CN101638239B - Silicon aluminum based mesoporous-microporous composite molecular sieve and synthetic method thereof - Google Patents

Silicon aluminum based mesoporous-microporous composite molecular sieve and synthetic method thereof Download PDF

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CN101638239B
CN101638239B CN2008101173981A CN200810117398A CN101638239B CN 101638239 B CN101638239 B CN 101638239B CN 2008101173981 A CN2008101173981 A CN 2008101173981A CN 200810117398 A CN200810117398 A CN 200810117398A CN 101638239 B CN101638239 B CN 101638239B
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composite molecular
molecular screen
mesoporous
molecular sieve
template
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CN101638239A (en
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沈志虹
魏兵
叶鹏
李聃
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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Abstract

The invention provides a novel silicon aluminum based mesoporous-microporous composite molecular sieve and a synthetic method thereof. The composite molecular sieve is obtained by adopting a silicon source and an aluminum source to stir for appropriate time under the action of a template agent to realize the crystallization and performing a one-step rapid synthetic method, and has regular mesopore and micropore structures at the same time. Methods such as XRD are utilized to characterize a synthetic molecular sieve structure, and can display that the synthetic molecular sieve has the regular mesopore and micropore structures. The mesoporous-microporous composite molecular sieve can be taken as a catalytic material, and is suitable for catalytic reactions in which macromolecules is involved.

Description

Mesoporous-microporous composite molecular screen of a kind of sial base and compound method thereof
Technical field
The present invention relates to aluminium base mesoporous-microporous composite molecular screen material of a kind of novel silicon and preparation method thereof, belong to the molecular screen material technical field.
Background technology
Mesopore molecular sieve is compared with traditional micro porous molecular sieve, and it is big to have an aperture, and characteristics such as pore size is adjustable, and the range of application of molecular screen material in fields such as catalysis, separation expanded in its appearance.
But all there are the limitation that himself is difficult to overcome in simple mesopore molecular sieve and micro porous molecular sieve, so research and application with the mesoporous-microporous composite molecular screen of the two effective bonded have just occurred.Mesoporous-microporous composite molecular screen has micropore and mesoporous double hole channel and distributes, and in conjunction with macropore advantage and the advantage of micro porous molecular sieve strongly-acid and high hydrothermal stability of mesoporous material, can make two kinds of material advantage complementations, synergy.Can optimize the duct distribution of molecular screen material and the reasonable disposition of active sites just because of mesoporous-microporous composite molecular screen; Having great application prospect and potential using value aspect macromolecular absorption and the catalysis, is example with the catalytic cracking reaction, mesoporous during with micropore when existing simultaneously in the catalyst molecule sieve crystal grain; The heavy oil macromole is realized a cracking earlier in mesoporous; Then, the small molecules that is cracked into gets into micropore canals again and carries out secondary reaction, thereby improves the effect of catalytic cracking reaction.
The preparation of the MCM-41/FAU matrix material that synthetic (MicroporousMaterials, 1996,6) such as Kloetstra that start from year Holland of mesoporous-microporous composite molecular screen are reported.It is template that this method is selected palmityl trimethyl ammonium chloride for use, and WHITE CARBON BLACK is the silicon source, and sodium metaaluminate is the aluminium source, at 120 ℃ of following crystallization 12h, can obtain mesoporous-microporous composite molecular screen.
In recent years,, the two is had complementary advantages, the existing public reported of much utilizing micro porous molecular sieve and the synthesising mesoporous-mesoporous-microporous composite molecular sieve of mesopore molecular sieve combination in order to overcome micro porous molecular sieve and mesopore molecular sieve limitation separately.Chinese patent 01119908.3; Denomination of invention is " compound method of mesoporous-microporous composite molecular sieve compsn in a kind of "; This patented process with micro porous molecular sieve as first silicon and aluminum source; Reaction mixture is through 40-300 hour hydrothermal crystallizing, realized compound with micro porous molecular sieve commonly used in shortening, the catalytic cracking catalyst and mesoporous molecular sieve.
One Chinese patent application 200410012548.4; Denomination of invention is " microporous-mesoporous composite molecular sieve and preparation method "; Wherein disclose a kind of microporous-mesoporous composite molecular sieve and preparation method thereof, the mesopore molecular sieve in this composite molecular screen is MCM-41 or MCM-48, and micropore is from not dissolved source micro-pore zeolite; The preparation method of this composite molecular screen is with by the silicon and aluminum source of alkaline solution dissolved micro-pore zeolite as synthesising mesoporous molecular sieve; And utilizing the self-assembly of tensio-active agent supramolecule, the synthetic mesopore molecular sieve has regular pore passage structure, forms microporous-mesoporous composite molecular sieve with the part micro-pore zeolite that remains; Be characterized in that micropore and mesoporous two kinds of active component content can realize modulation, need carry out the secondary hydrothermal crystallizing in the building-up process.
In the one Chinese patent application 200710010081.3; A kind of mesoporous-microporous composite material and compound method thereof are also disclosed; It is raw material with the zeolite molecular sieve, handles through Starso, the particulate fraction of zeolite molecular sieve is dissociated form the fragment with microvoid structure; Under the template effect, carry out the high pressure water thermal synthesis then, this patented claim claims that the method for being put down in writing goes for the synthetic of multiple material.
A kind of method of mesoporous molecular sieve overgrowth on microporous molecular sieve surface is disclosed in the one Chinese patent application 200410084099.4; This method is at first to prepare halogen-containing micro porous molecular sieve; Join then in the activated solution that contains tensio-active agent, acid (alkali) and zero(ppm) water, through 80-120 ℃ of following crystallization 12-72 hour.
Except that above-mentioned patent openly, the synthetic technology such as (MicroporousMesoporous Mater, 2003,64) of synthetic (MicroporMesopor Mater, 1999,27) of ZSM-5/MCM-41 composite molecular screen, β/MCM-48 composite molecular screen all has report.
It is synthetic that the compound method of these composite molecular screens all belonged to for two steps; Wherein need a step hydrothermal crystallizing at least; And all adopting micro porous molecular sieve is raw material (through hydro-thermal synthetic or be purchased), and the synthetic microporous molecular sieve of promptly first crystallization adds template again; Regulate basicity, and then hydrothermal crystallizing for some time.So no matter these present methods are synthetic or are purchased micro porous molecular sieve, all exist synthesis step loaded down with trivial details, the shortcoming that the action required time is long.
On the other hand, though the aforesaid method synthetic mesoporous-mesoporous-microporous composite molecular sieve has micropore and central hole structure simultaneously, owing to be that hydrothermal crystallizing forms on the basis of micro porous molecular sieve, in crystallization product, is difficult to realize the regular compound of mesoporous and microvoid structure.
Summary of the invention
The present invention is to provide the compound method of the mesoporous-microporous composite molecular screen of a kind of sial base, synthetic fast through a step, not only method is simple, and has regular mesoporous and microvoid structure in the composite molecular screen that obtains simultaneously.
The present invention also provides a kind of novel mesoporous-microporous composite molecular screen of sial base, has regular mesoporous and microvoid structure in this composite molecular screen simultaneously, therefore has better acidity and hydrothermal stability.
The invention provides the compound method of the mesoporous-microporous composite molecular screen of a kind of sial base, this compound method may further comprise the steps:
(1) preparation template solution: dissolve in template in the deionized water, in 20-70 ℃ of water bath with thermostatic control, be stirred to and be transparent colloidal solution;
(2) synthetic composite molecular screen: silicon source, aluminium source solution, deionized water are slowly evenly joined in the template solution, and the mol ratio of control material is (9-12) Na 2O: Al 2O 3: (30-50) SiO 2: (700-900) H 2O: (1-15) template at 20-70 ℃ of stirred in water bath 0.2-8h, through filtering, washing after drying, obtains sial base Jie-little composite molecular screen.
According to above-mentioned compound method, the silicon source of this composite molecular screen of preparation can be selected from water glass, silicon sol or silica gel microball in the step (2); The aluminium source of this composite molecular screen of preparation is optional from sodium metaaluminate, aluminum oxide or Tai-Ace S 150 in the step (2).
This case applicant finds, utilizes appropriate template agent and silicon, aluminium source can be had composite molecular screen regular and mesoporous significantly/microvoid structure simultaneously through suitable crystallization at a lower temperature according to suitable material ratio.Based on preferred synthesis method of the present invention, during the preparation template solution, template concentration can be 2-20; Material ratio when mixing the glue operation to satisfy is a purpose; But be not strict with, and, be stirred to transparent colloidal solution in preferred 50-60 ℃ of water bath with thermostatic control in 20-70 ℃.
The concrete scheme according to the present invention; The template of using can be the used template of common synthesising mesoporous molecular sieve, preferably cetyl trimethylammonium bromide (CTABr), palmityl trimethyl ammonium chloride, Mierocrystalline cellulose, TTAB, nano-sized carbon etc.Churning time to reaction mass when preferably, preparing composite molecular screen is controlled to be 0.5-2h.
According to compound method provided by the invention, the proportioning of control reaction mass has material impact for final result, generally need be controlled to be (9-12) Na 2O: Al 2O 3: (30-50) SiO 2: (700-900) H 2O: (1-15) template preferably can be controlled in (9-12) Na 2O: Al 2O 3: (30-50) SiO 2: (700-900) H 2O: (2-10) template.
The present invention also provides a kind of synthetic according to the method described above mesoporous-microporous composite molecular screen of sial base that obtains; Compare with the composite molecular screen that has report at present; Micropore and mesoporous constitutional features all clearly thereby have regular mesoporous and micropore composite structure in this composite molecular screen.Through retrieval, in the Jade5XRD DB, do not find to have the molecular sieve record of analog structure.
In a word, enforcement of the present invention has following beneficial effect:
Compound method of the present invention only needs at a lower temperature reaction mixture to be stirred, and need not hydrothermal crystallization process;
Mesoporous-microporous composite molecular screen of the present invention only needs silicon source, aluminium source and template are mixed through quick synthetic can the obtaining of single stage method, and generated time is short, and is simple to operate;
The mesoporous-microporous composite molecular screen of synthetic of the present invention has regular mesoporous and microvoid structure simultaneously, is expected to be used for the catalyzed reaction that macromole is participated in as catalytic material, has the practical value of highly significant.
Description of drawings
Fig. 1 is the XRD spectra of the synthetic MCM-41 molecular sieve that obtains among the embodiment 1.
Fig. 2 is the XRD spectra of the synthetic Y/MCM-41 composite molecular screen that obtains among the embodiment 2.
Fig. 3 is the XRD spectra of the synthetic novel mesoporous-microporous composite molecular screen of the present invention that obtains among the embodiment 3.
Fig. 4 is the XRD spectra of the synthetic mesoporous material that obtains among the embodiment 4.
Fig. 5 is the XRD spectra of the synthetic mesoporous material that obtains among the embodiment 5.
Embodiment
Below will make further description the present invention by specific embodiment, be intended to help read the reader and understand essence of the present invention place and the beneficial effect that is brought better, but but should not be construed as any qualification practical range of the present invention.
The preparation of embodiment 1:MCM-41 mesopore molecular sieve
Step 1, preparation template solution: CTABr is dissolved in the deionized water, stirs 15min in about 5%, the 60 ℃ of water bath with thermostatic control of concentration, can see that stirring back solution is transparence.
Step 2, mixed glue: according to 10Na 2O: Al 2O 3: 30SiO 2: 3300H 2The mole proportioning of O: 4CTABr is with NaAlO 2(Beijing Chemical Plant, CP), H 2O, water glass (Beijing Red Star water glass plant, modulus: 3.1-3.4) carry out mixing and stirring, get the opaque white color gel.
Step 3, hydrothermal crystallizing: above-mentioned white gels is packed in the crystallizing kettle, in 105 ℃ of crystallization 24 hours, sample after suction filtration, washing, drying the MCM-41 molecular sieve.
Step 4, sign: utilize XRD to characterize the structure of MCM-41, the result is as shown in Figure 1, and it has tangible MCM-41 characteristic peak.
Synthesizing of the mesoporous-microporous composite molecular screen of embodiment 2:Y/MCM-41
The preparation of step 1, Y molecular sieve presoma: according to 8Na 2O: Al 2O 3: 18SiO 2: 234H 2The mole proportioning of O is with NaAlO 2(Beijing Chemical Plant, CP), NaOH (Beijing Chemical Plant, CP, effective content ≮ 82%), H 2(Beijing Red Star water glass plant, modulus: 3.1-3.4) mix, in the crystallizing kettle of packing into behind the violent stirring 1h, 105 ℃ of following crystallization 48 hours obtain the Y molecular sieve presoma for O, water glass.
Step 2, according to the step 1 among the embodiment 1 preparation template solution.
Step 3, mix glue: Al in molar ratio 2O 3: 3.6CTABr; The Y presoma of preparation is joined in the template solution, and violent stirring becomes mixed glue in 60 ℃ of waters bath with thermostatic control, and regulates the pH value 9-10 of this mixed glue with sulfuric acid; Further be stirred well to reaction mass and mix, obtain the opaque white color gel.
Step 4, hydrothermal crystallizing: the gel of gained is packed in the autoclave pressure, place baking oven to be warming up to 105 ℃ of crystallization 24h, product obtains the Y/MCM-41 composite molecular screen after suction filtration, washing, drying.
Step 5, sign: utilize XRD to characterize the structure of resulting Y/MCM-41, the result is as shown in Figure 2, and it has the characteristic peak of tangible MCM-41 characteristic peak and faint Y zeolite.
Embodiment 3: the mesoporous-microporous composite molecular screen of sial base synthetic
Step 1, according to the method for embodiment 1 preparation template solution, but template concentration is controlled to be 10.4%.
Step 2, synthetic composite molecular screen: with NaAlO 2(Beijing Red Star water glass plant, modulus: 3.1-3.4) solution, deionized water slowly evenly join in the CTABr solution, and the control mol ratio is 10.54Na for (Beijing Chemical Plant, CP) solution, water glass 2O: Al 2O 3: 30SiO 2: 767H 2O: 3.95CTABr, behind the vigorous stirring 0.5h, suction filtration, washing and dry obtain the mesoporous-microporous composite molecular screen of sial base of the present invention in 60 ℃ of waters bath with thermostatic control.
Step 3, sign: utilize XRD to characterize the structure of this mesoporous-microporous composite molecular screen; The result is as shown in Figure 3; Can see that the composite molecular screen of present embodiment has tangible mesoporous peak at maller angle, but this peak position is different from the characteristic peak positions of the MCM-41 molecular sieve of embodiment 1; And have tangible pore characteristics peak (in the Jade5XRD DB, not finding to have the molecular sieve record of analog structure) simultaneously in wide-angle; That is, its mesoporous-microporous peak intensity of present embodiment synthetic composite molecular screen is all very strong, shows that this mesoporous-microporous composite molecular screen has very regular Jie, micropore composite structure.
Embodiment 4: synthetic-1 of mesoporous material
Step 1, preparation template solution: CTABr is dissolved in the deionized water, and concentration is about in 5%, 60 ℃ of water bath with thermostatic control and stirs 15min, can see that stirring back solution is transparence.
Step 2, mixed glue: according to 10Na 2O: Al 2O 3: 50SiO 2: 2100H 2The mole proportioning of O: 6.5CTABr is with NaAlO 2(Beijing Chemical Plant, CP), H 2O, water glass (Beijing Red Star water glass plant, modulus: 3.1-3.4) carry out mixing and stirring (2-3 hour), get the opaque white color gel.
Step 3, in 60 ℃ of waters bath with thermostatic control behind the vigorous stirring 0.5h, suction filtration, washing and dry.
Step 4, sign: utilize XRD to characterize this structures of samples, the result is as shown in Figure 4, and is bigger with embodiment 3 difference though this sample has mesoporous peak, should think mesopore molecular sieve.
Embodiment 5: synthetic-2 of mesoporous material
Step 1, preparation template solution: CTABr is dissolved in the deionized water, stirs 15min in 60 ℃ of waters bath with thermostatic control, can see that stirring back solution is transparence.
Step 2, mixed glue: according to 10Na 2O: Al 2O 3: 50SiO 2: 400H 2The mole proportioning of O: 6.5CTABr is with NaAlO 2(Beijing Chemical Plant, CP), H 2O, water glass (Beijing Red Star water glass plant, modulus: 3.1-3.4) carry out mixing and stirring (1-2 hour), get the opaque white color gel.
Step 3, in 60 ℃ of waters bath with thermostatic control behind the vigorous stirring 0.5h, suction filtration, washing and dry.
Step 4, sign: utilize XRD to characterize this structures of samples, the result is as shown in Figure 5, and is bigger with embodiment 3 difference though this sample has mesoporous peak, must think mesopore molecular sieve.
Comprehensive the foregoing description can know that the mesoporous-microporous composite molecular screen of synthetic of the present invention is different from the mesoporous-microporous composite molecular screen of other type, belongs to a kind of mesoporous-microporous composite molecular screen of brand-new type.Compare with the compound method of other mesoporous-microporous composite molecular screen, the synthesis step of mesoporous-microporous composite molecular screen of the present invention is simple, need not hydrothermal crystallizing, and synthesis condition is gentle, and saves the running time, so the present invention has important practical value.
Need to prove at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention; And not breaking away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (8)

1. the compound method of the mesoporous-microporous composite molecular screen of sial base, this compound method may further comprise the steps:
(1) preparation template solution: dissolve in template in the deionized water, in 20-70 ℃ of water bath with thermostatic control, be stirred to and be transparent colloidal solution;
(2) synthetic composite molecular screen: solution, the deionized water in silicon source, aluminium source are slowly evenly joined in this template solution, and the mol ratio of control material is (9-12) Na 2O: Al 2O 3: (30-50) SiO 2: (700-900) H 2O: (1-15) template, in 20-70 ℃ of water bath with thermostatic control, stir 0.2-8h, through filtering, washing after drying, obtain the mesoporous-microporous composite molecular screen of sial base.
2. compound method according to claim 1 is characterized in that, the silicon source of this composite molecular screen of preparation is selected from water glass, silicon sol or silica gel microball in the step (2).
3. compound method according to claim 1 is characterized in that, the aluminium source of this composite molecular screen of preparation is selected from sodium metaaluminate, aluminum oxide or Tai-Ace S 150 in the step (2).
4. compound method according to claim 1 is characterized in that, in 50-60 ℃ of water bath with thermostatic control, is stirred to transparent colloidal solution after the adding template.
5. compound method according to claim 1 is characterized in that, template used dose is selected from cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Mierocrystalline cellulose, TTAB or nano-sized carbon.
6. compound method according to claim 1 is characterized in that, when preparing this composite molecular screen according to step (2), and the churning time 0.5-2h of material.
7. according to claim 1 or 6 described compound methods, it is characterized in that when preparing this composite molecular screen according to step (2), Material control stirs in 50-60 ℃ of water bath with thermostatic control.
8. mesoporous-microporous composite molecular screen of sial base, this composite molecular screen is prepared from according to each said compound method of claim 1-7.
CN2008101173981A 2008-07-30 2008-07-30 Silicon aluminum based mesoporous-microporous composite molecular sieve and synthetic method thereof Expired - Fee Related CN101638239B (en)

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CN101864096B (en) * 2010-05-27 2012-05-30 南京工业大学 Organic/zeolite hybrid material and preparation method thereof
CN102718231B (en) * 2012-04-26 2014-06-25 华东师范大学 Preparation method of layered nano-mordenite molecular sieve
CN106430238B (en) * 2016-07-18 2018-10-12 辽宁石油化工大学 Method and the application of multilevel pore channel SAPO-11 molecular sieve are prepared using plant cellulose as template
US10272418B2 (en) * 2017-08-07 2019-04-30 Saudi Arabian Oil Company Mesoporous zeolites and methods for the synthesis thereof
CN110804204A (en) * 2018-08-06 2020-02-18 南京理工大学 Bacterial cellulose/X-type molecular sieve composite aerogel and preparation method thereof

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