CN102515195B - Method for synthesizing integral multi-stage pore canal molecular sieve in one step - Google Patents
Method for synthesizing integral multi-stage pore canal molecular sieve in one step Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an integral multi-stage pore canal molecular sieve in one step, which comprises the following steps that: a silicon source, an aluminum source, water and template agent are mixed and stirred to obtain a mixture; an alkali source is added into the mixture, and a gel mixture is obtained; and the gel mixture is moved into a synthesis reactor to be sealed and subjected to crystallization reaction, washed, dried and calcinated, and the multi-stage pore canal molecular sieve is obtained. According to the method for synthesizing the integral multi-stage pore canal molecular sieve in one step, any amorphous carrier is not added or any mesoporous or large-hole template agent is not used, the process is simple, the used amount of water is reduced, the crystallization time is short, the temperature is low and the production cost is low, and the method is applicable to industrialized production. The crystal of the prepared integral multi-stage pore canal molecular sieve is self-linked, the pore sizes are from micro to large, the distribution range of the pore sizes is wide, the activity and the hydrothermal stability are good, and the mechanical strength is high. The method for synthesizing the integral multi-stage pore canal molecular sieve in one step can be used in petroleum chemical industry, fine preparation of chemicals, environmental catalysis and other fields.
Description
Technical field
The invention belongs to a kind of molecular sieve preparation method, be specifically related to a kind of method of synthesizing integral multi-stage pore canal molecular sieve in one step.
Background technology
But the catalytic performance of the well-regulated micropore canals of zeolite molecular sieve tool, good shape selectivity, stability and modulation, fields such as being widely used in catalysis, ion-exchange, adsorbing and separating.In practical application, micropore canals due to channel diameter (＜2nm) littlely tend to affect catalytic process reactant and the mass transfer diffusion of product in its duct, cause active and transformation efficiency reduces, reduced the efficient of zeolite molecular sieve application.The mesopore/macropore material, although be conducive to macromolecular absorption and diffusion in reaction process, the amorphism of hole wall makes its hydrothermal stability, physical strength and catalytic activity relatively poor, fails to reach the requirement of industrial application.Therefore introduce mesoporous and macropore in conjunction with separately advantages both in zeolite, prepare a kind of novel multi-stage porous molecular sieve (two-stage micropore-mesopore/macropore, three grades of micropore-mesopore-macropores) is one of popular domain of studying at present.Up to the present, people have adopted a lot of methods to prepare the multi-stage artery structure zeolite molecular sieve, generally can be divided into two kinds of methods.A kind of is that synthetic zeolite molecular sieve is carried out modification, adopts the alkali desiliconization, and sour dealuminzation or steam treatment etc. can form mesoporous passage in the microporous molecular sieve duct, but cause silica alumina ratio to change, and catalytic performance descends.Another kind method is directly to synthesize the multi-stage porous molecular sieve in template with under without the template condition.This method has solved the problem that above-mentioned method of modifying exists from the source, but still there is little mesoporous mass transfer diffusion limit in the zeolite molecular sieve mesopore orbit size little (at scope 2-10nm) that obtains.In addition, the gained molecular sieve is generally powder.In industrial application, zeolite [molecular sieve is made whole column or sheet shape usually to eliminate the bed pressure drop of fixed-bed reactor.At present, the method for synthetic monolithic devices zeolite molecular sieve mainly contains two kinds: a kind of is to add SiO in molecular sieve molded process
2, Al
2O
3Deng mineral binder bond to be conducive to moulding.Although the method is simple, the pore passage structure of molecular sieve is easily destroyed, and the existence of mineral binder bond makes the density minimizing in molecular sieve active centre.Another kind is to utilize the monoblock type skeleton that has existed as carrier or macropore template, namely needs further to synthesize amorphous integral post.Utilize amorphous mesoporous SBA-15 monolithic devices molecular sieve column that silicon source and aluminium source are provided such as: Cho etc., in the situation that solid carbon supports above-mentioned framework of molecular sieve, they are directly changed into crystalline form ZSM-5 molecular sieve (S. I. Cho, S. D. Choi, J.-H. Kim, G.-J. Kim. Synthesis of ZSM-5 Films and Monoliths with Bimodal Micro/Mesoscopic Structures. Advanced Functional Materials. 14(2004) 49-54).Li etc. with the organic resorcinol-formaldehyde aerogel of monoblock type as template, add after the molecular sieve synthesis mother liquid in silicon source and make multi-stage porous Silicalite-1 molecular sieve after crystallization. W.C. Li, A.H. Lu, R. Palkovits, W. Schmidt, B. Spliethoff, F. Schuth. Hierarchically Structured Monolithic Silicalite-1 Consisting of Crystallized Nanoparticles and Its Performance in the Beckmann Rearrangement of Cyclohexanone Oxime. J. AM. CHEM. SOC. 127(2005) 12595-12600. Tong etc. is dipped into sucrose and thiosulfonic acid solution and makes carbon-silicon compound in the monolithic devices silica after carbonization, then it is joined in the zeolite synthesis mother liquor in siliceous source not, after removing, crystallization and carbon roasting make multi-stage porous Beta zeolite molecular sieve (Y. Tong, T. Zhao, F. Li, Y. Wang. Synthesis of Monolithic Zeolite Beta with Hierarchical Porosity Using Carbon as a Transitional Template. Chem. Mater. 18(2006) 4218-4220).Sachse etc. have prepared mesopore/macropore silica integral post as carrier, add wherein in molecular sieve synthesis mother liquid, make multi-stage porous SOD zeolite molecular sieve after crystallization.A.?Sachse,?A.?Galarneau,F.D.R.F.?Fajula,B.?Coq.?Synthesis?of?Zeolite?Monoliths?for?Flow?Continuous?Processes.?The?Case?of?Sodalite?as?a?Basic?Catalyst.?Chem.?Mater.,?22（2010）4123–4125)。Recently, Mori etc. have synthesized multi-stage porous micropore-macroporous structure Silicalite-1 monolithic devices molecular sieve column by two steps, first adopt the standby amorphous macroporous silica gel integral post of ice template agent legal system.Then, adopt hydro-thermal steam synthesis method to transform the amorphous wall surface of a part of macroporous silica gel and become crystalline form Silicalite-1 molecular sieve.H.?Mori,?K.?Aotani,?N.S.H.?Tamon.?Synthesis?of?a?hierarchically?micro–macroporous?structured?zeolite?monolith?by?ice-templating.?J.?Mater.?Chem.21（2011）5677-5681）。
Summary of the invention
The objective of the invention is the problem that exists in present monolithic devices Zeolite synthesis technology for solving, and the method for the simple synthesizing integral multi-stage pore canal molecular sieve in one step of a kind of technique is provided, synthetic molecular sieve has higher mechanical strength and hydrothermal stability.
The method of synthesizing integral multi-stage pore canal molecular sieve in one step of the present invention, its step is as follows:
Silicon source, aluminium source, water and template are mixed, 10 ~ 80
oC stirred after 2 ~ 24 hours, added wherein alkali source, got gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 80 ~ 200
oAfter C crystallization 6 ~ 72 hours, washing, drying, 550 ~ 650
oC roasting 4 ~ 12 hours obtains multistage pore canal monolithic devices molecular sieve;
The mol ratio of above-mentioned silicon source, aluminium source, water, template and alkali source is 1:0 ~ 0.1:5 ~ 80:0.1 ~ 0.8:0.08 ~ 0.4.
The molecular sieve that the present invention synthesized has MFI, β or y-type structure.
In the present invention, described alkali source is NaOH, KOH and NH
4The mixture of one or more in OH.Described silicon source is one or more mixing in silicon sol, water glass, silicon gel, tetraethyl orthosilicate and positive silicic acid propyl ester.Described aluminium source is one or more mixing in sodium aluminate, Tai-Ace S 150, aluminum isopropylate and tertiary butyl aluminium.Described template is organic amine (C
nH
2n+1)
4One or more mixing in NX, wherein n=1 – 22; X=OH, Br or Cl.
Beneficial effect of the present invention:
The present invention adopts one-step synthesis, need not add any unbodied carrier, need not mesoporous or macropore template, and technique is simple, reduces water, and crystallization time is short, and temperature is low, and production cost is low, is suitable for suitability for industrialized production.The crystal self join of prepared monolithic devices multi-stage pore canal molecular sieve, the hole is from the micropore to the macropore, and size distribution is wide, active, good hydrothermal stability, physical strength is high.Can be used for petrochemical complex, the fields such as fine chemicals preparation and environmental catalysis.
Description of drawings
Fig. 1 is the directly XRD spectra of synthetic product of single stage method.
Fig. 2 is the directly nitrogen absorption under low temperature of synthetic product-desorption isotherm figure of single stage method, and in figure, 1 is adsorption curve, and 2 is the desorption curve.
Fig. 3 obtains pore volume and aperture graph of a relation the adsorbing by BJH of product that single stage method is directly synthesized.
Fig. 4 is the directly stereoscan photograph of synthetic product of single stage method.
Embodiment
Embodiment 1:
Colloidal sol (2.8 wt.% Al with 5.13g tetraethyl orthosilicate, 3g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution to get gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 170
oC crystallization 24 hours obtains the product of monolithic devices molecular sieve, through washing, dry and 550
oAfter C roasting 6 hours, namely obtain monolithic devices multistage pore canal ZSM-5 molecular sieve.
Fig. 1 is the XRD characterization result of product, can see that by Fig. 1 product has typical MFI ZSM-5 molecular sieve structure, and sample has very high degree of crystallinity, shows that product has hydrothermal stability preferably.
Fig. 2 and Fig. 3 are respectively the nitrogen absorption under low temperature-desorption isotherm of product and obtain pore volume and aperture graph of a relation by BJH absorption.Can see that from spectrogram sample has mesoporous part (nitrogen adsorption isotherm line chart belongs to the H4 type).Mesoporous distribution of sizes is wide.
Fig. 4 is the SEM photo of sample, can see from the SEM photo, and the ZSM-5 molecular sieve crystal forms the duct and varies in size and form simultaneously the integral body of multistage pore canal ZSM-5 molecular sieve from being linked togather, and shows that product has higher physical strength.
Embodiment 2:
Colloidal sol (2.8 wt% Al with 5.13g tetraethyl orthosilicate, 1.5g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution to get gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 140
oC crystallization 24 hours obtains the product of monolithic devices molecular sieve, through washing, dry and 550
oAfter C roasting 6 hours, namely obtain monolithic devices multistage pore canal ZSM-5 molecular sieve.
Embodiment 3:
5.13g tetraethyl orthosilicate, 2g water and 4g TPAOH are mixed, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution to get gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 140
oC crystallization 24 hours obtains the product of monolithic devices molecular sieve, through washing, dry and 550
oAfter C roasting 6 hours, namely obtain monolithic devices multistage pore canal Silicalite-1 molecular sieve.
Embodiment 4:
5.13g tetraethyl orthosilicate, 2g water and 4g TPAOH are mixed, 25
oC stirred after 3 hours, added wherein 3ml 6% NaOH solution to get gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 140
oC crystallization 24 hours obtains the product of monolithic devices molecular sieve, through washing, dry and 550
oAfter C roasting 6 hours, namely obtain monolithic devices multistage pore canal Silicalite-1 molecular sieve.
Embodiment 5:
Colloidal sol (2.8 wt.% Al with 5.13g tetraethyl orthosilicate, 2g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, added wherein 3.5ml 6% NaOH solution to get gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 155
oC crystallization 24 hours obtains the product of monolithic devices molecular sieve, through washing, dry and 550
oAfter C roasting 6 hours, namely obtain monolithic devices multistage pore canal ZSM-5 molecular sieve.
The above is only several case study on implementation of the present invention, is not that the present invention is done any pro forma restriction.Protection scope of the present invention is not limited to this.
Claims (5)
1. the method for synthesizing integral multi-stage pore canal molecular sieve in one step is characterized in that step is as follows:
Silicon source, aluminium source, water and template are mixed, 10 ~ 80
oC stirred after 2 ~ 24 hours, added wherein alkali source, got gel mixture, this gel mixture was moved in the stainless steel synthesis reactor seal, 80 ~ 200
oAfter C crystallization 6 ~ 72 hours, washing, drying, 550 ~ 650
oC roasting 4 ~ 12 hours obtains multistage pore canal monolithic devices molecular sieve;
The mol ratio of above-mentioned silicon source, aluminium source, water, template and alkali source is 1:0 ~ 0.1:5 ~ 80:0.1 ~ 0.8:0.08 ~ 0.4; Described template is TPAOH.
2. the method for described synthesizing integral multi-stage pore canal molecular sieve in one step according to claim 1, is characterized in that the molecular sieve that is synthesized has MFI type structure.
3. the method for described synthesizing integral multi-stage pore canal molecular sieve in one step according to claim 1, is characterized in that described alkali source is NaOH, KOH and NH
4The mixture of one or more in OH.
4. the method for described synthesizing integral multi-stage pore canal molecular sieve in one step according to claim 1 is characterized in that described silicon source is one or more mixing in silicon sol, water glass, silicon gel, tetraethyl orthosilicate and positive silicic acid propyl ester.
5. the method for described synthesizing integral multi-stage pore canal molecular sieve in one step according to claim 1 is characterized in that described aluminium source is one or more mixing in sodium aluminate, Tai-Ace S 150, aluminum isopropylate and tertiary butyl aluminium.
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| CN101613113A (en) * | 2009-05-31 | 2009-12-30 | 华东理工大学 | A kind of method of nanometer hierarchical pore MFI molecular sieve one-step synthesis |
| CN101618337A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Method for improving catalytic property of methane aromatization catalyst |
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