CN102515195A - 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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- CN102515195A CN102515195A CN2011103706732A CN201110370673A CN102515195A CN 102515195 A CN102515195 A CN 102515195A CN 2011103706732 A CN2011103706732 A CN 2011103706732A CN 201110370673 A CN201110370673 A CN 201110370673A CN 102515195 A CN102515195 A CN 102515195A
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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 the method for the synthetic monolithic devices multistage pore canal molecular sieve of a kind of single stage method.
Background technology
But zeolite molecular sieve has the micropore canals of rule, the catalytic performance of good shape selectivity, stability and modulation, fields such as being widely used in catalysis, IX, adsorbing and separating.In the practical application, (< 2nm) lessly tends to influence catalytic process reactant and the mass transfer diffusion of product in its duct to micropore canals because channel diameter, causes active and transformation efficiency reduction, reduced the efficient of zeolite molecular sieve application.The mesopore/>macropore material, though help macromolecular absorption and diffusion in the reaction process, the amorphism of hole wall makes that its hydrothermal stability, physical strength and catalytic activity are relatively poor, fails to reach industrial application requirements.Therefore in zeolite, introduce mesoporous and the two advantage separately of macropore combination, preparing a kind of novel multistage porous molecular sieve (two-stage micropore-mesopore/macropore, three grades of micropore-mesopore-macropores) is one of popular domain of research 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 causes silica alumina ratio to change, catalytic performance decline.Another kind method is a directly synthetic multistage porous molecular sieve under template and no 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 generally is a 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 in molecular sieve molded process, to add SiO
2, Al
2O
3Deng mineral binder bond to help moulding.Though this method is simple, the pore passage structure of molecular sieve is destroyed easily, and the existence of mineral binder bond reduces the density in molecular sieve active site.Another kind is to utilize the monobloc(k)type skeleton that has existed as carrier or macropore template, promptly needs further synthetic amorphous integral post.For example: Cho etc. utilize amorphous mesoporous SBA-15 monolithic devices molecular sieve column that silicon source and aluminium source are provided; 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 (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 gas gel of monobloc(k)type as template; Make multistage hole Silicalite-1 molecular sieve after the crystallization behind the molecular sieve synthesis mother liquid in adding silicon source. 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. are dipped into sucrose and SULPHONIC ACID. solution and make carbon-silicon compound in the monolithic devices silica after the carbonization; Then it is joined in the zeolite synthesis mother liquor in siliceous source not, make multistage hole Beta zeolite molecular sieve (Y. Tong, T. Zhao after crystallization and carbon roasting remove; 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, to wherein adding in the molecular sieve synthesis mother liquid, make multistage hole SOD zeolite molecular sieve after the 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 multistage hole micropore-macroporous structure Silicalite-1 monolithic devices molecular sieve column through two steps, adopt ice template agent method to prepare amorphous macroporous silica gel integral post earlier.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 the present monolithic devices molecular sieve synthetic technology for solving, and the method for the synthetic monolithic devices multistage pore canal molecular sieve of the simple single stage method of a kind of technology is provided, the synthetic molecular sieve has higher mechanical strength and hydrothermal stability.
The method of the synthetic monolithic devices multistage pore canal molecular sieve of single stage method of the present invention, its step is following:
Silicon source, aluminium source, water and template are mixed, 10 ~ 80
oC stirred after 2 ~ 24 hours, to wherein adding alkali source, got gel mixture, this gel mixture was moved in stainless steel synthesis reactor seal, 80 ~ 200
oBehind the 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.
Institute of the present invention synthetic molecular sieve has MFI, β or y-type structure.
Among the present invention, described alkali source is NaOH, KOH and NH
4The mixture of one or more among the OH.Described silicon source is one or more mixing in silicon sol, water glass, silicon gel, positive tetraethyl orthosilicate and the positive silicic acid propyl ester.Described aluminium source is one or more mixing in sodium aluminate, Tai-Ace S 150, aluminum isopropylate and the tertiary butyl aluminium.Described template is organic amine (C
nH
2n+1)
4One or more mixing among the 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 technology 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 multistage 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, fields such as fine chemicals preparation and environmental catalysis.
Description of drawings
Fig. 1 is the XRD spectra of the direct synthetic product of single stage method.
Fig. 2 is the low temperature conditioning adsorption-desorption isothermal map of the direct synthetic product of single stage method, and 1 is adsorption curve among the figure, and 2 is the desorption curve.
Fig. 3 obtains pore volume and aperture graph of a relation adsorbing by BJH of the direct synthetic product of single stage method.
Fig. 4 is the stereoscan photograph of the direct synthetic product of single stage method.
Embodiment
Embodiment 1:
Colloidal sol (2.8 wt.% Al with the positive tetraethyl orthosilicate of 5.13g, 3g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, got gel mixture to wherein adding 3.5ml 6% NaOH solution, 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 the C roasting 6 hours, promptly 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 percent crystallinity, shows that product has hydrothermal stability preferably.
Fig. 2 and Fig. 3 are respectively the low temperature conditioning adsorption-desorption thermo-isopleth 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 together and varies in size and form the integral body of multistage pore canal ZSM-5 molecular sieve simultaneously from joining, and shows that product has higher physical strength.
Embodiment 2:
Colloidal sol (2.8 wt% Al with the positive tetraethyl orthosilicate of 5.13g, 1.5g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, got gel mixture to wherein adding 3.5ml 6% NaOH solution, 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 the C roasting 6 hours, promptly obtain monolithic devices multistage pore canal ZSM-5 molecular sieve.
Embodiment 3:
The positive tetraethyl orthosilicate of 5.13g, 2g water and 4g TPAOH are mixed, 25
oC stirred after 3 hours, got gel mixture to wherein adding 3.5ml 6% NaOH solution, 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 the C roasting 6 hours, promptly obtain monolithic devices multistage pore canal Silicalite-1 molecular sieve.
Embodiment 4:
The positive tetraethyl orthosilicate of 5.13g, 2g water and 4g TPAOH are mixed, 25
oC stirred after 3 hours, got gel mixture to wherein adding 3ml 6% NaOH solution, 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 the C roasting 6 hours, promptly obtain monolithic devices multistage pore canal Silicalite-1 molecular sieve.
Embodiment 5:
Colloidal sol (2.8 wt.% Al with the positive tetraethyl orthosilicate of 5.13g, 2g aluminum isopropylate
2O
3), 2g water and 4g TPAOH mix, 25
oC stirred after 3 hours, got gel mixture to wherein adding 3.5ml 6% NaOH solution, 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 the C roasting 6 hours, promptly obtain monolithic devices multistage pore canal ZSM-5 molecular sieve.
The above only is several kinds of 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 thereto.
Claims (6)
1. single stage method is synthesized the method for monolithic devices multistage pore canal molecular sieve, it is characterized in that step is following:
Silicon source, aluminium source, water and template are mixed, 10 ~ 80
oC stirred after 2 ~ 24 hours, to wherein adding alkali source, got gel mixture, this gel mixture was moved in stainless steel synthesis reactor seal, 80 ~ 200
oBehind the 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.
2. according to the method for the synthetic monolithic devices multistage pore canal molecular sieve of the described single stage method of claim 1, it is characterized in that institute's synthetic molecular sieve has MFI, β or y-type structure.
3. according to the method for the synthetic monolithic devices multistage pore canal molecular sieve of the described single stage method of claim 1, it is characterized in that described alkali source is NaOH, KOH and NH
4The mixture of one or more among the OH.
4. according to the method for the synthetic monolithic devices multistage pore canal molecular sieve of the described single stage method of claim 1, it is characterized in that described silicon source is one or more mixing in silicon sol, water glass, silicon gel, positive tetraethyl orthosilicate and the positive silicic acid propyl ester.
5. according to the method for the synthetic monolithic devices multistage pore canal molecular sieve of the described single stage method of claim 1, it is characterized in that described aluminium source is one or more mixing in sodium aluminate, Tai-Ace S 150, aluminum isopropylate and the tertiary butyl aluminium.
6. according to the method for the synthetic monolithic devices multistage pore canal molecular sieve of the described single stage method of claim 1, it is characterized in that described template is organic amine (C
nH
2n+1)
4One or more mixing among the NX, wherein n=1 – 22; X=OH, Br or Cl.
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