CN112239213B - SAPO-34 molecular sieve and preparation method thereof - Google Patents
SAPO-34 molecular sieve and preparation method thereof Download PDFInfo
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- CN112239213B CN112239213B CN201910641411.1A CN201910641411A CN112239213B CN 112239213 B CN112239213 B CN 112239213B CN 201910641411 A CN201910641411 A CN 201910641411A CN 112239213 B CN112239213 B CN 112239213B
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
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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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention discloses an ordered mesoporous SAPO-34 molecular sieve and a preparation method thereof. The SAPO-34 molecular sieve is in a similar cubic shape, a mesoporous structure penetrates through the whole crystal along the direction vertical to the similar cubic surface, and mesopores are arranged in a one-dimensional order in the similar cubic body. In the molecular sieve, mesopores are orderly arranged in a cubic body in one dimension, have a specific morphology structure, and are suitable for the fields of catalysis, adsorption, separation and the like.
Description
Technical Field
The invention relates to an SAPO-34 molecular sieve and a preparation method thereof, in particular to an ordered mesoporous SAPO-34 molecular sieve and a preparation method thereof.
Background
The zeolite material is made of AlO 4 、SiO 4 And PO 4 The three-dimensional crystal structure of tetrahedra formed by sharing oxygen atoms is classified as a microporous crystal because the pore diameters thereof are all less than 2 nm (m.moliner, c.martinez and a.corma, angelw.chem., int.ed.,2015,54, 3560-. The zeolite material is widely applied to industrial production and is a very important solid catalyst in the industrial production of the modern society, but the single microporous structure greatly limits the application range (J.Li, A.Corma and)J.Yu, chem.Soc.Rev.,2015, DOI 10.1039/C5CS 00023H; corma, chem.rev.,1997,97, 2373-2420; A.Corma, J.Catal.,2003,216, 298-. Inspired by ordered mesoporous materials, people propose to synthesize a hierarchical pore zeolite material to improve the mass transfer performance of the zeolite material in the catalysis process, and the improvement of the mass transfer performance can increase the diffusion of macromolecules in the catalysis process and improve the catalysis efficiency; meanwhile, the improvement of the mass transfer performance can reduce carbon deposition at the orifice, thereby improving the service life of the catalyst (L. -H.Chen, X. -Y.Li, J.C.Rooke, Y. -H.Zhang, X. -Y.Yang, Y.Tang, F. -S.X iao andB. -L.Su, J.Mater.chem.,2012,22, 17381-. To date, many strategies have been proposed for synthesizing hierarchical pore zeolitic materials, such as soft-template methods (m.choi, k.na, j.kim, y.sakamoto, t.osaamu and r.ryoo, Nature,2009,461,246.), hard-template methods (r.j.white, a.fischer, c.goebel and a.thomas, j.am.chem.soc.,2014,136, 2715-.
Silicoaluminophosphate zeolites are important members of the zeolite family, particularly the SAPO-34 molecular sieve materials thereof. The SAPO-34 molecular sieve has a CHA type crystal structure, and shows good catalytic performance (U.S. Olisbye, S.Svelle, M) in the aspect of preparing olefin (MTO) by methanol.
Beato, t.v.w.janssens, f.joensen, s.bordig and k.p.lillerud, angelw.chem., int.ed.,2012,51, 5810-. However, the eight-membered ring pores of SAPO-34 greatly limit the transport and diffusion of reactants, greatly shorten the life of the catalyst, and produce byproducts. Previous work demonstrated that the introduction of hierarchical pores in SAPO-34 molecular sieve materials can reduce coking and thereby greatly improve catalyst life (Qiming Sun, Ning Wang, Guanqi Guo, Xiaooxin Chen and Jihong Yu, J.Mater. chem.A,2015,3, 19783-.
Although many strategies have been proposed for synthesizing multi-stage pore SAPO-34, to date, ordered mesoporous SAPO-34 molecular sieves have not been synthesized. Until now, one has synthesized one-dimensionally ordered mesoporous MFI zeolites (m.choi, k.na, j.kim, y.sakamoto, t.osaamu and r.ryoo, Nature,2009,461,246.) and mesoporous two-dimensionally square arranged MFI zeolites (Xuefeng Shen, Wenting Mao, Yanhang Ma, Dongdong Xu, PengWu, Osamu teraki, dr.lu Han, Shunai Che, angew.chem.int.ed.2017,57,724-728.) using soft template method, but in most of the existing multi-stage pore SAPO-34 molecular sieves, the arrangement of the multi-stage pores is disordered, and the synthesis of ordered SAPO-34 materials remains a great challenge in the material science.
Disclosure of Invention
SAPO molecular sieves synthesized by the prior art have single structures, are mostly bulk crystals or have simple shapes. In addition, in the conventional preparation method, a pore-forming agent or a crystal growth inhibitor is usually added to prevent the crystal growth from forming hierarchical pores or nano crystals, and the hierarchical pore structure of the synthesized hierarchical pore SAPO-34 molecular sieve is disordered. In order to solve the technical problems, the invention provides an ordered mesoporous SAPO molecular sieve and a preparation method thereof. In the molecular sieve provided by the invention, mesopores are arranged in a one-dimensional order.
The invention provides an ordered mesoporous SAPO-34 molecular sieve, wherein the SAPO-34 molecular sieve is in a similar cubic shape, a mesoporous structure penetrates through the whole crystal along a direction vertical to a similar cubic surface, and mesopores are arranged in a one-dimensional order in the similar cubic body.
Further, the longest side length of the cubic-like body of the SAPO-34 molecular sieve is 2-15 mu m.
Further, the mesoporous size of the SAPO-34 molecular sieve is 2-5 nm.
The second aspect of the invention provides a preparation method of an ordered mesoporous SAPO-34 molecular sieve, which comprises the following steps:
crystallizing a mixture of an aluminum source, a phosphorus source, a silicon source, water, a crystal structure directing agent and a structure-assisting directing agent;
wherein the crystal structure directing agent is triethylamine;
wherein the auxiliary structure directing agent has the following structural general formula:
wherein n is an integer of 2 to 6, X - Is Cl - 、Br - Or I - 。
Further, the preparation method of the ordered mesoporous SAPO-34 molecular sieve can comprise the following specific processes: adding an aluminum source and a phosphorus source into water, and uniformly mixing; adding a crystal structure directing agent into the mixture, uniformly mixing, adding a structure-assisting directing agent, uniformly mixing, then dropwise adding a silicon source into the mixture, and uniformly mixing to obtain gel; and then carrying out crystallization treatment to obtain the ordered mesoporous SAPO-34 molecular sieve.
Further, the aluminum source is pseudo-boehmite; the silicon source is silica sol; the phosphorus source is phosphoric acid.
Further, the auxiliary structure guiding agent is obtained by reacting triethylamine and straight-chain alkane with two halogen atoms at two ends and 2-6 carbon atoms.
The preparation method of the auxiliary structure directing agent can comprise the following steps: adding triethylamine and straight-chain alkane with two halogen atoms at two ends and 2-6 carbon atoms into an organic solvent (such as acetonitrile), wherein the ratio of triethylamine: straight-chain alkane with two halogen atoms at two ends and 2-6 carbon atoms: the molar ratio of the organic solvent is (4-10): 1: (50-100) refluxing for 6-12 hours at 75-90 ℃; cooling the mixture, and removing the organic solvent to obtain a viscous substance; washing and drying the sticky matter to obtain the auxiliary structure directing agent; wherein, the drying conditions are as follows: drying for 1-5 hours at 20-50 ℃.
Further, said H 2 O：Al 2 O 3 ：H 3 PO 4 : crystal structure directing agent: SiO 2 2 : the molar ratio of the auxiliary structure guiding agent is (40-100): (0.5-2): (1.0-3.5): (2.5-4.7): (0.1-1.0): (0.1-0.4) wherein H 2 O is the total water content in the preparation process.
Further, the crystallization conditions were as follows: the crystallization temperature is 150-220 ℃, and the crystallization time is 1-4 days.
Further, the separation, washing and drying processes after crystallization can be carried out by conventional methods, for example, the separation can be carried out by centrifugal separation, the washing can be carried out by removing water, and the drying can be carried out in an oven.
The ordered mesoporous SAPO-34 molecular sieve is suitable for the fields of catalysis, adsorption, separation and the like, wherein the catalysis field can be a reaction for preparing olefin from an oxygen-containing compound.
Compared with the prior art, the invention has the following advantages:
1. the SAPO-34 molecular sieve provided by the invention is in a similar cubic shape, a mesoporous structure penetrates through the whole crystal along a direction vertical to a similar cubic surface, mesopores are arranged in a one-dimensional order in the similar cubic body, and the orifice shape of the mesopores is quadrilateral on the similar cubic surface and has a specific shape structure.
2. In the preparation method of the ordered mesoporous SAPO-34 molecular sieve, the ordered mesoporous SAPO-34 molecular sieve is synthesized by adopting a specific crystal structure guiding agent and a structure-assisting guiding agent and utilizing the coordination effect of the raw materials.
3. The preparation method of the ordered mesoporous SAPO-34 molecular sieve is simple, has low requirements on equipment and high product yield, so the method has good industrial application prospect.
Drawings
FIG. 1 is a structural formula of a structure-directing agent of the present invention;
FIG. 2 is an XRD spectrum of ordered mesoporous SAPO-34 molecular sieve A of example 1 of the invention;
FIG. 3 is a scanned graph of ordered mesoporous SAPO-34 molecular sieve A of example 1 of the present invention;
FIG. 4 is a transmission diagram of ordered mesoporous SAPO-34 molecular sieve A according to example 1 of the present invention;
FIG. 5 is an XRD spectrum of ordered mesoporous SAPO-34 molecular sieve B of example 2 of the invention;
FIG. 6 is a scanned graph of ordered mesoporous SAPO-34 molecular sieve B of example 2 of the invention;
FIG. 7 is an XRD spectrum of ordered mesoporous SAPO-34 molecular sieve C of example 3 of the invention;
FIG. 8 is a scanned graph of ordered mesoporous SAPO-34 molecular sieve C of example 3 of the invention;
FIG. 9 is an XRD spectrum of ordered mesoporous SAPO-34 molecular sieve D of comparative example 1;
FIG. 10 is a scan of ordered mesoporous SAPO-34 molecular sieve D of comparative example 1.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
In the method, XRD data is measured by a German Bruker AXS D8 advanced type X-ray diffractometer; SEM pictures were obtained from HITACHI S4800 field emission scanning electron microscope, Japan.
Example 1
(1) Preparing a structure-assisting directing agent:
adding triethylamine and 1, 4-dibromobutane into acetonitrile, and refluxing for 8 hours at 84 ℃; triethylamine: 1, 4-dibromobutane: acetonitrile (molar ratio) ═ 8: 1: 80; cooling the mixture and removing a large amount of acetonitrile to obtain a viscous substance; washing and drying the sticky matter to obtain the auxiliary structure directing agent; wherein the drying conditions are as follows: drying was carried out at 30 ℃ for 2 hours.
The molecular structure of the prepared co-structure directing agent is shown in figure 1.
(2) Preparation of ordered mesoporous SAPO-34 molecular sieve:
pseudo-boehmite (containing 70 weight percent of Al) 2 O 3 ) And phosphoric acid (containing 85 wt% H) 3 PO 4 ) Adding into water, stirring for 2 hours; then adding crystal structure directing agent triethylamine into the mixture, and stirring for 1.5 hours; then adding the synthesized auxiliary structure guiding agent into the obtained mixture, and stirring for 2 hours; then, a silica sol (containing 40% by weight of SiO) was added dropwise to the above mixture 2 ) Stirring for 2 hours to obtain gel; wherein H 2 O:Al 2 O 3 :H 3 PO 4 Triethylamine: SiO 2 2 The molar ratio of the auxiliary structure directing agent is 70: 1: 2: 4: 0.4: 0.1.
and crystallizing the finally obtained gel, and centrifuging, washing and drying the prepared sample. The crystallization temperature is 200 ℃, and the crystallization time is 3 days, thus obtaining the ordered mesoporous SAPO molecular sieve A.
The XRD spectrogram of the ordered mesoporous SAPO-34 molecular sieve A is shown in figure 2, and as can be seen from figure 2, the synthesized SAPO-34 molecular sieve has a better peak type, a sharper diffraction peak and an obvious intensity, and is obviously attached to the XRD spectrogram of SAPO-34, and no other crystals are generated on the XRD spectrogram.
As shown in FIG. 3, the material can be seen to have a cubic morphology from the scanning picture, and it can be seen from the high-power scanning picture that the SAPO-34 molecular sieve has a large number of mesopores on the surface, wherein the mesopores are quadrilateral pores.
As shown in fig. 4, is a selected area diffraction picture and a corresponding transmission electron microscope picture of the synthesized SAPO-34 molecular sieve with an ordered mesostructure. The picture a is a low-power transmission picture, and a large number of hierarchical pores exist on the bulk crystal, wherein mesopores are arranged in a one-dimensional order. From the corresponding selected area electron diffraction, the area is SAPO-34 crystals, diffraction points of mesostructure are simultaneously present in the electron diffraction picture except diffraction points of the crystal structure (marked by white arrows), and the diffraction points of the mesostructure are orderly generated by the mesostructure, which indicates that the mesostructure is arranged along the diffraction points of the mesostructure and is consistent with the transmission electron microscope picture.
Example 2
The preparation is identical to example 1, except that 1, 4-dibromobutane in example 1 is replaced by 1, 2-dibromoethane. Obtaining the ordered mesoporous SAPO-34 molecular sieve B. Wherein the XRD diffraction peak is shown in figure 5, and the scanning electron microscope picture is shown in figure 6. The cubic morphology of the synthesized material can be seen from the scanning picture, and the mesostructure exists in the product.
Example 3
The preparation method is the same as that of example 1, except that 1, 4-dibromobutane in example 1 is replaced by 1, 6-dibromohexane. Obtaining the ordered mesoporous SAPO-34 molecular sieve C. Wherein the XRD diffraction peak is shown in figure 7, and the scanning electron microscope picture is shown in figure 8. The cubic morphology of the synthesized material can be seen from the scanning picture, and the mesostructure exists in the product.
Comparative example 1
The preparation method is the same as example 1, except that no structure-directing agent is added, and a material D is obtained. Wherein the XRD diffraction peak is shown in figure 9, and the scanning electron microscope picture is shown in figure 10. The scanning picture can show the cubic morphology of the synthesized material, and the product has no multilevel pores.
It can be seen from the XRD spectrum that the mesostructure of the invention can not be synthesized and the appearance of the invention can not be obtained without adding the auxiliary structure directing agent of the invention.
Claims (7)
1. The ordered mesoporous SAPO-34 molecular sieve is in a similar cubic shape, a mesoporous structure penetrates through the whole crystal along the direction vertical to the surface of the similar cubic body, and mesopores are arranged in a one-dimensional order in the similar cubic body.
2. The ordered mesoporous SAPO-34 molecular sieve of claim 1, wherein the cuboid-like shape of the SAPO-34 molecular sieve has a longest side length of 2-15 μm.
3. The ordered mesoporous SAPO-34 molecular sieve of claim 1, wherein the SAPO-34 molecular sieve has a mesoporous size of 2-5 nm.
4. A preparation method of an ordered mesoporous SAPO-34 molecular sieve comprises the following steps:
adding an aluminum source and a phosphorus source into water, and uniformly stirring; adding a crystal structure directing agent into the mixture, adding a structure-assisting directing agent after uniformly stirring, dropwise adding a silicon source into the mixture after uniformly stirring, and stirring to obtain gel; then, carrying out crystallization treatment to obtain the ordered mesoporous SAPO-34 molecular sieve;
wherein the crystal structure directing agent is triethylamine;
wherein the auxiliary structure directing agent has the following structural general formula:
wherein n is an integer of 2 to 6, X - Is Cl - 、Br - Or I - 。
5. The method of claim 4, wherein the aluminum source is pseudoboehmite; the silicon source is silica sol; the phosphorus source is phosphoric acid.
6. The method of claim 5, wherein H is 2 O：Al 2 O 3 ：H 3 PO 4 : crystal structure directing agent: SiO 2 2 : the molar ratio of the auxiliary structure guiding agent is (40-100): (0.5-2): (1.0-3.5): (2.5-4.7): (0.1-1.0): (0.1 to 0.4) wherein H 2 O is the total water content in the preparation process.
7. The method according to claim 4, wherein the crystallization conditions are as follows: the crystallization temperature is 150-220 ℃, and the crystallization time is 1-4 days.
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