CN104261423A - Preparation method of single crystal hierarchical porous Beta molecular sieve - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention belongs to the technical field of synthesis of inorganic porous materials and particularly relates to a preparation method of a single crystal hierarchical porous Beta molecular sieve. The preparation method comprises the following steps: firstly, adding an inorganic alkali source and an aluminum source into an aqueous solution of a microporous template (TEA<+>); then, adding a proper amount of N-methyl-2-pyrrolidone (NMP) and a silicon source to uniformly stir; and synthesizing the single crystal hierarchical porous Beta molecular sieve (HP-Beta) by using a simple hydrothermal method. The HP-Beta has the double advantages of a microporous molecular sieve and a mesoporous material. Based on retaining the inherent microporous frame, the acidity and the stability of the Beta molecular sieve, the HP-Beta has abundant mesopores and a relatively large surface area and has a wide application prospect in the fields such as catalysis, adsorption and separation. The preparation method provided by the invention, using non-toxic and cheap NMP as a mesoporous forming agent, is an economic, efficient and environment-friendly synthetic method.
Description
Technical field
The invention belongs to inorganic porous material preparing technical field, be specifically related to a kind of preparation method of monocrystalline multi-stage porous Beta molecular sieve.
Background technology
1967, Mobil oil company of the U.S. successfully develops a kind of novel molecular sieve-Beta zeolite molecular sieve, it is the supersiliceous zeolite uniquely with twelve-ring three-dimensional open-framework, structural dislocation and defect are covered with its skeleton, but still can keep loading capacity completely, be also the large pore zeolite uniquely with chirality duct decussate texture simultaneously.Beta zeolite molecular sieve stability is high, and acid strong, silica alumina ratio is adjustable, synthetic ratio scope is large, duct is homogeneous and be straight hole road, is widely used in absorption, is separated and the field such as catalysis (such as, alkylation, hydrocracking, hydroisomerization, hydrocarbon cracking etc.).But the micropore canals that Beta molecular sieve is intrinsic (being less than 2nm) is unfavorable for macromolecular diffusion and transmission in catalyzed reaction, easily cause the problems such as carbon distribution, catalytic efficiency are low, catalyst deactivation, limit its further application in macromole Industrial Catalysis.
In order to solve this diffusional limitation problem, people attempt introducing meso-hole structure in Beta molecular sieve, prepare multi-stage porous Beta molecular sieve.The plurality of advantages such as multi-stage porous molecular sieve has that the acidity of micro porous molecular sieve is strong, the mass transfer velocity of good stability and mesoporous material is fast, show good catalytic effect, are still the focus of academia and industry member research so far in bulky molecular catalysis.
The people such as Xiao (Feng-Shou Xiao, Lifeng Wang, Chengyang Yin, et al.Angew.Chem.Int.Ed., 2006,118,3162-3165) with the high polyquaternium cationic (diallyl dimethyl ammoniumchloride of mesoporous yardstick, PDADMAC) be mesoporous template, by the synthesising mesoporous Beta molecular sieve of space steric effect success; The people such as Serrano (David P.Serrano, Jos é Aguado, Jos é M.Escola, et al.Chem.Mater., 2006,18,2462-2464) adopt organosilane phenylamino propyl trimethoxy silicane (PHAPTMS) as mesoporous template, under organic amine (TEAOH) system, synthesis has the Beta molecular sieve of hierarchical porous structure.
The mesoporous template complex structure of these polymers, is difficult to preparation, and cost is large compared with high and toxicity, is unfavorable for that large-scale commercial is produced.Therefore, develop a kind of environmental friendliness, cheap mesoporous pore-creating agent prepares multi-stage porous Beta molecular sieve for mass-producing important realistic meaning.
Summary of the invention
The object of the invention is to for the problem existing for above-mentioned prior art and defect, the preparation method of monocrystalline multi-stage porous Beta molecular sieve of a kind of economy, efficient, environmental protection is provided.
In the present invention we with nontoxic, cheap METHYLPYRROLIDONE (NMP) for mesoporous pore-creating agent, replace expensive mesoporous template, by simple water heat transfer monocrystalline multi-stage porous Beta molecular sieve (hierarchical porous Beta, HP-Beta).HP-Beta molecular sieve has larger specific surface area and outer surface area, abundant mesopore orbit and stronger acidity and stability, there is the two-fold advantage of micro porous molecular sieve and mesoporous material, on the basis retaining Beta molecular sieve intrinsic porous skeleton, acidity and stability, have a wide range of applications in bulky molecular catalysis, absorption with in being separated etc.
For achieving the above object, the invention provides a kind of preparation method of Beta molecular sieve of monocrystalline multi-stage porous, its step is as follows:
(1) inorganic alkali source, aluminium source are joined micropore template (TEA
+) the aqueous solution in, stir;
(2) in the solution of step (1), add METHYLPYRROLIDONE (NMP), stir;
(3) in the solution of step (2), add silicon source, stir;
(4) product step (3) obtained loads in reactor, airtight, thermostatic crystallization is carried out in spontaneous pressure, after crystallization, solid product is through centrifugal, washing, drying, organic formwork agent is removed in calcining in atmosphere, thus obtains the monocrystalline Beta molecular sieve with hierarchical porous structure.
In the present invention, inorganic alkali source according to reason opinion generates M
2o gauge, aluminium source generates Al by theoretical
2o
3gauge, silicon source generates SiO by theoretical
2gauge, in above-mentioned reaction system, the mol ratio of each component is M
2o:Al
2o
3: SiO
2: H
2o:TEA
+: NMP=0.003 ~ 0.21:0.005 ~ 0.067:1:8.0 ~ 72.5:0.085 ~ 1.3:0.05 ~ 4.0; Be preferably M
2o:Al
2o
3: SiO
2: H
2o:TEA
+: NMP=0.0063 ~ 0.1:0.0091 ~ 0.033:1:10.0 ~ 31.2:0.1 ~ 0.85:0.25 ~ 2.52; M represents K or Na.
In step (1), described inorganic alkali source is one or more in sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, be preferably sodium hydroxide, potassium hydroxide, most preferably be sodium hydroxide.
In step (1), described aluminium source is one or more in sodium aluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate, pseudo-boehmite, aluminum oxide, aluminium hydroxide, aluminum acetate, aluminium carbonate, pure aluminum, aluminum isopropylate, is preferably sodium aluminate.
In step (1), described micropore template is one or more in tetraethyl ammonium hydroxide (TEAOH), tetraethylammonium bromide, etamon chloride, tetraethyl ammonium fluoride, is preferably tetraethyl ammonium hydroxide.
In step (3), described silicon source is one or more in white carbon black, water glass, silicon sol, silica gel, diatomite, tetraethoxy, is preferably white carbon black.
In step (4), described crystallization temperature is 100 ~ 200 DEG C, and be preferably 130 ~ 180 DEG C, crystallization time is 0.5 ~ 96h, is preferably 3 ~ 72h.
In step (4), described calcining temperature is 500 ~ 700 DEG C, and be preferably 550 ~ 600 DEG C, calcination time is 0.5 ~ 24h, and be preferably 4 ~ 8h, temperature rise rate is 0.2 ~ 5 DEG C of min
-1, be preferably 0.5 ~ 2 DEG C of min
-1.
Relative to prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention is mesoporous pore-creating agent with nontoxic, cheap METHYLPYRROLIDONE, replace expensive mesoporous template, by simple water heat transfer monocrystalline multi-stage porous Beta molecular sieve, be the synthetic method of a kind of economy, efficient, environmental protection, be expected to large-scale commercial and produce.
(2) the monocrystalline multi-stage porous Beta molecular sieve synthesized by the present invention has good stability, acid strong, mesopore orbit abundant and specific surface area and the feature such as external surface area is large, therefore, have a wide range of applications in bulky molecular catalysis, absorption with in being separated etc.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of monocrystalline multi-stage porous Beta molecular sieve prepared by embodiment 3.
Fig. 2 is scanning electron microscope (SEM) photo of monocrystalline multi-stage porous Beta molecular sieve prepared by embodiment 3.
Fig. 3 is transmission electron microscope (TEM) and selected area electron diffraction (SAED) photo of monocrystalline multi-stage porous Beta molecular sieve prepared by embodiment 3.Wherein, Fig. 3 a is low power TEM photo, and Fig. 3 b is high power TEM photo, and Fig. 3 c is selected area electron diffraction (SAED) photo that Fig. 3 b is corresponding.
Fig. 4 is the N of monocrystalline multi-stage porous Beta molecular sieve prepared by embodiment 3
2adsorption/desorption isothermal curve.Wherein, curve 1 represents N
2adsorption curve, curve 2 represents N
2desorption curve.
Fig. 5 is the BJH graph of pore diameter distribution of monocrystalline multi-stage porous Beta molecular sieve prepared by embodiment 3.
Embodiment
In conjunction with following instance the present invention made and further describing, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
(1) 0.04g sodium hydroxide, 0.075g sodium aluminate are added in the aqueous solution (massfraction 25%) of 7.5g tetraethyl ammonium hydroxide, stir to clarify solution;
(2) in the settled solution of step (1), add the METHYLPYRROLIDONE of 2g, stir;
(3) (speed is about 0.1g min in the solution of step (2), slowly to add 0.2g white carbon black
-1), after dissolving to be mixed, then (speed is about 0.1g min to add 0.4g white carbon black
-1), continue to stir 1h, obtaining constitutive molar ratio is Na
2o:Al
2o
3: SiO
2: H
2the transparent and homogeneous colloidal sol of O:TEAOH:NMP=0.048:0.023:1:15.6:0.636:1;
(4) loaded in reactor by the colloidal sol of step (3), at autogenous pressures, 140 DEG C of crystallization 12h, after crystallization terminates, naturally cool to room temperature.By centrifugal for product 8000rpm 5min collection and with deionized water wash to neutral, then use washing with alcohol secondary, in 70 DEG C of oven drying 24h.Finally, in atmosphere 550 DEG C calcining 5h (temperature rise rate is 1 DEG C of min
-1) removing organic formwork agent, obtain monocrystalline multi-stage porous Beta molecular sieve.X-ray diffraction (XRD) figure and Fig. 1 of gained Beta product is substantially identical, and scanned photograph is similar to Fig. 2, and sample particle diameter is about 326nm.
Embodiment 2
(1) 0.04g sodium hydroxide, 0.068g sodium aluminate are added in the aqueous solution (massfraction 25%) of 7.5g tetraethyl ammonium hydroxide, stir to clarify solution;
(2) in the settled solution of step (1), add 4g METHYLPYRROLIDONE, stir;
(3) (speed is about 0.1g min in the solution of step (2), slowly to add 0.2g white carbon black
-1), after dissolving to be mixed, then (speed is about 0.1g min to add 0.4g white carbon black
-1), continue to stir 0.5h, obtaining constitutive molar ratio is Na
2o:Al
2o
3: SiO
2: H
2the transparent and homogeneous colloidal sol of O:TEAOH:NMP=0.046:0.021:1:15.6:0.636:2;
(4) loaded in reactor by the colloidal sol of step (3), at autogenous pressures, 140 DEG C of crystallization 12h, after cooling 6h under room temperature, then in 140 DEG C of crystallization 60h.After crystallization terminates, naturally cool to room temperature.By centrifugal for product 6000rpm 3min collection and with deionized water wash to neutral, then use washing with alcohol secondary, in 70 DEG C of oven drying 24h.Finally, in atmosphere 600 DEG C calcining 4h (temperature rise rate is 1 DEG C of min
-1) removing organic formwork agent, obtain monocrystalline multi-stage porous Beta molecular sieve.XRD figure and Fig. 1 of gained Beta product are similar, and peak width is slightly narrow, and particle diameter is about 430nm.
Embodiment 3
(1) 0.04g sodium hydroxide, 0.075g sodium aluminate are added in the aqueous solution (massfraction 25%) of 7.5g tetraethyl ammonium hydroxide, stir to clarify solution;
(2) in the settled solution of step (1), add 2g METHYLPYRROLIDONE, stir;
(3) (temperature rise rate is 1 DEG C of min in the solution of step (2), slowly to add 0.2g white carbon black
-1), after dissolving to be mixed, then (temperature rise rate is 1 DEG C of min to add 0.4g white carbon black
-1), continue to stir 1h, obtaining constitutive molar ratio is Na
2o:Al
2o
3: SiO
2: H
2the transparent and homogeneous colloidal sol of O:TEAOH:NMP=0.048:0.023:1:15.6:0.636:1;
(4) loaded in reactor by the colloidal sol of step (3), at autogenous pressures, 140 DEG C of crystallization 12h, after cooling 6h under room temperature, then in 140 DEG C of crystallization 48h.After crystallization terminates, naturally cool to room temperature.By centrifugal for product 8000rpm 5min collection and with deionized water wash to neutral, then use washing with alcohol secondary, in 70 DEG C of oven drying 24h.Finally, in atmosphere 550 DEG C calcining 6h (temperature rise rate is 1 DEG C of min
-1) removing organic formwork agent, obtain monocrystalline multi-stage porous Beta molecular sieve.
Phenetic analysis is carried out to monocrystalline multi-stage porous Beta molecular sieve (HP-Beta) prepared by embodiment 3.
Adopt Rigaku D/MAX-2550 type X-ray diffractometer (Japan) to carry out thing to HP-Beta product to characterize mutually.Result as shown in Figure 1, the XRD spectra of HP-Beta sample and the characteristic peak of typical Beta molecular sieve completely the same, there is not any assorted peak, and degree of crystallinity is good.
JEOL JSM-6700F type scanning electronic microscope (Japan) is adopted to carry out morphology characterization to HP-Beta product.As shown in Figure 2, the pattern of HP-Beta sample is homogeneous " dice " shape to result, and particle diameter is about 300 ~ 350nm, and surface exists obvious nanoparticle.
JEOL JSM-3010F type transmission electron microscope (Japan) is adopted to carry out Characterization for Microstructure to HP-Beta product.(Fig. 3 a) shows HP-Beta sample and presents obvious multilevel hierarchy low power transmission electron microscope (TEM) photo, and abundant is mesoporous high-visible; High power transmission electron microscope (TEM) photo (Fig. 3 b) shows that primary particle particle diameter is about 10 ~ 30nm, and consistent lattice fringe orientation shows that HP-Beta sample is single crystal structure; In addition, the corresponding selected area electron diffraction of Fig. 3 b (SAED) point (Fig. 3 c) presents obvious discrete state, illustrates that the general performance of HP-Beta sample is single crystal structure and crystallinity is good.
Adopt Micromeritics ASAP 2020M type N
2sorption Analyzer (U.S.) carries out microstructure analysis to HP-Beta product.N
2as shown in Figure 4, curve shows as typical IV-type adsorption isothermal line to adsorption/desorption isothermal curve, shows that HP-Beta has micro-Jie's combined multi-stage pore property.Be 770m by calculating its BET specific surface area
2g
-1, outer surface area is 203m
2g
-1.As shown in Figure 5, mesoporous pore size, roughly between 3.3 ~ 30nm, concentrates near 9.2nm the BJH graph of pore diameter distribution of HP-Beta.
The above is only several case study on implementation of the present invention, and not do any pro forma restriction to the present invention, protection scope of the present invention is not limited thereto.
Claims (8)
1. a preparation method for monocrystalline multi-stage porous Beta molecular sieve, its step is as follows:
(1) inorganic alkali source, aluminium source are joined in the aqueous solution of micropore template, stir;
(2) in the solution of step (1), add METHYLPYRROLIDONE, stir;
(3) in the solution of step (2), add silicon source, stir;
(4) product step (3) obtained loads in reactor, airtight, thermostatic crystallization is carried out in spontaneous pressure, after crystallization, solid product is through centrifugal, washing, drying, organic formwork agent is removed in calcining in atmosphere, thus obtains the monocrystalline Beta molecular sieve with hierarchical porous structure;
Inorganic alkali source according to reason opinion generates M
2o gauge, aluminium source generates Al by theoretical
2o
3gauge, silicon source generates SiO by theoretical
2gauge, in above-mentioned reaction system, the mol ratio of each component is M
2o:Al
2o
3: SiO
2: H
2o:TEA
+: NMP=0.003 ~ 0.21:0.005 ~ 0.067:1:8.0 ~ 72.5:0.085 ~ 1.3:0.05 ~ 4.0, M represents K or Na.
2. the preparation method of a kind of monocrystalline multi-stage porous Beta molecular sieve as claimed in claim 1, is characterized in that: in above-mentioned reaction system, the mol ratio of each component is M
2o:Al
2o
3: SiO
2: H
2o:TEA
+: NMP=0.0063 ~ 0.1:0.0091 ~ 0.033:1:10.0 ~ 31.2:0.1 ~ 0.85:0.25 ~ 2.52.
3. the preparation method of a kind of monocrystalline multi-stage porous Beta molecular sieve as claimed in claim 1, it is characterized in that: in step (1), described inorganic alkali source is one or more in sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus.
4. the preparation method of a kind of monocrystalline multi-stage porous Beta molecular sieve as claimed in claim 1, it is characterized in that: in step (1), described aluminium source is one or more in sodium aluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate, pseudo-boehmite, aluminum oxide, aluminium hydroxide, aluminum acetate, aluminium carbonate, pure aluminum, aluminum isopropylate.
5. the preparation method of a kind of monocrystalline multi-stage porous Beta molecular sieve as claimed in claim 1, it is characterized in that: in step (1), described micropore template is one or more in tetraethyl ammonium hydroxide, tetraethylammonium bromide, etamon chloride, tetraethyl ammonium fluoride.
6. the preparation method of a kind of monocrystalline multi-stage porous Beta molecular sieve as claimed in claim 1, it is characterized in that: in step (3), described silicon source is one or more in white carbon black, water glass, silicon sol, silica gel, diatomite, tetraethoxy.
7. the preparation method of a kind of monocrystalline multi-stage porous Beta molecular sieve as claimed in claim 1, it is characterized in that: in step (4), described crystallization temperature is 100 ~ 200 DEG C, and crystallization time is 0.5 ~ 96h.
8. the preparation method of a kind of monocrystalline multi-stage porous Beta molecular sieve as claimed in claim 1, it is characterized in that: in step (4), described calcining temperature is 500 ~ 700 DEG C, and calcination time is 0.5 ~ 24h, and temperature rise rate is 0.2 ~ 5 DEG C of min
-1.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271287A (en) * | 2015-10-10 | 2016-01-27 | 吉林大学 | Method for preparation of Beta molecular sieve from modified diatomite without organic template |
| CN107020145A (en) * | 2016-01-29 | 2017-08-08 | 中国石油化工股份有限公司 | A kind of mesoporous IM-5 molecular sieves and preparation method |
| CN108217684A (en) * | 2018-02-11 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of method for promoting Beta Zeolite synthesis |
| CN108217675A (en) * | 2018-01-26 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of hollow monocrystalline Beta molecular sieves |
| CN109721078A (en) * | 2019-02-26 | 2019-05-07 | 吉林大学 | A method of mesopore molecular sieve is prepared without mesoporous template Direct Hydrothermal method in the system that mesoporous silicon oxide is silicon source presoma |
| CN110054200A (en) * | 2019-04-17 | 2019-07-26 | 中国科学院大连化学物理研究所 | A kind of preparation method of hollow Beta molecular sieve |
| CN112939008A (en) * | 2019-11-26 | 2021-06-11 | 中国科学院大连化学物理研究所 | Rapid synthesis method of Beta molecular sieve with controllable particle size |
| CN115872413A (en) * | 2022-12-14 | 2023-03-31 | 吉林大学 | Hierarchical pore molecular sieve and preparation method and application thereof |
| CN115893443A (en) * | 2022-11-09 | 2023-04-04 | 成都中科凯特科技有限公司 | Preparation method and application of multistage Kong molecular sieve |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271287A (en) * | 2015-10-10 | 2016-01-27 | 吉林大学 | Method for preparation of Beta molecular sieve from modified diatomite without organic template |
| CN107020145A (en) * | 2016-01-29 | 2017-08-08 | 中国石油化工股份有限公司 | A kind of mesoporous IM-5 molecular sieves and preparation method |
| CN108217675A (en) * | 2018-01-26 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of hollow monocrystalline Beta molecular sieves |
| WO2019144253A1 (en) * | 2018-01-26 | 2019-08-01 | 中国科学院大连化学物理研究所 | Preparation method for hollow single crystal beta molecular sieve |
| CN108217684A (en) * | 2018-02-11 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of method for promoting Beta Zeolite synthesis |
| CN109721078A (en) * | 2019-02-26 | 2019-05-07 | 吉林大学 | A method of mesopore molecular sieve is prepared without mesoporous template Direct Hydrothermal method in the system that mesoporous silicon oxide is silicon source presoma |
| CN110054200A (en) * | 2019-04-17 | 2019-07-26 | 中国科学院大连化学物理研究所 | A kind of preparation method of hollow Beta molecular sieve |
| CN112939008A (en) * | 2019-11-26 | 2021-06-11 | 中国科学院大连化学物理研究所 | Rapid synthesis method of Beta molecular sieve with controllable particle size |
| CN112939008B (en) * | 2019-11-26 | 2022-09-16 | 中国科学院大连化学物理研究所 | Rapid synthesis method of Beta molecular sieve with controllable particle size |
| CN115893443A (en) * | 2022-11-09 | 2023-04-04 | 成都中科凯特科技有限公司 | Preparation method and application of multistage Kong molecular sieve |
| CN115872413A (en) * | 2022-12-14 | 2023-03-31 | 吉林大学 | Hierarchical pore molecular sieve and preparation method and application thereof |
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