CN111099634B - SCM-21 metal phosphoaluminate and preparation method thereof - Google Patents

SCM-21 metal phosphoaluminate and preparation method thereof Download PDF

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CN111099634B
CN111099634B CN201811248435.2A CN201811248435A CN111099634B CN 111099634 B CN111099634 B CN 111099634B CN 201811248435 A CN201811248435 A CN 201811248435A CN 111099634 B CN111099634 B CN 111099634B
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袁志庆
付文华
滕加伟
乔健
赵胜利
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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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Abstract

The invention relates to a novel SCM-21 metal aluminophosphate and a preparation method thereof, wherein a skeleton of the metal aluminophosphate has the following composition in molar ratio: (M)xAlyPz)O2Wherein M is one of zinc, cobalt and magnesium, x is more than or equal to 0.01 and less than or equal to 0.6, z is more than or equal to 0.2 and less than or equal to 0.6, and x + y + z is equal to 1. The metal phosphoaluminate has a unique X-ray diffraction pattern, and can be used as an adsorbent, a catalyst or a catalyst carrier.

Description

SCM-21 metal phosphoaluminate and preparation method thereof
Technical Field
The invention relates to a metal phosphoaluminate and a preparation method thereof.
Background
Most metalloaluminophosphates belong to one of a large family of molecular sieves. Molecular sieves are a porous crystalline material, and the currently discovered molecular sieves with known structures are more than 230, and molecular sieves with new structures are still emerging. Most molecular sieves have large internal specific surface areas and open internal spaces that serve both as sites for reactions to occur and to hold guest molecules such as metals, metal oxides, organic molecules, water molecules, and the like. The molecular sieve has uniform and regular pore channels, and the size of the pore channels is in the same order of magnitude as that of molecules, so that the entrance and exit of the molecules can be selected, and the shape-selective effect is obtained. Because of the above characteristics, molecular sieves are widely used as catalysts, carriers of catalysts, adsorbents, detergents and the like, and are widely applied in the fields of petrochemical industry, environmental protection, adsorption and separation. The framework of molecular sieves is generally composed of coordinating Tetrahedra (TO)4) Connected by common vertices (typically oxygen atoms), and for zeolitic molecular sieves the tetrahedra in the framework predominateIs SiO4Tetrahedron and AlO4 -The tetrahedra being replaced by other tetrahedra to form a plurality of molecular sieves of various framework structures or of various framework compositions, e.g. AlO4 -The tetrahedron may be GaO4 -Or ZnO4 2-Tetrahedron substitution, thereby reacting with SiO4The tetrahedron together form the framework of the heteroatom molecular sieve, and Ge and Si have similar coordination property, and Ge can also form a tetrahedron coordination structure, and GeO is adopted4And SiO4The linkages of (a) can form a large number of novel germanium-containing molecular sieve structures.
If SiO4Tetrahedral PO4 +The tetrahedra are substituted to form another large class of molecular sieve family, the aluminophosphate molecular sieves, also known as aluminophosphates, which have a framework which is crossed by AlO4 -And PO4 +The oxygen atoms are linked, so that the whole molecular sieve skeleton is electrically neutral. Of course, like zeolitic molecular sieves, the aluminoxy tetrahedra or the phosphoxy tetrahedra of the aluminophosphate molecular sieve can also be replaced by other tetrahedra, the most common of which are the silicon-oxy tetrahedra and the zinc-oxy tetrahedra, which, due to the introduction of these tetrahedra, give the aluminophosphate type molecular sieve new characteristics. The artificial synthesis of aluminophosphate molecular sieves is studied later than zeolite molecular sieves. In 1971, Flanigen et al reported synthesis of aluminum phosphate Molecular sieves [ Molecular Sieve Zeolites-I, ACS, Washingtom D.C ], and under hydrothermal synthesis conditions, mixing oxides of aluminum, silicon and phosphorus to obtain silicoaluminophosphate Molecular sieves having the same crystal structures as analcime, chabazite, phillips-harmome, L-type Molecular Sieve, A-type Molecular Sieve and B-type Molecular Sieve, wherein the phosphorus content is 5-25% (in terms of P-type Molecular Sieve, etc.)2O5Meter), but no structure was found to be distinct from the zeolitic molecular sieve. 1982, U.S. Pat. No. 4310440, which uses organic amine or quaternary ammonium compound as template agent, hydrothermally synthesizes a series of aluminum phosphate molecular sieves, which include: AlPO4-5,AlPO4-8,AlPO4-9,AlPO4-11,AlPO4-12,AlPO4-14,AlPO4-16,AlPO4-17,AlPO4-18,AlPO4-20,AlPO4-21,AlPO4-22,AlPO4-23,AlPO4-25,AlPO4-26,AlPO4-28,AlPO431, the type of organic template is one of the key factors for determining the structure of the aluminophosphate molecular sieve, and so far, organic amine is the most widely used template in the synthesis of the aluminophosphate molecular sieve. Compared with a silicon-aluminum zeolite molecular sieve, the industrial application of the phosphorus-aluminum molecular sieve is rare, and only the SAPO-34 molecular sieve and the SAPO-11 molecular sieve are industrially applied at present. Recently published articles [ Science,2016,351,1065-1068 ] disclose that SAPO molecular sieves can be applied to a part of coupled catalysts in reactions for preparing olefins from synthesis gas, so as to obtain better catalytic effect, and in addition, potential applications of the aluminum phosphate molecular sieves also include that the aluminum phosphate molecular sieves are used as adsorbents or good carriers of catalysts.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel metal phosphoaluminate and a synthetic method thereof, which are not related in the prior art.
In order to solve the technical problems, the invention provides SCM-21 metal aluminophosphate, wherein the skeleton of the aluminophosphate has the following composition in molar ratio: (M)xAlyPz)O2Wherein M is at least one of Zn, Co and Mg, X is 0.01-0.6, z is 0.2-0.6, and X + y + z is 1, the above aluminophosphate has the following X-ray diffraction data:
Figure BDA0001841086010000021
Figure BDA0001841086010000031
the preferable molar ratio of the skeleton of the metal aluminophosphate is as follows: (M)xAlyPz)O2X is more than or equal to 0.01 and less than or equal to 0.4, z is more than or equal to 0.4 and less than or equal to 0.6, and x + y + z is equal to 1. Preferably, wherein M is zinc.
The preparation method of the SCM-21 metalloaluminophosphate comprises the following steps:
a) mixing transition metal compound, aluminum source, phosphorus source, organic matter R and water according to (0.01-0.6) MO2O3:；
(1.0～3.0)P2O5:(3.6～6.0)R:(50～500)H2Mixing the O in proportion to obtain a synthetic mother solution;
b) putting the synthetic mother liquor into a closed reaction container for crystallization;
c) washing and drying the product obtained in the step b) to obtain SCM-21 metal phosphoaluminate;
wherein the organic matter R is double quaternary ammonium base.
In the above technical scheme, preferably, the metal compound, the aluminum source, the phosphorus source, the organic matter R and the water are (0.01-0.4) MO (Al)2O3:(1.0～3.0)P2O5:(3.6～4.8)R:(50～500)H2And uniformly mixing the O in proportion to obtain the synthetic mother liquor.
In the above technical solution, preferably, the transition metal compound is a metal salt of zinc, cobalt, magnesium or a combination thereof, and more preferably, the transition metal compound has a relatively large soluble zinc salt, cobalt salt and magnesium salt, which include zinc nitrate, zinc sulfate, zinc chloride, zinc acetate, cobalt nitrate, cobalt acetate, magnesium chloride, magnesium sulfate, and the like.
In the above technical solution, preferably, the aluminum source is at least one of pseudoboehmite, aluminum isopropoxide or aluminum sol, and more preferably at least one of pseudoboehmite or isopropanol.
In the above technical solution, preferably, the phosphorus source is one or more selected from phosphoric acid, phosphorous acid or phosphorus pentoxide.
In the above technical solution, preferably, the organic matter R mainly plays a role in structure guidance in the system, and the organic matter R is N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide, and its chemical structural formula is represented as:
Figure BDA0001841086010000032
in the above technical solution, preferably, the above synthesis mother liquor is crystallized in a closed reaction vessel, which generally has an inner wall made of stainless steel, and more preferably an inner wall lined with polytetrafluoroethylene, so as to prevent the wall from polluting the reaction system.
In the technical scheme, preferably, the reaction pressure is the autogenous pressure of the system, the crystallization temperature is 150-185 ℃, the crystallization time is 48-160 hours, and the more preferable crystallization temperature and crystallization conditions are 150-170 ℃ and 60-120 hours respectively.
The SCM-21 metal aluminophosphate synthesized by the steps contains a certain amount of residual organic compounds, the residual organic compounds can be removed by a heat treatment method under an air atmosphere, and in order to keep the stability of the aluminophosphate structure to the maximum extent, special methods such as a heat treatment method adopting ozone as an oxidant or an organic solvent extraction method can be adopted.
The metal phosphorus aluminum molecular sieve obtained after the treatment of the organic template agent has an open pore system, can be used as an adsorbent, can also be used as a carrier of a catalyst or a solid acid catalyst taking Lewis acid catalysis as a main body.
The invention provides SCM-21 metal phosphoaluminate, which is directionally obtained by simultaneously controlling the feeding ratio among reaction raw materials under the combined action of a metal compound, an aluminum source, a phosphorus source and an organic matter R.
Drawings
FIG. 1 is an XRD pattern of the SCM-21 metalloaluminophosphate molecular sieve obtained in example 1.
The invention is further illustrated by the following examples, which do not limit the scope of the invention.
Detailed Description
[ example 1 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.17 g of zinc acetate while stirring, then slowly dropwise adding 2.30 g of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.12ZnO:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the above synthetic mother liquor in a sealed reaction container at 150 deg.C for 60 hr, washing and drying the crystallized product to obtain metal aluminophosphate with XRD pattern shown in figure 1, and skeleton composition of the obtained aluminophosphate is Zn0.04Al0.46P0.5O2。
[ example 2]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide solution, adding 0.43 g of aluminum isopropoxide and 0.17 g of zinc acetate while stirring, then slowly dropwise adding 2.30 g of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.12ZnO:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 160 deg.C for 60 hr, washing and drying the crystallized product to obtain metal aluminophosphate with skeleton Zn0.04Al0.46P0.5O2。
[ example 3 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide solution, adding 0.43 g of aluminum isopropoxide solution while stirring, adding 0.698 g of pseudo-boehmite and 0.17 g of zinc acetate while stirring, slowly dropwise adding 2.30 g of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.12ZnO:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the above synthetic mother liquor in a closed reaction container at 170 deg.C for 60 hr, washing and drying the crystallized product to obtain metal aluminophosphate with skeleton Zn0.04Al0.46P0.5O2。
[ example 4 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide solution, adding 0.43 g of aluminum isopropoxide and 0.17 g of zinc acetate while stirring, then slowly dropwise adding 2.30 g of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.12ZnO:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 140 deg.C for 60 hr, washing and drying the crystallized product to obtain metal aluminophosphate with skeleton Zn0.04Al0.46P0.5O2。
[ example 5 ]
Weighing 22 g of 16.31 mass percent ammonium hydroxide solution of N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane), adding 0.43 g of aluminum isopropoxide and 0.34 g of zinc acetate while stirring, then slowly dropwise adding 2.30 g of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.25ZnO:1.0Al2O3:2.4P2O5:4.8R:190H2O
putting the synthetic mother liquor in a containerCrystallizing in a closed reaction container at 160 deg.C for 60 hr, washing and drying to obtain metal aluminophosphate with Zn skeleton0.08Al0.42P0.5O2。
[ example 6 ]
Weighing 22 g of 16.31 mass percent ammonium hydroxide solution of N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane), adding 0.43 g of aluminum isopropoxide and 0.57 g of zinc acetate while stirring, then slowly dropwise adding 2.30 g of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.40ZnO:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 160 deg.C for 60 hr, washing and drying the crystallized product to obtain metal aluminophosphate with skeleton Zn0.13Al0.37P0.5O2。
[ example 7 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide solution, adding 0.43 g of aluminum isopropoxide and 0.71 g of zinc acetate while stirring, then slowly dropwise adding 2.30 g of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.50ZnO:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 160 deg.C for 60 hr, washing and drying the crystallized product to obtain metal aluminophosphate with skeleton Zn0.15Al0.35P0.5O2。
[ example 8 ]
27.51 g of 16.31% by weight of N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide solution are weighed, 0.43 g of aluminum isopropoxide and 0.17 g of zinc acetate are added while stirring, 2.30 g of 85% phosphoric acid solution is slowly added dropwise, and the mixture is stirred uniformly to obtain a synthetic mother liquor with the following molar ratio:
0.12ZnO:1.0Al2O3:2.4P2O5:6.0R:570H2O
crystallizing the synthetic mother liquor in a closed reaction container at 160 deg.C for 60 hr, washing and drying the crystallized product to obtain metal aluminophosphate with skeleton Zn0.04Al0.46P0.5O2。
[ example 9 ]
27.51 g of 16.31% by weight of N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide solution are weighed, 0.43 g of aluminum isopropoxide and 0.17 g of zinc acetate are added while stirring, 2.30 g of 85% phosphoric acid solution is slowly added dropwise, and the mixture is stirred uniformly to obtain a synthetic mother liquor with the following molar ratio:
0.12ZnO:1.0Al2O3:2.4P2O5:6.0R:570H2O
crystallizing the synthetic mother liquor in a closed reaction container at 150 deg.C for 80 hr, washing and drying the crystallized product to obtain metal aluminophosphate with skeleton Zn0.05Al0.45P0.5O2。
[ example 10 ]
Weighing 16.5 g of 16.31 percent by mass of N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide solution, adding 0.43 g of aluminum isopropoxide and 0.17 g of zinc acetate while stirring, then slowly dropwise adding 2.30 g of 85 percent phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.12ZnO:1.0Al2O3:2.4P2O5:3.6R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 160 deg.C for 60 hr, washing and drying the crystallized product to obtain metal aluminophosphate with skeleton Zn0.04Al0.46P0.5O2。

Claims (8)

1. An SCM-21 metalloaluminophosphate, the skeleton of which has a composition in terms of mole ratios as follows: (M)xAlyPz)O2Wherein M is at least one of Zn, Co and Mg, X is 0.01-0.6, z is 0.2-0.6, and X + y + z is 1, the above aluminophosphate has the following X-ray diffraction data:
Figure FDA0003055558810000011
2. the SCM-21 metalloaluminophosphate according to claim 1, wherein the metalloaluminophosphate has a composition with a framework having the following molar ratio: (M)xAlyPz)O2Wherein M is at least one of zinc, cobalt and magnesium, x is more than or equal to 0.01 and less than or equal to 0.4, z is more than or equal to 0.4 and less than or equal to 0.6, and x + y + z is 1.
3. The SCM-21 metalloaluminophosphate according to claim 1, wherein M is zinc.
4. The method of preparing SCM-21 metalloaluminophosphate according to claim 1, comprising the steps of:
a) the metal salt is calculated as MO, and the aluminum source is calculated as Al2O3In terms of phosphorus source, P2O5Metering organic matterR and water according to (0.01-0.6) MO: Al2O3:(1.0～3.0)P2O5:(3.6～6.0)R:(50～500)H2Uniformly mixing the molar ratio of O to obtain a synthetic mother liquor;
b) putting the synthetic mother liquor into a closed reaction container for crystallization;
c) washing and drying the product obtained in the step b) to obtain SCM-21 metal phosphoaluminate;
wherein the organic matter R is N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide;
wherein the crystallization temperature is 150-185 ℃, and the crystallization time is 48-160 hours.
5. The method for preparing SCM-21 metallophosphoaluminates according to claim 4, characterized in that the metal salt is calculated as MO and the aluminum source is calculated as Al2O3In terms of phosphorus source, P2O5Calculated by the ratio of (0.01-0.4) MO to Al of the organic matter R and water2O3:(1.0～3.0)P2O5:(3.6～4.8)R:(50～500)H2And (4) uniformly mixing the molar ratio of O to obtain the synthetic mother liquor.
6. The method of preparing SCM-21 metalloaluminophosphate according to claim 4, wherein the aluminium source is at least one of pseudoboehmite, aluminium isopropoxide or an aluminium sol.
7. The method of claim 4, wherein the metal salt is at least one soluble metal salt of zinc, cobalt, or magnesium.
8. The method of claim 4, wherein the phosphorus source is selected from one or more of phosphoric acid, phosphorous acid, or phosphorous pentoxide.
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CN101491773A (en) * 2008-01-25 2009-07-29 北京石油化工学院 MCM-41 molecular sieve catalyst containing phosphor aluminum structure unit, preparation method and use thereof
CN104891527A (en) * 2015-05-28 2015-09-09 山西大同大学 Method for synthesizing mordenite
CN106809860A (en) * 2015-11-27 2017-06-09 中国科学院大连化学物理研究所 A kind of ion process for thermosynthesizing of ATS types Metal-aluminophosphate Molecular Siever
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