CN112239216B - Silicon-aluminum phosphate molecular sieve and preparation method thereof - Google Patents
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Abstract
The invention discloses a silicoaluminophosphate molecular sieve with a flower-ball-shaped structure and a preparation method thereof. The flower-spherical silicoaluminophosphate molecular sieve is a nano-sheet assembly, all nano-sheets are arranged outwards in a staggered mode, pore channels formed among the nano-sheets are opened on the outer surface of the molecular sieve, and the thickness of each nano-sheet is 15-25 nm. The molecular sieve has the characteristics of special crystal structure and novel appearance, and is suitable for the fields of catalysis, adsorption, separation and the like.
Description
Technical Field
The invention relates to a silicoaluminophosphate molecular sieve and a preparation method thereof, in particular to a flower-ball-shaped silicoaluminophosphate molecular sieve and a preparation method thereof.
Background
Silicoaluminophosphate molecular sieves (SAPO molecular sieves) were originally invented by Union Carbide Corporation (UCC) of the United states (Lok, B.M.; messina, C.A.; patton, R.L.; gajek, R.T.; cannan, T.R.; flanigen, E.M.J.Am. Chem.Soc.1984,106, 6092). The SAPO molecular sieve is made of AlO 4 、SiO 4 And PO 4 The tetrahedra form a three-dimensional crystal structure by sharing oxygen atoms, in which Si is present in the channels of the crystal 4+ Partially substituted P 5+ Or Al 3+ Producing acidity. SAPO series molecular sieves have good thermal and hydrothermal stability, moderate acidity, high specific surface area, and highly ordered microporous channels<20 nm) and cage structures, their pore channelsThe size of the molecular sieve is close to that of a plurality of alkane molecules, and the molecular sieve is widely applied to the modern petroleum processing industry, for example, SAPO-34 molecular sieve shows very good catalytic performance in Methanol To Olefin (MTO) reaction: the conversion rate of the methanol reaches 100 percent; ethylene and propylene selectivities can exceed 90% (Qiming Sun, ning Wang, guanqi Guo, xiaooxin Chen and Jihong Yu, J.Mater. Chem.A,2015,3,19783-19789 A.M.Prakash, martin Hartmann, and Larry Kevan, chem.Mater.1998,10,3, 932-941). Although much work has been done on the synthesis of SAPO molecular sieves, the existing SAPO molecular sieves and the synthesis strategies for SAPO molecular sieves still do not meet the increasing demands of the industry.
The synthesis of silicoaluminophosphate molecular sieves is generally carried out under hydrothermal conditions, although microwave methods (f.m. shalman, s.askari and r.haladj, rev.chem.eng.,2013,29, 99-122.) and xerogel conversion methods (s.askari, z.segighi and r.haladj, microporus mesophorus mater, 2014,197, 229-236.) and the like may also be used. The raw materials for synthesizing the silicoaluminophosphate molecular sieve generally comprise alumina, phosphoric acid, silica sol, organic amine or quaternary ammonium salt and other template agents. The synthesis of the silicoaluminophosphate molecular sieve is mostly synthesized in a weakly acidic medium, SAPO-5 and SAPO-34 type molecular sieves can be synthesized in a non-acidic medium, and the two molecular sieves have perfect crystal growth and high crystallinity, so that the synthesis method is convenient to research and widely apply. In the process of synthesizing the SAPO molecular sieve, the template also plays an important role, an amorphous phase or a compact phase crystal material is usually synthesized under the condition of no template, the template plays a role in crystal orientation in the synthesis process, and different templates have different influences on the formed framework structure (Liuli, zhangjun, gaoshuang and the like. The template plays a role in the synthesis of the SAPO-11 molecular sieve [ J ]. The chemical engineering and technological market, 2006,29 (3): 36-40.).
In view of the foregoing, there remains a great need and challenge for new SAPO molecular sieves and synthetic strategies for SAPO molecular sieves. In view of this, the development of a preparation route of the SAPO molecular sieve with a novel structure has important practical significance.
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 polymerization inhibitor is usually added to hinder the crystal growth from forming multilevel pores or nanocrystals, so that the appearance cannot be orderly controlled. In order to solve the technical problems, the invention provides a flower-ball-shaped silicoaluminophosphate molecular sieve and a preparation method thereof. The molecular sieve provided by the invention has the characteristics of special crystal structure and novel appearance.
The invention provides a flower-ball-shaped silicoaluminophosphate molecular sieve, which is a nano-sheet assembly, wherein nano sheets are outwards and staggered, pore channels formed among the nano sheets are opened on the outer surface of the molecular sieve, and the thickness of the nano sheets is 15-25 nm.
Further, the XRD diffraction pattern of the silicoaluminophosphate molecular sieve shows diffraction peaks at 2 θ, including: 7.62 +/-0.06, 10.61 +/-0.10, 14.72 +/-0.05, 15.29 +/-0.20, 18.37 +/-0.09, 20.21 +/-0.09, 21.57 +/-0.11, 23.07 +/-0.27, 24.23 +/-0.27, 26.36 +/-0.50, 28.94 +/-0.19, 29.69 +/-0.20, 30.59 +/-0.12, 34.48 +/-0.28 and 35.45 +/-0.22.
Further, the XRD diffraction pattern of the silicoaluminophosphate molecular sieve shows diffraction peaks at 2 θ, which also includes: 16.28 +/-0.14, 17.96 +/-0.13, 27.31 +/-0.37, 32.63 +/-0.47, 36.04 +/-0.21, 38.59 +/-0.11, 42.55 +/-0.34, 44.14 +/-0.33 and 45.53 +/-0.78.
Furthermore, in the silicoaluminophosphate molecular sieve, the length of a nanosheet is 500-1500 nm, and the width of the nanosheet is 100-1000 nm.
Furthermore, the external diameter of the silicoaluminophosphate molecular sieve is 1.5-5 μm.
The second aspect of the present invention provides a method for preparing a flower-ball-shaped silicoaluminophosphate molecular sieve, comprising the following steps:
crystallizing a mixture of an aluminum source, a phosphorus source, an alkali source, a silicon source, water and a structure directing agent;
wherein, the structure directing agent has the following structural general formula:
wherein n is an integer of 2 to 12, X - Is Cl - 、Br - Or I - 。
Further, the preparation method of the flower-ball-shaped silicoaluminophosphate molecular sieve can comprise the following specific processes: adding an aluminum source and a phosphorus source into water, and uniformly mixing; adding an alkali source into the mixture, and adjusting the pH value of the system to 7.5-9.5; then adding a structure directing agent into the mixture, uniformly mixing, then dropwise adding a silicon source, and uniformly mixing to obtain gel; and then crystallizing to obtain the flower-ball-shaped silicoaluminophosphate molecular sieve.
Further, the aluminum source is pseudo-boehmite; the silicon source is silica sol; the phosphorus source is phosphoric acid; the alkali source is ammonia water.
Further, the structure directing agent can be obtained by reacting triethylamine and linear alkane with two halogen atoms at two ends and 2-12 carbon atoms.
The preparation method of the structure directing agent can comprise the following steps: adding triethylamine and linear alkane with 2-12 carbon atoms and two halogen atoms at two ends into an organic solvent (such as acetonitrile), wherein the ratio of triethylamine: linear paraffin having 2 to 12 carbon atoms, each having one halogen atom at both ends: 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 structure directing agent; wherein, the drying condition can be as follows: drying for 1-5 hours at 20-50 ℃.
Further, said H 2 O：Al 2 O 3 ：H 3 PO 4 ：SiO 2 : the molar ratio of the structure directing agent is (40-100): 1: (0.5-3.5): (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 flower-ball-shaped silicoaluminophosphate molecular sieve is suitable for the fields of catalysis, adsorption, separation and the like, wherein the catalysis field can be the reaction for preparing olefin from oxygen-containing compounds.
Compared with the prior art, the invention has the following advantages:
1. the flower-ball-shaped silicoaluminophosphate molecular sieve has the characteristics of special crystal structure and novel appearance.
2. In the preparation method of the silicoaluminophosphate molecular sieve, a flower-ball-shaped silicoaluminophosphate molecular sieve is synthesized by adopting a specific structure directing agent and utilizing the cooperation effect of raw materials.
3. The preparation method of the flower-ball-shaped silicoaluminophosphate molecular sieve is simple, has low requirements on equipment and high product yield, and therefore, the flower-ball-shaped silicoaluminophosphate molecular sieve has a 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 a spherulitic silicoaluminophosphate molecular sieve A of example 1 of the present invention;
FIG. 3 is a scanning electron microscope photograph of a spherulitic silicoaluminophosphate molecular sieve A of example 1 of the present invention;
FIG. 4 is an XRD spectrum of a spherulitic silicoaluminophosphate molecular sieve B of example 2 of the present invention;
FIG. 5 is a scanning electron microscope photograph of a spherulitic silicoaluminophosphate molecular sieve B of example 2 of the present invention;
FIG. 6 is an XRD spectrum of a spherulitic silicoaluminophosphate molecular sieve C of example 3 of the present invention;
FIG. 7 is a scanning electron microscope photograph of a spherulitic silicoaluminophosphate molecular sieve C of example 3 of the present invention;
FIG. 8 is an XRD spectrum of the flower-ball-shaped silicoaluminophosphate molecular sieve D of example 4 of the present invention;
FIG. 9 is a scanning electron microscope photograph of a spherulitic silicoaluminophosphate molecular sieve D of example 4 of the present invention;
FIG. 10 is an XRD spectrum of the spherulitic silicoaluminophosphate molecular sieve E of example 5 of the present invention;
FIG. 11 is a scanning electron microscope photograph of a spherulitic silicoaluminophosphate molecular sieve E of example 5 of the present invention;
FIG. 12 is an XRD spectrum of material F of comparative example 1;
FIG. 13 is a scanning electron microscope photograph of comparative example 1, material F.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples.
In the method, XRD data is measured by adopting a German Bruker AXS D8 advanced X-ray diffractometer; SEM pictures were obtained from HITACHI S4800 field emission scanning electron microscope, japan.
Example 1
(1) Preparation of structure directing agent:
triethylamine and 1, 12-dibromododecane are added into acetonitrile and refluxed for 8 hours at 84 ℃; triethylamine: 1, 12-dibromododecane: 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 a 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 structure directing agent is shown in figure 1.
(2) Preparing a flower-ball-shaped silicoaluminophosphate 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 ammonia water with the mass concentration of 25-28% into the mixture, and stirring for 1.5 hours; wherein, the adding amount of ammonia water is that the pH value of the adjusting system is 8; then adding the synthesized structure directing 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 :SiO 2 The molar ratio of the structure directing agent is 70:1:2:0.4:0.3.
and crystallizing the finally obtained gel, and centrifuging, washing and drying the prepared sample. The crystallization temperature is 200 ℃, and the crystallization time is 2 days, thus obtaining the flower-shaped silicon aluminum phosphate molecular sieve A.
The XRD spectrogram of the flower-ball-shaped silicoaluminophosphate molecular sieve A is shown in figure 2, and as can be seen from figure 2, the synthesized silicoaluminophosphate molecular sieve has the peak shape of the SAPO molecular sieve, the diffraction peak is relatively sharp, the intensity is obvious, and the novel SAPO molecular sieve material is obtained.
The XRF results of the materials obtained in the table 1 are combined, so that Al, si and P exist in the materials at the same time, and the molar ratio is Al: si: p =1:0.1:1.1. therefore, the material provided by the invention is a flower-ball-shaped silicoaluminophosphate molecular sieve.
Table 1 example 1 XRF element molar ratio of flower-ball-shaped silicoaluminophosphate molecular sieves
| Al 2 O 3 | SiO 2 | P 2 O 5 | |
| Mole percent of | 43.6 | 8.6 | 47.7 |
FIG. 3 is a scanning picture of a silicoaluminophosphate molecular sieve. The figure shows that the morphology of the material presents a flower ball shape, the flower ball shape is formed by stacking nano sheets, and the thickness of the nano sheets can be seen to be about 20 nanometers from a high-power scanning picture.
Example 2
The preparation method is the same as example 1, except that H in example 2 2 O：Al 2 O 3 ：H 3 PO 4 ：SiO 2 : the molar ratio of the structure directing agent is 70:1:2:0.4:0.1, obtaining the flower-ball-shaped silicoaluminophosphate molecular sieve B. Wherein the XRD diffraction peak is shown in figure 4, and the scanning electron microscope picture is shown in figure 5. The thickness of the nano-sheet is about 20 nanometers as can be seen from a high-power scanning picture.
Example 3
The preparation process is the same as example 1, except that H in example 3 2 O:Al 2 O 3 :H 3 PO 4 :SiO 2 The molar ratio of the structure directing agent is 70:1:2:0.4:0.4, obtaining the flower-ball-shaped silicoaluminophosphate molecular sieve C. Wherein the XRD diffraction peak is shown in figure 6, and the scanning electron microscope picture is shown in figure 7. The thickness of the nanosheet is about 20 nm as can be seen from the high power scanning picture.
Example 4
The preparation process is the same as in example 1 except that 1, 12-dibromododecane in example 1 is replaced by 1, 2-dibromoethane. Obtaining the flower-ball-shaped silicoaluminophosphate molecular sieve D. Wherein the XRD diffraction peak is shown in figure 8, and the scanning electron microscope picture is shown in figure 9. From the high-power scanning picture, the thickness of the nano-sheet is about 15 nanometers.
Example 5
The preparation method is the same as that of example 1 except that 1, 12-dibromododecane in example 1 is replaced by 1, 4-dibromobutane. Obtaining the flower-ball-shaped silicoaluminophosphate molecular sieve E. Wherein the XRD diffraction peak is shown in figure 10, and the scanning electron microscope picture is shown in figure 11. The thickness of the nanosheet is about 20 nm as can be seen from the high power scanning picture.
Comparative example 1
The preparation method is the same as example 1, except that no structure-directing agent is added. A material F was obtained. Wherein the XRD diffraction peak is shown in figure 12, and the scanning electron microscope picture is shown in figure 13. The scanning pictures show that the synthesized material is irregular blocks, the size of the product is 5-20 microns, and no sheet is generated.
From XRD spectrogram, the target product of the invention can not be synthesized without adding the structure directing agent of the invention, and from the result of a scanning electron microscope, the appearance of the invention can not be obtained without adding the structure directing agent of the invention.
Claims (8)
1. A flower-ball-shaped silicoaluminophosphate molecular sieve is a nano-sheet assembly, all nano-sheets are arranged outwards in a staggered mode, pore channels formed among the nano-sheets are opened on the outer surface of the molecular sieve, and the thickness of each nano-sheet is 15-25 nm;
diffraction peaks appearing at 2 theta in the XRD diffraction pattern of the silicoaluminophosphate molecular sieve comprise: 7.62 +/-0.06, 10.61 +/-0.10, 14.72 +/-0.05, 15.29 +/-0.20, 18.37 +/-0.09, 20.21 +/-0.09, 21.57 +/-0.11, 23.07 +/-0.27, 24.23 +/-0.27, 26.36 +/-0.50, 28.94 +/-0.19, 29.69 +/-0.20, 30.59 +/-0.12, 34.48 +/-0.28 and 35.45 +/-0.22.
2. The flowered, spheroidal aluminophosphate molecular sieve of claim 1, wherein the silicoaluminophosphate molecular sieve has a diffraction pattern with diffraction peaks occurring at 2 Θ, further comprising: 16.28 plus or minus 0.14, 17.96 plus or minus 0.13, 27.31 plus or minus 0.37, 32.63 plus or minus 0.47, 36.04 plus or minus 0.21, 38.59 plus or minus 0.11, 42.55 plus or minus 0.34, 44.14 plus or minus 0.33 and 45.53 plus or minus 0.78.
3. The flower-ball-shaped silicoaluminophosphate molecular sieve of claim 1, wherein in the silicoaluminophosphate molecular sieve, the length of the nanosheet is 500-1500 nm, and the width is 100-1000 nm.
4. The flower ball shaped silicoaluminophosphate molecular sieve of claim 1, wherein the external diameter of the silicoaluminophosphate molecular sieve is 1.5 to 5 μm in the silicoaluminophosphate molecular sieve.
5. A method of making a flower-ball-shaped silicoaluminophosphate molecular sieve as claimed in any of claims 1 to 4, comprising the steps of:
crystallizing a mixture of an aluminum source, a phosphorus source, an alkali source, a silicon source, water and a structure directing agent;
wherein the structure directing agent has the following general structural formula:
wherein n is an integer of 2 to 12, X - Is Cl - 、Br - Or I - 。
6. The method of claim 5, wherein the aluminum source is pseudoboehmite; the silicon source is silica sol; the phosphorus source is phosphoric acid; the alkali source is ammonia water.
7. The method of claim 6, wherein H is 2 O：Al 2 O 3 ：H 3 PO 4 ：SiO 2 : the molar ratio of the structure directing agent is (40-100): 1: (0.5-3.5): (0.1-1.0): (0.1-0.4) wherein H 2 O is the total water content in the preparation process.
8. The method according to claim 5, 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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| CN104649288A (en) * | 2015-02-05 | 2015-05-27 | 烟台万润精细化工股份有限公司 | Nanosheet self-assembled SAPO-34 molecular sieve and preparation method thereof |
| CN104986780A (en) * | 2015-08-06 | 2015-10-21 | 青岛理健新材料科技有限公司 | Nanoscale sheet-SAPO-34 molecular sieve and synthetizing method thereof |
| CN106517229A (en) * | 2016-10-19 | 2017-03-22 | 浙江大学 | Method for preparing nanosheet-shaped SAPO-11 molecular sieve through hydrothermal synthesis method |
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