Mol ratio is that 15～100 ZSM-5 is the nuclear phase molecular sieve, with SiO
2/ Al
2O
3Mol ratio is that 60～≤ 100 ZSM-5 is a shell phase molecule sieve, and the periphery of nuclear phase ZSM-5 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.
2. according to the described ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of claim 1, it is characterized in that the SiO of nuclear phase molecular sieve
2/ Al
2O
3Mol ratio is 15～70.
3. according to the described ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of claim 2, it is characterized in that the SiO of nuclear phase molecular sieve
2/ Al
2O
3Mol ratio be 15～50.
4. according to the described ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of claim 1, it is characterized in that the SiO of shell phase molecule sieve
2/ Al
2O
3Mol ratio is 60～80.
5. according to the described ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of claim 1, the thickness that it is characterized in that shell is 20～500nm.
6. according to the described ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of claim 5, it is characterized in that shell thickness is 100～200nm.
7. according to the described ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of claim 1, it is characterized in that weight ratio is 50/50～98/2 between nuclear phase and shell are mutually.
8. according to the described ZSM-5/ZSM-5 core-shell type zeolite molecular sieve of claim 7, it is characterized in that weight ratio is 80/20～90/10 between nuclear phase and shell are mutually.
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| CN112694101B (en) * | 2019-10-23 | 2023-09-29 | 中国石油化工股份有限公司 | Core-shell molecular sieve, synthesis method and application thereof |
| CN113368889A (en) * | 2021-06-30 | 2021-09-10 | 华东交通大学 | Hollow microsphere core-shell catalyst and preparation method and application thereof |
| CN113368889B (en) * | 2021-06-30 | 2022-08-12 | 华东交通大学 | Hollow microsphere core-shell catalyst and preparation method and application thereof |
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