CN103214003B - Mesoporous Y-type zeolite molecular sieve and preparation method thereof - Google Patents
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Abstract
The invention discloses a mesoporous Y-type zeolite molecular sieve and a preparation method thereof. The preparation method comprises the following steps of: firstly preparing a Y-type zeolite guiding agent; and then guiding synthesis of the mesoporous Y-type zeolite molecular sieve by using amphiphilic organosilane N,N-dimethyl-N-[3-(trimethoxysilane)propyl]octadecyl ammonium chloride (TPOAC) as a mesoporous template, wherein siloxane group at the organosilane terminal is firstly hydrolyzed into silicon hydroxyl; then the silicon hydroxyl is linked to a skeleton on the zeolite surface through chemical bonds; and other alkyl terminals are polymerized and then participate in pore expansion. According to the method disclosed by the invention, mesoporous zeolites can be synthesized by using a one-step hydrothermal process; the method is simple in preparation process, easy to operate and low in cost and good in connectivity between mesopores and micropores, and facilitates macromolecular diffusion. As the prepared mesoporous zeolite molecular sieve has the mesopores and the micropores, the defect of a single pore structure is avoided; and the mesoporous Y-type zeolite molecular sieve has broad application prospect in the catalytic field, in particular in macromolecular diffusion-limited reaction.
Description
Technical field
The present invention relates to a kind of molecular sieve and preparation method thereof, be specifically related to utilize organosilane to be the method that the preparation of mesoporous template contains the Y-type zeolite molecular sieve of meso-hole structure.
Background technology
Y zeolite Si/Al is than general between 1.5 ~ 3, and belong to faujasite-type (FAU) molecular sieve, have three-dimensional twelve-ring pore passage structure, diameter is approximately 0.74 nm.Due to the pore passage structure of Y zeolite uniqueness, applicable acidity and thermostability, be widely used in petrochemical industry, especially in thermopnore catalytic cracking (FCC) reaction, irreplaceable effect [Stao K. Nishimura Y. Honna K. Matsubayashi N. Shimada H. Role of HY Zeolite Mesopores in Hydrocracking of Heavy Oils. J. Catal is served, 2001,200 (2): 288-297].But the heavy oil molecules causing diameter larger due to the pore passage structure of Y-type zeolite molecular sieve relative narrowness is difficult to enter into the duct that aperture only has about 0.74 nm, in addition, the resistance to mass transfer of less aperture also augmenting response thing and resultant, make reaction product can not form carbon distribution at catalyst surface by diffusional deposition in time, reduce catalytic activity.Therefore, less aperture limits micro-pore zeolite and is relating to the application in macromolecular reaction.
Mesoporous material is as MCM-41s [Kresge C.T. Leonowicz M.E. Roth W.J. Vartuli J.C. Beck J.S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature, 359:710-712] and SBA-n [Zhao D.Y. Feng J.L. Huo Q.S. Melosh N. Fredrickson G.H. Chmelka B.F. Stucky G.D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science, 279:548-552] compare with conventional zeolite molecular sieve, there is larger aperture advantage.Allow larger-diameter molecule to enter duct, catalysis can relate to macromolecular reaction.On the other hand, larger aperture reduces resistance to mass transfer, is conducive to the diffusion of reactant and resultant.But, due to the unbodied hole wall structure of mesopore molecular sieve cause its acidity and hydrothermal stability poor, especially much lower compared with micro-pore zeolite, these factors limit its application in catalysis.
In order to overcome micro-pore zeolite and mesopore molecular sieve limitation separately, Many researchers is devoted to find a kind of novel material in conjunction with both microporous zeolitic material and mesoporous material advantage, not only there is high hydrothermal stability and comparatively high acid strength but also include larger aperture, make the two have complementary advantages, larger application can be obtained at catalytic field.People [the Karlsson A. Stocker M. Schmidt R. Composites of micro-and mesoporous materials:simultaneous syntheses of MFI/MCM-41 like phases by a mixed template approach. Microporous Mesoporous Mater such as Karlsson Arne, 1999, 27 (2-3): 181-192] mesoporous template cetyl trimethylammonium bromide (CTAB) is joined in the cohesion solution of the synthesis MFI zeolite containing tetrapropyl ammonium (TPA), expect that CTAB can lead the formation of meso-hole structure, the formation of micropore and micropore template TPA can lead on mesoporous wall, thus form the composite molecular screen with micro-meso-hole structure.But in fact two kinds of template are assemblings of vying each other, formation be the mixture of mesoporous material and poromerics.2008, people [the Fan W. Snyder M.A. Kumar S. Lee P.S. Yoo W.C. Mccormick A.V. Penn R.L. Stein A. Tsapatsis M. Hierarchical nanofabrication of microporous crystals with ordered mesoporosity. Nature Mater such as Fan Wei, 2008,7:984-991] prepare aperture adjustable three-dimensional ordered mesoporous (3DOm) carbon hard template, utilize this hard template to successfully synthesize orderly nano crystal, create intergranular mesoporous.Ryoo Ryong seminar [Na K. Jo C. Kim J. Cho K. Jung J. Seo Y. Messinger R.J. Chmelka B.F. Ryoo R. Directing Zeolite Structures into Hierarchically Nanoporous Architectures. Science in 2011,2011,333:328-332] creatively synthesize a series of bifunctional quaternary surfactant, this tensio-active agent can lead mesoporous and generation that is micropore simultaneously.These achievements in research achieve the pore passage structure of multi-stage porous molecular sieve, and material both containing mesoporous, had again the hole wall structure of crystallization, but these methods synthesis high cost, preparation process complexity etc., be unfavorable for suitability for industrialized production.
Summary of the invention
For the problem existing for above-mentioned prior art and defect, the object of the invention is to seek a kind ofly synthesize that cost is low, the preparation method of the mesoporous Y-type zeolite molecular sieve of preparation process simple possible.
The present invention with the water glass of cheapness for silicon source, first Y-type zeolite molecular sieve directed agents has been prepared, then mesoporous template organosilane is joined in the colloidal sol-gelling system of preparation Y-type zeolite molecular sieve, hydrothermal method is adopted to prepare mesoporous y-type zeolite, after crystallization, template is removed in roasting, obtains mesoporous Y-type zeolite molecular sieve.
In order to achieve the above object, present invention employs following technical scheme:
A preparation method for mesoporous Y-type zeolite molecular sieve, it comprises the following steps:
(1) by water glass, sodium hydroxide, sodium metaaluminate and water according to mol ratio SiO
2: Na
2o:Al
2o
3: H
2o=(0.8 ~ 1.2): (1.0 ~ 1.5): (0.04 ~ 0.1): (20 ~ 26) mix, at 30 ~ 35 DEG C, aging 24 ~ 48 h obtain y-type zeolite directed agents;
(2) directed agents that water glass, water, step (1) obtain at room temperature is mixed, after stirring 1 ~ 4h, again N, N-dimethyl-N-[3-(trimethoxy silicon) propyl group] chlorination octadecyl ammonium (TPOAC) is slowly added, continue stirring 2 ~ 6h; The last mixed aqueous solution adding the aluminum sulfate octadecahydrate aqueous solution and sodium metaaluminate and sodium hydroxide again, at room temperature stirs 1 ~ 3h, obtains thick aluminosilicate gels; Mol ratio Na in last mixed system
2o:Al
2o
3: SiO
2: TPOAC:H
2o=(3.8 ~ 4.5): (0.8 ~ 1.3): (8.5 ~ 9.7): (0.28 ~ 0.36): (158 ~ 179);
(3) material will made through step (2) loads in the stainless steel cauldron of sealing, crystallization 24 ~ 60h at 90 ~ 110 DEG C, after crystallization terminates, solid product after suction filtration, washing and drying more in atmosphere at 550 ~ 600 DEG C roasting 5 ~ 8h remove organic formwork agent TPOAC, thus obtain mesoporous Y-type zeolite molecular sieve.
Further optimization, in step (1), in described y-type zeolite directed agents, the mol ratio of each material is: SiO
2: Na
2o:Al
2o
3: H
2o=(0.95 ~ 1.1): (1.2 ~ 1.4): (0.06 ~ 0.1): (22 ~ 25).
Further optimization, in step (1), the described aging time is 32 ~ 40h.
Further optimization, in step (2), described aluminum sulfate octadecahydrate aqueous solution massfraction is 23 ~ 25 wt%, and the massfraction of the mixed aqueous solution of sodium metaaluminate and sodium hydroxide is respectively 16.9 ~ 18.2 wt% and 8.2 ~ 9.8 wt%.
Further optimization, in step (3), described crystallization temperature is 95 ~ 105 DEG C, and the time is 36 ~ 50h.
Further optimization, in step (3), the temperature of described roasting is 560 ~ 580 DEG C, and the time is 7 ~ 8h.
Further optimization, the SiO of described mesoporous Y-type zeolite molecular sieve
2/ Al
2o
3mol ratio is 3.4 ~ 4.1, and the aperture of meso-hole structure is 3.1 ~ 4.3 nm.
Further optimization, the modulus of described water glass is 3.1 ~ 3.4.
Present invention also offers the mesoporous Y-type zeolite molecular sieve obtained by above-mentioned preparation method.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the present invention has made y-type zeolite directed agents by oneself, utilize N, N-dimethyl-N-[3-(trimethoxy silicon) propyl group] chlorination octadecyl ammonium amphiphilic organosilane is as mesoporous template, this organosilane can act synergistically with y-type zeolite directed agents, and silane moiety can interact with silico-aluminate in gel, form stable Si-C key, it is mesoporous that long alkyl chain part then can assemble formation, play structure-directing effect, form mesoporous Y-type zeolite molecular sieve;
(2) the present invention is with water glass, sodium metaaluminate and sodium hydroxide for raw material, is cheaply easy to get, and adopts hydrothermal synthesis method, simplifies synthesis step, and preparation technology is simple, and cost is low;
(3) the mesoporous Y-type zeolite molecular sieve prepared of the present invention, there is the hole wall structure of crystallization, the zeolite molecular sieve of this hierarchical porous structure can avoid the defect of single pore structure, be the very valuable catalytic material of one, particularly relating to macromole and be subject to have broad application prospects in the reaction of diffusional limitation.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram that the mesoporous Y-type zeolite molecular sieve prepared of the present invention and common y-type zeolite contrast.
Fig. 2 is the stereoscan photograph of mesoporous Y-type zeolite molecular sieve material prepared by the present invention.
Fig. 3 is the transmission electron microscope photo of mesoporous Y-type zeolite molecular sieve material prepared by the present invention.
Fig. 4 a is the nitrogen adsorption-desorption isotherm of the mesoporous Y-type zeolite molecular sieve prepared of the present invention and common y-type zeolite, and Fig. 4 b is the pore size distribution curve calculated according to BJH model.
Embodiment
Below in conjunction with example and accompanying drawing, enforcement of the present invention is described further, but enforcement of the present invention and protection domain are not limited thereto.
embodiment 1
(1) by sodium metaaluminate (the 44.7 wt% Na of the sodium hydroxide of 5.425g, 1.065g
2o, 52.0 wt% Al
2o
3), 22.511g water glass (modulus is 3.1), the water of 42.5ml mixes, and at 30 DEG C, aging 24h obtains y-type zeolite directed agents.
(2) directed agents that the water of 29.0ml water glass (modulus is 3.1), 3.0ml, 4.0ml step (1) obtain at room temperature is mixed, after stirring 1h, again 3.5ml TPOAC (60 wt%, J ￡ K) is slowly added, continue to stir 2h.Last in mixture, add 5.0ml aluminum sulfate octadecahydrate (24 wt%) aqueous solution and 6.0ml sodium metaaluminate and sodium hydroxide mixed aqueous solution (17.8 wt% NaAlO again
2, 9.5 wt% NaOH), at room temperature stir 1h, obtain thick aluminosilicate gels.
(3) material will made through step (2) loads in the stainless steel cauldron of sealing, crystallization 24h at 90 DEG C, after crystallization terminates, solid product after suction filtration, washing and drying more in atmosphere at 550 DEG C roasting 8h remove organic formwork agent, thus obtain mesoporous Y-type zeolite molecular sieve.
embodiment 2
(1) by sodium metaaluminate (the 44.7 wt% Na of the sodium hydroxide of 6.0g, 1.5g
2o, 52.0 wt% Al
2o
3), 21.0g water glass (modulus is 3.4), the water of 45.0ml mixes, and at 35 DEG C, aging 48h obtains y-type zeolite directed agents.
(2) directed agents that the water of 35.0ml water glass (modulus is 3.4), 6.0ml, 7.0ml step (1) obtain at room temperature is mixed, after stirring 4h, again 5.0ml TPOAC (60 wt%, J ￡ K) is slowly added, continue to stir 6h.Last in mixture, add 7.5ml aluminum sulfate octadecahydrate (24 wt%) aqueous solution and 8.0ml sodium metaaluminate and sodium hydroxide mixed aqueous solution (17.8 wt% NaAlO again
2, 9.5 wt% NaOH), at room temperature stir 3h, obtain thick aluminosilicate gels.
(3) material will made through step (2) loads in the stainless steel cauldron of sealing, crystallization 60h at 110 DEG C, after crystallization terminates, solid product after suction filtration, washing and drying more in atmosphere at 600 DEG C roasting 5h remove organic formwork agent, thus obtain mesoporous Y-type zeolite molecular sieve.
embodiment 3
(1) by sodium metaaluminate (the 44.7 wt% Na of the sodium hydroxide of 8.0g, 2.5g
2o, 52.0 wt% Al
2o
3), 23.0g water glass (modulus is 3.2), the water of 50.0ml mixes, and at 32 DEG C, aging 36h obtains y-type zeolite directed agents.
(2) directed agents that the water of 32.0 water glass (modulus is 3.2), 5.0ml, 6.0ml step (1) obtain at room temperature is mixed, after stirring 2.5h, again 4.0ml TPOAC (60 wt%, J ￡ K) is slowly added, continue to stir 5h.Last in mixture, add 6.0ml aluminum sulfate octadecahydrate (24 wt%) aqueous solution and 7.5ml sodium metaaluminate and sodium hydroxide mixing solutions (17.8 wt% NaAlO again
2, 9.5 wt% NaOH), at room temperature stir 2h, obtain thick aluminosilicate gels.
(3) material will made through step (2) loads in the stainless steel cauldron of sealing, crystallization 40h at 100 DEG C, after crystallization terminates, solid product after suction filtration, washing and drying more in atmosphere at 570 DEG C roasting 8h remove organic formwork agent, thus obtain mesoporous Y-type zeolite molecular sieve.
Structural characterization is carried out to mesoporous Y-type zeolite molecular sieve prepared by embodiment.
D8 Advance type X-ray diffractometer (Bruker company, Germany) is adopted to characterize sample.As shown in Figure 1, sample presents the characteristic diffraction peak of typical y-type zeolite to result, and mate with common y-type zeolite diffraction peak relatively good, illustrate in product to there is y-type zeolite phase.
ZEISS Ultra 55 type field emission scanning electron microscope (Carl Zeiss company, Germany) is adopted to characterize the surface topography of sample.As shown in Figure 2, sample presents homogeneous stratiform pattern to result.
JEM-2100HR type transmission electron microscope (electronics corporation JEOL, Japan) is adopted to characterize product.As shown in Figure 3, mesoporous Y-type zeolite molecular sieve of the present invention presents intracrystalline meso-hole structure.
Adopt ASAP 2020 type N
2sorption Analyzer (Merck & Co., Inc, the U.S.) is analyzed the pore structure of product.As shown in Fig. 4 (a), mesoporous Y zeolite molecular sieve of the present invention shows H3 type sorption hysteresis ring, exists mesoporous in illustrative material.At 0.0 <
p/P 0 <'s 0.1 is low
p/P 0 district, adsorptive capacity with
p/P 0 increase and sharply increase, this is due to N
2in the filling in micropore district; At 0.5 <
p/P 0 there is desorption hysteresis loop in < 0.9 district, this is due to N
2capillary condensation in mesoporous causes; Be greater than
p/P 0 the region of=0.9, adsorptive capacity rises again, is due to N
2absorption in the macropore formed between particle.The pore size distribution curve of Fig. 4 (b) for calculating according to desorption BJH model, illustrate that mesoporous Y-type zeolite molecular sieve of the present invention exists narrower mesoporous pore size distribution, its mean pore size is 3.8 nm.
Claims (8)
1. a preparation method for mesoporous Y-type zeolite molecular sieve, is characterized in that, comprises the following steps:
(1) by water glass, sodium hydroxide, sodium metaaluminate and water according to mol ratio SiO
2: Na
2o:Al
2o
3: H
2o=(0.8 ~ 1.2): (1.0 ~ 1.5): (0.04 ~ 0.1): (20 ~ 26) mix, at 30 ~ 35 DEG C, aging 24 ~ 48 h obtain y-type zeolite directed agents;
(2) directed agents that water glass, water, step (1) obtain at room temperature is mixed, after stirring 1 ~ 4h, again N, N-dimethyl-N-[3-(trimethoxy silicon) propyl group] chlorination octadecyl ammonium (TPOAC) is slowly added, continue stirring 2 ~ 6h; The last mixed aqueous solution adding the aluminum sulfate octadecahydrate aqueous solution and sodium metaaluminate and sodium hydroxide again, at room temperature stirs 1 ~ 3h, obtains thick aluminosilicate gels; Mol ratio Na in last mixed system
2o:Al
2o
3: SiO
2: TPOAC:H
2o=(3.8 ~ 4.5): (0.8 ~ 1.3): (8.5 ~ 9.7): (0.28 ~ 0.36): (158 ~ 179);
(3) material will made through step (2) loads in the stainless steel cauldron of sealing, crystallization 24 ~ 60h at 90 ~ 110 DEG C, after crystallization terminates, solid product after suction filtration, washing and drying more in atmosphere at 550 ~ 600 DEG C roasting 5 ~ 8h remove organic formwork agent, thus obtain mesoporous Y-type zeolite molecular sieve.
2. preparation method according to claim 1, is characterized in that, in step (1), in described y-type zeolite directed agents, the mol ratio of each material is: SiO
2: Na
2o:Al
2o
3: H
2o=(0.95 ~ 1.1): (1.2 ~ 1.4): (0.06 ~ 0.1): (22 ~ 25).
3. preparation method according to claim 1, is characterized in that, in step (1), the described aging time is 32 ~ 40h.
4. preparation method according to claim 1, it is characterized in that, in step (2), described aluminum sulfate octadecahydrate aqueous solution massfraction is 23 ~ 25 wt%, and the massfraction of the mixed aqueous solution of sodium metaaluminate and sodium hydroxide is respectively 16.9 ~ 18.2 wt% and 8.2 ~ 9.8 wt%.
5. preparation method according to claim 1, is characterized in that, in step (3), described crystallization temperature is 95 ~ 105 DEG C, and the time is 36 ~ 50h.
6. preparation method according to claim 1, is characterized in that, in step (3), the temperature of described roasting is 560 ~ 580 DEG C, and the time is 7 ~ 8h.
7. preparation method according to claim 1, is characterized in that, the SiO of described mesoporous Y-type zeolite molecular sieve
2/ Al
2o
3mol ratio is 3.4 ~ 4.1, and the aperture of meso-hole structure is 3.1 ~ 4.3 nm.
8. the preparation method according to any one of claim 1 ~ 7, is characterized in that the modulus of described water glass is 3.1 ~ 3.4.
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