CN106745055A - A kind of synthetic method of the molecular sieves of monoblock type multi-stage porous ZSM 5 - Google Patents
A kind of synthetic method of the molecular sieves of monoblock type multi-stage porous ZSM 5 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
The invention provides a kind of synthetic method of the molecular sieves of monoblock type multi-stage porous ZSM 5, comprise the following steps：（1）Silicon source, NaOH, organic formwork agent and deionized water are added into beaker（1）In stir, then silicon source is gradually added into beaker, be stirred vigorously to form homogeneous gel, pour into the stainless steel cauldron of polytetrafluoroethyllining lining in crystallization 1 ~ 7 day at 100 ~ 220 DEG C；（2）By step（1）In the product that obtains deionized water cyclic washing to pH value close to neutrality, in 90 ~ 110 DEG C of drying, obtain the type molecular sieves of ZSM 5；（3）The type molecular sieves of ZSM 5 are calcined, removal organic formwork agent obtains the molecular sieves of monoblock type multi-stage porous ZSM 5.This invention simplifies the step of existing preparation monoblock type multi-stage porous catalyst technology, it is not necessary to the auxiliary material such as expensive structure directing agent and special monolithic substrate, preparation cost is reduced.
Description
Technical field
The invention belongs to the preparing technical field of molecular sieve, and in particular to a kind of monoblock type multi-stage porous ZSM-5 molecular sieve
Synthetic method.
Background technology
Mobil companies of the U.S. reported the synthesis (USP3702886) of ZSM-5 molecular sieve in 1972 first, because it has
Orderly microcellular structure, larger specific surface area, hot and hydrothermal stability, skeleton acid site, tradable cation higher
Turn into Deng excellent properties and industrially apply one of most catalyst.But, the less micropore canals of micropore ZSM-5 molecular sieve
Bigger molecule is hindered into being adsorbed and catalytic reaction in zeolite cavity, the diffusion of macromolecular is limited.In order to overcome list
The limitation in one duct, researchers consider the solution route that duct features at different levels are combined together, such as in conventional microporous ZSM-5
Introduced in the synthetic system of molecular sieve and meso-hole structure or nanocrystal be piled into molecular sieve congeries, thus improve reactant and
The diffusion rate of product, improves the hydrothermal stability of hole wall, improves catalytic reaction activity.
Patent CN200410012548.4 discloses a kind of preparation method of micropore-mesoporous composite molecular sieve, it is characterized in that
The intercrystalline amorphous silica-alumina of micro-pore zeolite and appropriateness dissolving crystal edge part sial are made full use of, as synthesising mesoporous point
The silicon and aluminum source of son sieve, adds the template used by synthesising mesoporous molecular sieve, can be obtained after crystallization with micro- mesoporous compound molecule
Sieve.
Patent CN200410019886.0 is then disclosed to be synthesized with the cheap silicon and aluminum source such as waterglass and aluminum sulfate and is contained ZSM-5
The method of the mesopore molecular sieve of zeolite primary structure unitses, is self-assembled into the mesoporous of ZSM-5 zeolite primary structure unitses
MCM-41 molecular sieves, there is B acid sites in it, main Types are L acid, while having high hydrothermal stability.
Patent CN104030314A is disclosed and is being added mesoporous template synthesis multi-stage porous ZSM-5 with aluminum sulfate and Ludox
The method of molecular sieve, mixture 1 is obtained with aluminum sulfate, NaOH and deionized water, with Ludox, 4-propyl bromide, is gone
Ionized water obtains mixture 2, under agitation mixes two kinds of mixtures, then obtained with micropore and Jie by two sections of crystallization
The ZSM-5 molecular sieve of pore structure.ZSM-5 molecular sieve particle size range 100nm-20um.
Xiao Fengshou research groups are successfully closed using polystyrene -4-vinylpyridine (PSt-co-P4VP) chelating polymer template
Into the mesoporous ZSM-5 molecular sieve that mesopore orbit is arranged along b direction of principal axis, and shown in macromolecular conversion reaction excellent
Catalytic performance.
Multi-stage porous molecular sieve has composite holes more than two-stage or two-stage, the multistage with larger specific surface area and prosperity
Pore structure, has the characteristic better than single microcellular structure molecular sieve at aspects such as diffusion, mass transfers.In the prior art, using
During template synthesis ZSM-5 molecular sieve, then add a kind of special surface activating agent C22H45-N (CH3) 2-C6H12-N
(CH3) 2-C6H13The monoblock type multi-stage porous ZSM-5 molecular sieve of the interlamellar spacing about interlaced structure of the lamella of 2nm is synthesized.
Reported in document with amorphous mesoporous SiO2Ball (MSS) is raw material, and isopropylamine (iPA) is template under 443 K
Dynamic Hydrothermal crystallization prepares ZSM-5 molecular sieve (MFI structure), during to extending crystallization under the weaker structure directing abilities of iPA
Between, reduce crystallization rate, MSS Situ Hydrothermals are converted into ZSM-5 molecular sieve, while ZSM-5 molecular sieve crystallization is realized protect
The shape of raw material ball is held, depending on obtaining monolithic construction ZSM-5 molecular sieve microballoon its shape by MSS shapes, but its Jie for having
Pore structure is the mesoporous SiO of raw material2Ball carries mesoporous rather than the meso-hole structure generated in building-up process.
Zhang Mengyao mixes drop ball method with shitosan using molecular sieve, prepares spherical integral ZSM-5 zeolite molecular sieves
Catalyst.Chitosan aqueous solution is mixed with ZSM-5 molecular sieve powders, constant speed is added drop-wise in TPAOH solution,
Spheric granules is obtained, monoblock type molecular sieve is obtained through drying, calcining.
Shao Xiuli et al. is with quaternary ammonium salt cheap and easy to get（NDZ-1 it is) structure directing agent, in addition pure silicon Silicalite-
Under conditions of 1 molecular sieve gel crystal seed, Centimeter Level is obtained in conventional hydrothermal condition next step using addition CTAB (soft template method)
The monoblock type multi-stage porous ZSM-5 molecular sieve catalyst of size.
But, the synthesis nano-lamellar structure multi-stage porous ZSM-5 molecular sieve of document report is the powder of micron-scale size,
Binding agent or surfactant need to be added makes it be molded or improve intensity.The use of additive can block molecular sieve pore passage, cause
Catalyst activity component content reduction, so as to reduce its catalytic performance.Although also there is researcher to prepare integral catalyzer,
Multi step strategy is needed in building-up process or special carrier is added, with complicated operation sequence, synthesis cost higher etc.
There is still a need for the difficult point for overcoming.Therefore, development one kind is relatively simple, prepare monoblock type multi-stage porous ZSM- without using additive
The method of 5 molecular sieve catalysts, as the key issue that patent of the present invention is solved.
The content of the invention
First technical problem to be solved by this invention be:In view of the shortcomings of the prior art, there is provided a kind of relative
The multi-stage porous ZSM-5 molecular sieve with monolithic construction that crystallinity is high, crystal formation is complete.
Second technical problem to be solved by this invention be:In view of the shortcomings of the prior art, there is provided one kind synthesis
The preparation method of the multi-stage porous ZSM-5 molecular sieve with monolithic construction that step is simple, combined coefficient is high.
To achieve the above object, the technical solution adopted by the present invention is, a kind of conjunction of monoblock type multi-stage porous ZSM-5 molecular sieve
Into method, comprise the following steps：
（1）Stirred during silicon source, NaOH, organic formwork agent and deionized water are added into beaker (1), then by silicon source gradually
Add in beaker, be stirred vigorously to form homogeneous gel, pour into the stainless steel cauldron of polytetrafluoroethyllining lining in 100 ~ 220 DEG C
Lower crystallization 1 ~ 7 day；
（2）The product that will be obtained in step (1) deionized water cyclic washing to pH value close to neutrality, dries in 90 ~ 110 DEG C,
Obtain type ZSM 5 molecular sieve；
（3）Type ZSM 5 molecular sieve is calcined, removal organic formwork agent obtains monoblock type multi-stage porous ZSM-5 molecular sieve.
The step（1）Middle silicon source is with Al2O3Meter, NaOH is with Na2O is counted, and silicon source is with SiO2Meter, products therefrom rubs
Your composition is n (Na2O):n(SiO2):N (organic formwork agent):n(Al2O3):n(H2O) = 8~21:20~200: 0.5~20:1:
1000~5000。
The step（1）In silicon source can be one kind in Ludox, sodium metasilicate, tetraethyl orthosilicate and white carbon etc. or
It is several.
The step（1）In silicon source be in Alumina gel, aluminum sulfate, aluminium isopropoxide, sodium metaaluminate and sodium aluminate etc.
Plant or several.
The step（1）In template to press salt structure directing agent, preferably TPAOH, tetrapropyl bromine season
Change one or more in ammonium, benzyl triethyl ammonium bromide and benzyl tributyl ammonium bromide.
The step（1）Middle silicon source is with Al2O3Meter, organic formwork agent is n (organic formwork agent) with the mol ratio of silicon source:n
(Al2O3) =0.5~20:1。
The step（1）The temperature of middle crystallization is 150 ~ 180 DEG C.
The step（3）Process conditions be：4 ~ 8 h are calcined at 500 ~ 650 DEG C.
In the method that the present invention is provided, involved mixing plant can be magnetic stirring equipment, mechanical stirring equipment, only
Gel state, well mixed purpose are reached, the present invention is not limited by institute using mixing plant.
In the method that the present invention is provided, involved heating（As dried or being calcined）Equipment can be baking oven, tube furnace, horse
Not stove or other firing equipments, of the invention not receive to be used as long as can reach heating-up temperature and keep time enough
The limitation of firing equipment.
The beneficial effect comprise that：The preparation method that the present invention is provided, simplifies existing preparation monoblock type multistage
The step of pore catalyst technology, it is not necessary to the auxiliary material such as expensive structure directing agent and special monolithic substrate, drop
Low preparation cost.This preparation method has the advantages that crystallinity is high, yield is high, operating procedure is simple and is easily isolated.This hair
The ZSM-5 molecular sieve of bright preparation is interaction between organic formwork agent and crystal seed gel, inorganic species in suitable pressure
The congeries with multi-stage artery structure of lower self assembly, with larger specific surface area, shorter diffusion path and compared with
Good stability, is serially connected insertion between the multistage hole of ZSM-5 molecular sieve, can give full play to their mutual diffusions special
Point, for catalytic reaction.
Brief description of the drawings
Accompanying drawing 1 show the XRD spectrum of the monoblock type multi-stage porous ZSM-5 molecular sieve synthesized in the embodiment of the present invention 1；
Accompanying drawing 2 show the XRD spectrum of the monoblock type multi-stage porous ZSM-5 molecular sieve synthesized in the embodiment of the present invention 2；
Accompanying drawing 3 show the monoblock type multi-stage porous ZSM-5 molecular sieve product synthesized in the embodiment of the present invention 1 and amplifies 100,000 times
SEM photograph；
Accompanying drawing 4 show the SEM spectrum of monoblock type multi-stage porous ZSM-5 molecular sieve in the embodiment of the present invention 2；
Accompanying drawing 5 show the monoblock type multi-stage porous ZSM-5 molecular sieve product N synthesized in the embodiment of the present invention 12Isothermal adsorption desorption is bent
Line；
Accompanying drawing 6 show what the monoblock type multi-stage porous ZSM-5 molecular sieve product BJH methods synthesized in the embodiment of the present invention 1 were calculated
Pore-size distribution；
Accompanying drawing 7 show the monoblock type multi-stage porous ZSM-5 molecular sieve product N synthesized in the embodiment of the present invention 22Isothermal adsorption desorption is bent
Line.
Specific embodiment
Embodiment 1
A kind of synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve, comprises the following steps：
（1）By sodium metaaluminate, NaOH, 4-propyl bromide（TPABr）Stirred in adding beaker with deionized water, then
Sodium metasilicate is gradually added into beaker, is stirred vigorously to form homogeneous gel, pour into the stainless steel cauldron of polytetrafluoroethyllining lining
In crystallization 3 days at 160 DEG C, products therefrom mole composition（Silicon source is with Al2O3Meter, NaOH is with Na2O is counted, and silicon source is with SiO2Meter）
It is n (Na2O) :n(SiO2): n(TPABr):n(Al2O3):n(H2O) = 10.5 : 20: 20 :1: 5000；
（2）The product that will be obtained in step (1) deionized water cyclic washing to pH value close to neutrality, in 100 DEG C of drying, obtains
Type ZSM 5 molecular sieve；
（3）Type ZSM 5 molecular sieve is calcined 6 hours for 550 DEG C under oxygen atmosphere in Muffle furnace stove, monoblock type multi-stage porous are obtained
ZSM-5 molecular sieve.
Embodiment 2
A kind of synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve, comprises the following steps：
（1）By sodium metaaluminate, NaOH, 4-propyl bromide（TPABr）Stirred in adding beaker with deionized water, then
Tetraethyl orthosilicate is gradually added into beaker, is stirred vigorously to form homogeneous gel, the stainless steel for pouring into polytetrafluoroethyllining lining is anti-
Answer in kettle crystallization 7 days, mole composition of products therefrom at 150 DEG C（Silicon source is with Al2O3Meter, NaOH is with Na2O count, silicon source with
SiO2Meter）It is n (Na2O):n(SiO2): n(TPABr) :n(Al2O3):n(H2O) = 10 : 50: 20: 1: 1000；
（2）The product that will be obtained in step (1) deionized water cyclic washing to pH value close to neutrality, in 100 DEG C of drying, obtains
Type ZSM 5 molecular sieve；
（3）Type ZSM 5 molecular sieve is calcined 8 hours for 500 DEG C under oxygen atmosphere in Muffle furnace stove, monoblock type multi-stage porous are obtained
ZSM-5 molecular sieve.
Embodiment 3
A kind of synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve, comprises the following steps：
（1）By aluminum sulfate, NaOH, TPAOH（TPAOH）Stirred in adding beaker with deionized water, then
Ludox is gradually added into beaker, is stirred vigorously to form homogeneous gel, pour into the stainless steel cauldron of polytetrafluoroethyllining lining
In crystallization 2 ~ 7 days at 150 ~ 180 DEG C, mole composition of products therefrom（Silicon source is with Al2O3Meter, NaOH is with Na2O is counted, silicon source
With SiO2Meter）It is n (Na2O) :n(SiO2) :n(TPAOH) :n(Al2O3):n(H2O) = 15: 100: 10:1: 1500；
（2）The product that will be obtained in step (1) deionized water cyclic washing to pH value close to neutrality, in 100 DEG C of drying, obtains
Type ZSM 5 molecular sieve；
（3）Type ZSM 5 molecular sieve is calcined 4 hours for 650 DEG C under oxygen atmosphere in Muffle furnace stove, monoblock type multi-stage porous are obtained
ZSM-5 molecular sieve.
Embodiment 4
A kind of synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve, comprises the following steps：
（1）By aluminium isopropoxide, NaOH, benzyl triethyl ammonium bromide（BTEAB）Stirring is equal in adding beaker with deionized water
It is even, then white carbon is gradually added into beaker, it is stirred vigorously to form homogeneous gel, the stainless steel for pouring into polytetrafluoroethyllining lining is anti-
Answer in kettle crystallization 2 days, mole composition of products therefrom at 180 DEG C（Silicon source is with Al2O3Meter, NaOH is with Na2O count, silicon source with
SiO2Meter）It is n (Na2O):n(SiO2): n(BTEAB) :n(Al2O3):n(H2O) =18: 125: 5:1: 2500；
（2）The product that will be obtained in step (1) deionized water cyclic washing to pH value close to neutrality, in 100 DEG C of drying, obtains
Type ZSM 5 molecular sieve；
（3）Type ZSM 5 molecular sieve is calcined 6 hours for 550 DEG C under oxygen atmosphere in Muffle furnace stove, monoblock type multi-stage porous are obtained
ZSM-5 molecular sieve.
It is the Bruker for using Bruker companies of Germany that the characteristic peak of monoblock type ZSM-5 molecular sieve is characterized in embodiment 1-2
D8 Advance types x-ray powder diffraction instruments are analyzed to the composite molecular screen for preparing, and determine the crystal formation and thing phase group of sample
Into.Test condition is：Radiographic source is Cu Ka, the kV of tube voltage 40, the mA of tube current 40,5-50 ° of sweep limits.Accompanying drawing 1 show
The XRD spectrum of the monoblock type multi-stage porous ZSM-5 molecular sieve synthesized in the embodiment of the present invention 1, as seen from the figure in 2 θ=7.9 °, 8.9
°, 23.1 °, 23.9 °, 24.4 ° of X-ray diffraction peaks of appearance, are ZSM-5 molecular sieve topological structure characteristic feature peaks；The institute of accompanying drawing 2
The XRD spectrum of the monoblock type multi-stage porous ZSM-5 molecular sieve of synthesis in the embodiment of the present invention 2 is shown as, equally in 2 θ=7.9 °, 8.9
°, 23.1 °, 23.9 °, 24.4 ° there is its characteristic peak.
Using the type field emission scanning electron microscopes of Nova NanoSEM 450 of FEI Co. of the U.S., the shape of sample is observed
Looks and size.Accompanying drawing 3 show the monoblock type multi-stage porous ZSM-5 molecular sieve product synthesized in the embodiment of the present invention 1 and amplifies
100000 times of SEM photograph；Accompanying drawing 4 show the SEM spectrum of monoblock type multi-stage porous ZSM-5 molecular sieve in the embodiment of the present invention 2.
Using with Full-automatic physical/chemical adsorption instrument（Autosorb-iQ-MP-C）（Kang Ta companies of the U.S.）Molecular sieve is done
Isothermal nitrogen adsorption desorption is tested, and determines its pore-size distribution in specific surface area.Accompanying drawing 5 show what is synthesized in the embodiment of the present invention 1
Monoblock type multi-stage porous ZSM-5 molecular sieve product N2Isothermal adsorption desorption curve, is had by curve and significantly returns the molecule knowable to stagnant ring
Sifter device has meso-hole structure；Accompanying drawing 6 show the monoblock type multi-stage porous ZSM-5 molecular sieve product synthesized in the embodiment of the present invention 1 and uses
BJH methods calculate pore-size distribution, as seen from the figure its mesoporous pore size be mainly distributed between 3-5nm；Accompanying drawing 7 show of the invention real
Apply the monoblock type multi-stage porous ZSM-5 molecular sieve product N synthesized in example 22Isothermal adsorption desorption curve, its also have significantly return stagnant ring
Understand that the molecular sieve has meso-hole structure.
Claims (8)
1. a kind of synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve, it is characterised in that comprise the following steps：
（1）By silicon source, NaOH, organic formwork agent and deionized water mixing and stirring, silicon source is added, stirring forms solidifying
Glue, pours into reactor in crystallization 1 ~ 7 day at 100 ~ 220 DEG C；
（2）By step（1）In the product that obtains be washed with deionized, dry, obtain type ZSM 5 molecular sieve；
（3）Type ZSM 5 molecular sieve is calcined, monoblock type multi-stage porous ZSM-5 molecular sieve is obtained.
2. the synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve as claimed in claim 2, it is characterised in that the step（1）
Middle silicon source is with Al2O3Meter, NaOH is with Na2O is counted, and silicon source is with SiO2Meter, a mole composition for products therefrom is n (Na2O):n
(SiO2):N (organic formwork agent):n(Al2O3):n(H2O) = 8~21: 20~200: 0.5~20:1:1000~5000。
3. the synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, it is characterised in that the step（1）
In silicon source can be Ludox, sodium metasilicate, tetraethyl orthosilicate and white carbon in any one or several.
4. the synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, it is characterised in that the step（1）
In silicon source be any one or several in Alumina gel, aluminum sulfate, aluminium isopropoxide, sodium metaaluminate and sodium aluminate.
5. the synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, it is characterised in that the step（1）
In organic formwork agent be TPAOH, 4-propyl bromide, benzyl triethyl ammonium bromide and benzyl tributyl bromination
Any one of ammonium is several.
6. the synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, it is characterised in that the step（1）
The temperature of middle crystallization is 150 ~ 180 DEG C.
7. the synthetic method of monoblock type multi-stage porous ZSM-5 molecular sieve as claimed in claim 1, it is characterised in that the step（3）
The process conditions of middle roasting are：4 ~ 8 h are calcined at 500 ~ 650 DEG C.
8. the ZSM-5 molecular sieve for being prepared using any synthetic methods of claim 1-7.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814392A (en) * | 2017-10-12 | 2018-03-20 | 河南师范大学 | A kind of preparation method of the molecular sieves of ZSM 22 |
| CN112047358A (en) * | 2019-06-06 | 2020-12-08 | 中国石油天然气股份有限公司 | Zinc or/and nickel-containing ZSM-5 molecular sieve with multi-stage structure and preparation method and application thereof |
| CN112264087A (en) * | 2020-10-19 | 2021-01-26 | 西安工程大学 | Preparation method of hierarchical porous iron-titanium dioxide/ZSM-5 molecular sieve |
| CN113149026A (en) * | 2020-09-28 | 2021-07-23 | 中国石油大学(华东) | Preparation method of molecular sieve with stepped pore structure |
| CN113351158A (en) * | 2021-06-28 | 2021-09-07 | 上海中船临港船舶装备有限公司 | Zeolite molecular sieve adsorbing material for concentrating VOCs (volatile organic compounds), and preparation method and application thereof |
| CN114380302A (en) * | 2022-01-26 | 2022-04-22 | 吉林大学 | Hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof |
| CN115010146A (en) * | 2021-03-05 | 2022-09-06 | 中国石油化工股份有限公司 | Hierarchical pore ZSM-5 nano aggregate molecular sieve and preparation method thereof |
| CN115364893A (en) * | 2022-08-08 | 2022-11-22 | 蚌埠学院 | Preparation method and application of BETA-ZSM composite hierarchical pore molecular sieve |
| CN115594194A (en) * | 2022-10-21 | 2023-01-13 | 南通大学（Cn） | Preparation method of molecular sieve for purifying styrene |
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