CN101973561A - Synthesis method of molecular sieve with meso-microporous sequence structure - Google Patents
Synthesis method of molecular sieve with meso-microporous sequence structure Download PDFInfo
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Abstract
The invention discloses a synthesis method of a molecular sieve (NUS-5) with a meso-microporous sequence structure, which comprises the following steps: mixing tetraethyl orthosilicate (TEOS), sodium meta-aluminate (NaAlO2), tetrapropylammonium hydroxide (TPAOH), n-hexane trimethyl ammonium bromide (HTAB) and water according to a certain proportion, and stirring at room temperature to obtain settled solution; transferring the settled solution into a synthesis kettle, heating to 170 DEG C, and carrying out static crystallization for 24-168h; and filtering and washing the obtained solid product with deionized water, drying at the temperature of 60 DEG C for 3-5h, and roasting the dried white powder at the temperature of 550 DEG C for 8h to obtain the molecular sieve product with the meso-microporous sequence structure. In the method, the HTAB as a mesoporous template and the TPAOH as a microporous template are utilized to synthetize the molecular sieve. The synthesis method has simple process route and solves the technical problems of complicated synthesis process and high production cost in the prior art. The NUS-5 can be applied to multiple technical fields related to larger organic molecules such as a plurality of petrochemistry-related processes, separation and purification of macromolecules, solid support of enzyme, DNA sequencing and the like.
Description
Technical field the invention belongs to the porous material chemosynthesis technical field, relate to the process that a kind of preparation has the sequence structure zeolite crystal material (called after NUS-5) of micropore-mesopore sequence pore passage structure and MFI framework of molecular sieve, be specifically related to a kind of synthetic method of Jie's of having micropore sequence structure molecular screen.
Background technology NUS-5 material can be used as solid catalyst and sorbent material is used for bigger organic molecule, as the catalytic conversion of heavy oil molecules with separate purification, and traditional micro-pore zeolite is because the less processing requirement that do not reach in duct.
The requirement of the chemical technology that environment is good has caused the huge research interest of people to novel porous developing material.Big I according to aperture of porous material is divided into three classes with porous material: the aperture is less than the poromerics of 2nm; The mesoporous material of aperture between 2～50nm; The aperture is greater than the large pore material of 50nm, and the micro-pore zeolite molecular sieve has been widely used in fields such as refining of petroleum, fine chemistry industry and fractionation by adsorption as effective solid acid catalyst.(Tao Y., et al., Chem.Rev., 2006,106:896; Egebald K., et al., Chem.Mater., 2008,20:946;
J.et al., Catal.Rev.-Sci.Eng., 2007,49,457) outstanding feature of zeolite molecular sieve is can modulation acidity, can provide the ducts of different sizes and hole to play simultaneously and select the shape effect.Yet micro-pore zeolite has diffusional limitation to more macromolecular reactant and product.Therefore, it is more and more stronger to handle the serious hope of macromolecular substance with novel porous material.
(WO 91/11390 since the researchist by Mobil company in 1992 utilizes the supramolecule self-assembly effect of tensio-active agent to synthesize M41S series mesopore molecular sieve, 1991) since, that has reported at present has types such as MCM-41 and MCM-48, this mesoporous material (MCM-41 and MCM-48) with its adjustable regular duct (its aperture can be in the 1.5-10nm scope modulation, broken the limitation that conventional molecular sieve bore diameter can not surpass 1.2nm.Yet, the amorphous hole wall of these pure aluminium silicate mesoporous materials make its stability and thermostability relatively poor, surface acidity is also lower, thereby is unfavorable for its practical application.In order to improve the performance of mesoporous material, people attempt to have structure (Liu Y., et al., J.Am.Chem.Soc., 2000, the 122:8791 of mesoporous zeolitic material; Zhang Z.T., et al., J.Am.Chem.Soc., 2001,123,5014).Can be made up by zeolite crystal although it is believed that the skeleton of so-called mesoporous zeolite, the material in the reality is still unbodied, thereby acid and still not raising of hydrothermal stability.
Say that from another point of view by reducing the intracrystalline diffusion path length, the nanocrystalline preparation of zeolite is used to solve diffusion problem always.Yet separating superfine sieve particle from reaction mixture also is very thorny and expensive problem.In addition, the physicochemical property of molecular sieve also are very different with traditional zeolite.
Different with above effort is, the investigator has confirmed to introduce mesopore in the crystalline microporous zeolite to make up Jie/micropore sequence zeolite be a very promising technology.Because this method can not only strengthen quality transfering rate, and can keep the physicochemical property of traditional zeolite.Creating mesoporous trial in early days on micro-pore zeolite is the method for coming dealuminzation or desiliconization by alkali or acid extraction, but the mesoporous of these processes development is not mutual banded, thereby almost can not strengthen rate of diffusion.
The template synthesis method has caused the interest of quick growth as the research of synthetic sequence zeolite.With hard template (as, gac, carbon fiber, aerosol and polymkeric substance etc.) and two kinds of template of soft template all be proved effectively.Consider the adjustability and the ease for operation of pore structure, soft template method is more feasible on industrial application.Several soft template methods be in the news (Choi M., et al., Nat.Mater., 2006,5:718 are arranged; Wang H., et al., Angew.Chem.Int.Ed., 2006,45,7603) or complicatedsynthesis procedures (Lei Q., et al., Chem.Comm., 2006,1769; Wang J., et al., Chem.Comm., 2007,4653), but all well-designed templates of need or complicated building-up process also do not have synthetic method report simple and with low cost at present.
Summary of the invention the objective of the invention is to solve the technical problem that prior art exists synthesis technique complexity, production cost costliness, and a kind of synthetic method of Jie's of having micropore sequence structure molecular screen is provided.
The present invention has the synthetic method of Jie's micropore sequence structure molecular screen, and its main points are to be undertaken by following technology:
1), batching: with tetraethoxy, sodium metaaluminate, TPAOH, normal hexane trimethylammonium bromide and water is raw material, and the mol ratio of each component is followed successively by: 11-32: 1: 3-8: 5-13: 1138;
2), synthetic: that said components is mixed in proportion, obtain settled solution after the stirring at room, shift and in synthesis reactor, be heated to 170 ℃, static crystallization 24～168 hours, solid product after filtration, behind the deionized water wash, 60 ℃ of dryings 3～5 hours, exsiccant white powder art promptly got the micropore sequence structure molecular screen product that is situated between in 550 ℃ of roastings 8 hours.
Jie's micropore sequence structure molecular screen, called after NUS-5.
The chemistry abbreviation of tetraethoxy, sodium metaaluminate, TPAOH, normal hexane trimethylammonium bromide is respectively: TEOS, NaAlO
2, TPAOH, HTAB.
The present invention adopts cheap normal hexane trimethylammonium bromide (HTAB) to make the micropore template as mesoporous template and tripropyl ammonium hydroxide (TPAOH), adopt " one kettle way " synthetic, because NUS-5 is a kind of molecular sieve, can be used for the relevant process of many and traditional molecular sieve, as, heterogeneous catalyst, absorption, separation and ion-exchange.Especially for the chemical conversion of big organic molecule, handle as heavy oil, NUS-5 has the plurality of advantages that surpasses traditional molecular sieve, as low diffusional resistance.Operational path of the present invention is simple, has solved the technical problem that prior art exists synthesis technique complexity, production cost costliness.
Description of drawings
Fig. 1 is the XRD spectra of embodiment 1 Central Plains powder (Si/Al=32);
Fig. 2 is the N of roasting sample (Si/Al=32) among the embodiment 1
2Adsorption isothermal line (a) and pore distribution (b);
Fig. 3 is the SEM figure of embodiment 1 Central Plains powder (Si/Al=32);
Fig. 4 is the SEM figure of roasting sample (Si/Al=32) among the embodiment 1;
Fig. 5 is the TEM (a) and the SAED figure of roasting sample among the embodiment 1;
Fig. 6 is the N of roasting sample (Si/Al=11) among the embodiment 2
2Adsorption isothermal line (a) and pore distribution (b);
Fig. 7 is the XRD spectra of embodiment 2 Central Plains powder (Si/Al=11);
Fig. 8 is the TEM figure of roasting sample among the embodiment 2;
Fig. 9 is the N of roasting sample (Si/Al=32) among the embodiment 3
2Adsorption isothermal line (a) and pore distribution (b);
Figure 10 is the XRD spectra of embodiment 3 Central Plains powder (Si/Al=32);
Figure 11 is the SEM figure of embodiment 3 Central Plains powder (Si/Al=32);
Figure 12 is the XRD spectra of embodiment 4 Central Plains powder (Si/Al=14);
Figure 13 is the N of roasting sample (Si/Al=14) among the embodiment 4
2Adsorption isothermal line (a) and pore distribution (b);
Figure 14 is the N of roasting sample (Si/Al=32) among the embodiment 5
2Adsorption isothermal line (a) and pore distribution (b)
Figure 15 is the XRD spectra of embodiment 5 Central Plains powder (Si/Al=32);
Figure 16 is the SEM figure of embodiment 5 Central Plains powder (Si/Al=32);
Figure 17 is the N of roasting sample (Si/Al=32) among the embodiment 6
2Adsorption isothermal line (a) and pore distribution (b);
Figure 18 is the XRD spectra of embodiment 6 Central Plains powder (Si/Al=32);
Figure 19 is the SEM spectrogram of embodiment 6 Central Plains powder (Si/Al=32);
Figure 20 is the N of roasting sample (Si/Al=32) among the embodiment 7
2Adsorption isothermal line (a) and pore distribution (b);
Figure 21 is the XRD spectra of embodiment 7 Central Plains powder (Si/Al=32).
Embodiment is further set forth the inventive method below in conjunction with specific embodiment.
Embodiment 1: with tetraethoxy (TEOS), sodium metaaluminate (NaAlO
2), TPAOH (TPAOH), normal hexane trimethylammonium bromide (HTAB) and water is according to 32TEOS: 1NaAlO
2: 8TPAOH: 13HTAB: 1138H
2The mixed of O obtains settled solution after the stirring at room, shift in synthesis reactor, to be heated to the 170C static crystallization 48 hours, solid product after filtration, deionized water wash and in 60 ℃ of dryings 5 hours, the exsiccant white powder can in 550 ℃ of roastings 8 hours.
The XRD spectra of Fig. 1 shows that former powder has the crystalline texture of typical ZSM-5 zeolite, and sharp-pointed and strong spectrum peak shows that molecular sieve has higher degree of crystallinity.N among Fig. 2 a
2Adsorption isothermal line shows that the sample of roasting has meso-hole structure, and Fig. 2 b shows that material has broad and bigger aperture from 7nm to 100nm, but mainly is distributed in about 20nm, and the BET surface-area is 368m
2/ g, total pore volume are 0.36cm
3/ g.SEM image among Fig. 3 shows that former powder material has the sequence structure of corynebacterium, and sample keeps the pattern of former powder after the roasting.As can be seen, stub is in layer to be piled up by the molecular sieve thin slice to form (Fig. 4 b).Fig. 5 a shows the TEM image of typical of molecular sieves thin slice, and the molecular sieve thin slice is formed meso-hole structure and formed by nanocrystalline the interlinking of many molecular sieves as can be seen, and SAED figure shows the single crystal structure of molecular sieve thin layer.
Embodiment 2: with tetraethoxy (TEOS), sodium metaaluminate (NaAlO
2), TPAOH (TPAOH), normal hexane trimethylammonium bromide (HTAB) and water is according to 11TEOS: 1NaAlO
2: 3TPAOH: 5HTAB: 1138H
2The mixed of O obtains settled solution after the stirring at room, shift in synthesis reactor, to be heated to the 170C static crystallization 48 hours, solid product after filtration, deionized water wash and with 60 ℃ of dryings 5 hours, the exsiccant white powder was in 550 ℃ of roastings 8 hours.
After the crystallization, sample is a gelatinous product, the N among Fig. 6 a
2Adsorption isothermal line is typical IV type thermoisopleth, shows that the sample of roasting has meso-hole structure, and the BET surface-area is 423m
2/ g, total pore volume are 1.1cm
3/ g.Fig. 6 b shows that product has pore size distribution narrower among the embodiment 1, and scope is from 4nm to 30nm, but mainly is distributed in about 11nm.It is zeolite structured that the XRD spectra of Fig. 7 shows that former powder has a ZSM-5, yet relatively have low degree of crystallinity with embodiment 1.The TEM of Fig. 8 shows that the roasting sample has " worm " class pore structure.
Embodiment 3: with tetraethoxy (TEOS), sodium metaaluminate (NaAlO
2), TPAOH (TPAOH), normal hexane trimethylammonium bromide (HTAB) and water is according to 32TEOS: 1NaAlO
2: 8TPAOH: 13HTAB: 1138H
2The mixed of O obtains settled solution after the stirring at room, shift in synthesis reactor, to be heated to 170 ℃ of static crystallizations 24 hours, solid product after filtration, deionized water wash and with 60 ℃ of dryings 5 hours.The exsiccant white powder was in 550 ℃ of roastings 8 hours.
Fig. 9 illustrates product meso-hole structure, and pore size is from 5nm to 30nm, but mainly is distributed in about 15nm, and the BET surface-area is 409m
2/ g, total pore volume are 0.47cm
3/ g.It is zeolite structured that the XRD spectra of Figure 10 shows that former powder is that crystallization well has a ZSM-5.The SEM of Figure 11 shows that sample has the sequence structure of continuous shape.
Embodiment 4: with tetraethoxy (TEOS), sodium metaaluminate (NaAlO
2), TPAOH (TPAOH), normal hexane trimethylammonium bromide (HTAB) and water is according to 14TEOS: 1NaAlO
2: 8TPAOH: 13HTAB: 1138H
2The mixed of O obtains settled solution after the stirring at room, shift in synthesis reactor, to be heated to 170 ℃ of static crystallizations 72 hours, solid product after filtration, deionized water wash and with 60 ℃ of dryings 5 hours.The exsiccant white powder was in 550 ℃ of roastings 8 hours.
The XRD spectra of Figure 12 shows that product is the good ZSM-5 crystallization of zeolites of a crystallization structure.N among Figure 13 a
2Adsorption isothermal line shows that the sample of roasting has meso-hole structure, and Figure 13 b shows that material has broad and bigger aperture from 4nm to 120nm, but mainly is distributed in about 12nm.The BET surface-area is 276m
2/ g, total pore volume are 0.44cm
3/ g.
Embodiment 5: with tetraethoxy (TEOS), sodium metaaluminate (NaAlO
2), TPAOH (TPAOH), normal hexane trimethylammonium bromide (HTAB) and water is according to 32TEOS: 1NaAlO
2: 8TPAOH:: 13HTAB: 1138H
2The mixed of O obtains settled solution after the stirring at room, shift in synthesis reactor, to be heated to 170 ℃ of static crystallizations 96 hours, solid product after filtration, deionized water wash and with 60 ℃ of dryings 5 hours, the exsiccant white powder was in 550 ℃ of roastings 8 hours.
N among Figure 14 a
2Adsorption isothermal line shows that the sample of roasting has meso-hole structure, and Figure 14 b shows that material has broad and bigger aperture from 7nm to 130nm, but mainly is distributed in about 18nm, and the BET surface-area is 358m
2/ g, total pore volume are 0.43cm
3/ g.The XRD spectra of Figure 15 shows that product is the good ZSM-5 crystallization of zeolites of a crystallization structure iron.SEM image in 16 shows that former powder material has the sequence structure of corynebacterium.
Embodiment 6: with tetraethoxy (TEOS), sodium metaaluminate (NaAlO
2), TPAOH (TPAOH), normal hexane trimethylammonium bromide (HTAB) and water is according to 32TEOS: 1NaAlO
2: 8TPAOH: 13HTAB: 1138H
2The mixed of O obtains settled solution after the stirring at room, shift in synthesis reactor, to be heated to 170 ℃ of static crystallizations 161 hours, solid product after filtration, deionized water wash and with 60 ℃ of dryings 5 hours, the exsiccant white powder was in 550 ℃ of roastings 8 hours.
N among Figure 18 a
2Adsorption isothermal line shows that the sample of roasting has meso-hole structure, and Figure 18 b shows that material has broad and bigger aperture from 8nm to 130nm, but mainly is distributed in about 18nm, and the BET surface-area is 368m
2/ g, total pore volume are 0.31cm
3/ g.The XRD spectra of Figure 15 shows that product is the good ZSM-5 crystallization of zeolites of a crystallization structure iron.SEM image in 19 shows that former powder material has the sequence structure of corynebacterium.
Embodiment 7: with tetraethoxy (TEOS), sodium metaaluminate (NaAlO
2), TPAOH (TPAOH), normal hexane trimethylammonium bromide (HTAB) and water is according to 32TEOS: 1NaAlO
2: 8TPAOH: 13HTAB: 1138H
2The mixed of O obtains settled solution after the stirring at room, shift in synthesis reactor, to be heated to 170 ℃ of static crystallizations 144 hours, solid product after filtration, deionized water wash and with 60 ℃ of dryings 5 hours, the exsiccant white powder is little in 550 ℃ of roastings 8.
N among Figure 20 a
2Adsorption isothermal line shows that the sample of roasting has meso-hole structure, and Figure 20 b shows that material has broad and bigger aperture from 5nm to 30nm, but mainly is distributed in about 12nm, and the BET surface-area is 493m
2/ g, total pore volume are 0.77cm
3/ g.The XRD spectra of Figure 21 shows that product is the good ZSM-5 crystallization of zeolites of a crystallization structure.
Claims (1)
1. synthetic method with Jie's micropore sequence structure molecular screen is characterized in that being undertaken by following technology:
1), batching: with tetraethoxy, sodium metaaluminate, TPAOH, normal hexane trimethylammonium bromide and water is raw material, and the mol ratio of each component is followed successively by: 11-32: 1: 3-8: 5-13: 1138;
2), synthetic: that said components is mixed in proportion, obtain settled solution after the stirring at room, shift and in synthesis reactor, be heated to 170 ℃, static crystallization 24～168 hours, solid product after filtration, behind the deionized water wash, 60 ℃ of dryings 3～5 hours, the exsiccant white powder promptly got the micropore sequence structure molecular screen product that is situated between in 550 ℃ of roastings 8 hours.
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| CN102416344A (en) * | 2011-10-20 | 2012-04-18 | 中国石油天然气集团公司 | Preparation method of step hole ZSM-5 zeolite composite material-based low-temperature sulfur transfer catalyst for FCC (Fluid Catalytic Cracking) petroleum |
| CN102423718A (en) * | 2011-10-20 | 2012-04-25 | 中国石油大学(北京) | Preparation method for novel FCC (Fluid Catalytic Cracking) gasoline low-temperature sulfur transfer catalyst |
| CN105038090A (en) * | 2015-07-20 | 2015-11-11 | 广西中烟工业有限责任公司 | Method for preparing novel antibacterial electronic cigarette appearance material |
| CN105084381A (en) * | 2015-09-23 | 2015-11-25 | 成都艾比科生物科技有限公司 | Production device with microporous structure molecular sieve |
| CN105329914A (en) * | 2014-08-11 | 2016-02-17 | 中国石油天然气集团公司 | Micropore-mesoporous composite ZSM-5 zeolite and preparation method thereof |
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| CN110872123A (en) * | 2019-11-11 | 2020-03-10 | 内蒙古民族大学 | Preparation method of inorganic porous material |
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| CN114956112A (en) * | 2022-06-09 | 2022-08-30 | 中国地质大学（北京） | Preparation method of mesoporous zeolite with virus as soft template |
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| CN102423718A (en) * | 2011-10-20 | 2012-04-25 | 中国石油大学(北京) | Preparation method for novel FCC (Fluid Catalytic Cracking) gasoline low-temperature sulfur transfer catalyst |
| CN102423718B (en) * | 2011-10-20 | 2013-05-15 | 中国石油大学(北京) | Preparation method for novel FCC (Fluid Catalytic Cracking) gasoline low-temperature sulfur transfer catalyst |
| CN102416344B (en) * | 2011-10-20 | 2013-08-28 | 中国石油天然气集团公司 | Preparation method of step hole ZSM-5 zeolite composite material-based low-temperature sulfur transfer catalyst for FCC (Fluid Catalytic Cracking) petroleum |
| CN105329914A (en) * | 2014-08-11 | 2016-02-17 | 中国石油天然气集团公司 | Micropore-mesoporous composite ZSM-5 zeolite and preparation method thereof |
| CN105038090A (en) * | 2015-07-20 | 2015-11-11 | 广西中烟工业有限责任公司 | Method for preparing novel antibacterial electronic cigarette appearance material |
| CN105038090B (en) * | 2015-07-20 | 2018-03-02 | 广西中烟工业有限责任公司 | A kind of preparation method of antibacterial electronic cigarette appearance material |
| CN105084381A (en) * | 2015-09-23 | 2015-11-25 | 成都艾比科生物科技有限公司 | Production device with microporous structure molecular sieve |
| CN108126731A (en) * | 2017-12-08 | 2018-06-08 | 河南省科学院能源研究所有限公司 | A kind of solid acid catalyst that levulic acid is prepared for biomass by hydrolyzation |
| CN108126731B (en) * | 2017-12-08 | 2020-12-22 | 河南省科学院能源研究所有限公司 | Solid acid catalyst for preparing levulinic acid by hydrolyzing biomass |
| CN110872123A (en) * | 2019-11-11 | 2020-03-10 | 内蒙古民族大学 | Preparation method of inorganic porous material |
| CN112939016A (en) * | 2021-03-10 | 2021-06-11 | 成都理工大学 | Chain-shaped ZSM-5 micro mesoporous molecular sieve formed by egg protein induction and synthesis method thereof |
| CN114956112A (en) * | 2022-06-09 | 2022-08-30 | 中国地质大学（北京） | Preparation method of mesoporous zeolite with virus as soft template |
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Application publication date: 20110216 |