CN108217685B - Preforming synthesis method of heteroatom metal aluminum phosphate molecular sieve with AFO structure - Google Patents
Preforming synthesis method of heteroatom metal aluminum phosphate molecular sieve with AFO structure Download PDFInfo
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Abstract
A pre-forming synthesis method of a heteroatom metal aluminum phosphate molecular sieve with an AFO structure belongs to the technical field of catalyst preparation. The method comprises the steps of mixing an aluminum source, a phosphorus source, a metal source, a fluorine source, organic amine, ionic liquid and water in proportion to prepare gel, then processing and molding the obtained gel according to an expected shape, and crystallizing the molded gel under certain conditions to obtain a molded body completely composed of a molecular sieve. The formed AFO type heteroatom metal aluminum phosphate molecular sieve prepared by one step can be directly used as a catalyst carrier or an adsorbent, and the preparation process of the catalyst or the adsorbent is simplified. Compared with the traditional method, the method has the advantages of simple preparation process, high utilization rate of raw materials, low discharge amount of waste liquid and wide application prospect.
Description
Technical Field
The invention relates to the technical field of molecular sieve preparation, and provides a pre-forming synthesis method of a heteroatom metal aluminum phosphate molecular sieve with an AFO structure.
Background
A heteroatomic metalloaluminophosphate molecular sieve with AFO structure (Atlas of Zeolite Framework Types,6th ed., Elsevier, Amsterdam, 2017; http:// www.izo-structure. org/databases /) has one-dimensional oval 10-membered ring straight channels with a pore size of 0.43nm x 0.70 nm. Because the pore structure size and the geometric configuration of the molecular sieve are very favorable for forming the single-branch paraffin hydrocarbon isomer, the Pt-Pd/AFO silicon aluminum phosphate molecular sieve loaded with the platinum-palladium noble metal shows good catalytic activity and selectivity in the isomerization reaction of straight-chain paraffin hydrocarbon.
In 1984, Flanigen et al for the first time disclosed the synthesis of AFO structure silicoaluminophosphate molecular sieves in the patents US4, 440, 871, however, it was difficult to obtain pure phase AFO structure molecular sieves during the synthesis process, and heterogeneous phases such as AEL and ATO structure silicoaluminophosphate, etc. often appeared in the products. Many methods for the synthesis or modification of AFO-structured silicoaluminophosphate molecular sieves have since emerged (J.Catal.,1997,169, 55-66; Microporous Mesoporous Mater.,1998,26, 161-173; CN 1448336A; CN 1456502A; CN 1194890C; CN 1541942A; CN 1923688A).
The method adopts a hydrothermal synthesis method to prepare the molecular sieve powder, the method takes water as a solvent, the materials are mixed according to a certain proportion to prepare sol, the sol is crystallized at 80-200 ℃ under the autogenous pressure of the water, and after the crystallization is finished, the product is filtered, washed and dried to obtain the molecular sieve powder. The formation of the adsorbent and the catalyst requires that the molecular sieve powder is mixed with additives such as a binder, a plasticizer, an extrusion aid, a pore-forming agent and the like to obtain a plastomer, and then the plastomer is kneaded, formed, cured, dried and roasted to obtain a finished product.
The method firstly prepares the molecular sieve powder, then mixes the molecular sieve powder with additives such as a binder and the like to form, dries and calcines the molecular sieve powder to prepare the finished products of the catalyst and the adsorbent, and has long process flow and complex process. In addition, the hydrothermal crystallization process of the molecular sieve is carried out under high pressure, so that potential safety hazards exist; a large amount of waste water is generated in the process of filtering and washing the powder, so that the environmental pollution is caused; due to the introduction of the binder, the content of the molecular sieve in the finished product of the molecular sieve catalyst and the adsorbent is generally 60-80%, which cannot reach 100%, and the performance of the molecular sieve is influenced.
In order to solve the above problems, many researches are made on simplifying the preparation process of the molecular sieve catalyst and the adsorbent and improving the content of the molecular sieve in the formed body.
The raw material with a certain shape is used instead of powder, so that the preparation process of the molecular sieve catalyst and the adsorbent can be simplified.
For example, as SiO by Sachse et al2The monolithic material is used as a raw material to prepare the formed ZSM-5 catalyst. The method is to mix SiO2The monolithic material is arranged at a molar ratio of SiO2:NaOH:NaAlO2:TPAOH:H2Crystallization at 150 ℃ for 24 h in a solution of O =1:0.15:0.09:0.004:33 gives a shaped catalyst (Micropor. meso. Mater., 2011, 140(1-3): 58-68). The method adopts SiO2The whole material is used as a silicon source for molecular sieve synthesis, the crystallization process keeps solid phase, but the aluminum source NaAlO2And other raw materials still exist in the aqueous solution, and the crystallization is still a hydrothermal process. Although the finished molecular sieve product keeps the shape of the whole material, the reaction process is limited by mass transfer because the reaction raw materials are divided into a solid phase and a liquid phase, crystallization cannot be complete, and the content of ZSM-5 in the finished product is only 38%.
Barg, S. et al prepared a shaped X-type molecular sieve adsorbent from a foamed aluminum monolith. The method comprises the steps of treating a foamed aluminum integral material for 2 hours at 820 ℃ in an air atmosphere to convert partial Al into Al3O2Then placing it at a molar ratio of Na2O:K2O:SiO2:H2Crystallizing at 80 deg.C in solution of O =70:20:10:1500 to obtain shaped adsorbent comprising X-type molecular sieve and Al2O3Formed (J. ports Mat., 2011, 18(1): 89-98).
The method crystallizes partial raw materials in the form of integral materials under the hydrothermal condition, and prepares the integral catalyst and the adsorbent in one step, thereby simplifying the preparation process. But other raw materials still exist in the aqueous solution, and the crystallization is still a hydrothermal process, so that potential safety hazards exist; the reaction raw material is divided into solid and liquid phases, the reaction process is limited by mass transfer, and the finished product contains unconverted raw material and has low molecular sieve content. In addition, the methods adopt raw materials with overall material shapes, are limited by the materials of the raw materials, and have single shapes. The actual finished products of the existing molded catalyst and adsorbent have rich shapes, including spherical, strip-shaped, cylindrical, honeycomb-shaped, clover-shaped, external gear-shaped, nonporous external gear-shaped, plum blossom-shaped, porous plum blossom-shaped, seven-hole spherical, nonporous spherical, seven-rib wheel-shaped, four-hole-shaped, four-leaf butterfly-shaped and the like.
In order to increase the molecular sieve content in the finished molecular sieve catalyst and adsorbent products, researchers have done a lot of work to crystallize the additives such as the binder added during the molding process into the molecular sieve.
For example, patent CN1105906A discloses a method for preparing a zeolite catalyst. The method comprises the steps of mixing ZSM-5 powder and a silicon dioxide binder, forming, carrying out hydrothermal treatment in organic amine or organic quaternary ammonium alkali aqueous solution or steam to obtain an integrated molecular sieve, and roasting to obtain a catalyst finished product.
Patent CN1915820A discloses a preparation method of a small-grained zeolite catalyst. The method comprises the steps of mixing and molding molecular sieve seed crystals, a silicon source and a binder, then carrying out gas-solid phase treatment on the molecular sieve seed crystals and organic amine and water vapor to convert the molecular sieve seed crystals into an integrated molecular sieve, and roasting the molecular sieve seed crystals to obtain a catalyst finished product.
The method is used for recrystallizing the formed body prepared by mixing the molecular sieve powder and the binder to convert the binder into the molecular sieve. Although the method can obtain a formed body completely composed of the molecular sieve, the method still needs to synthesize the molecular sieve raw powder; the molding process adds a crystallization step and increases the manufacturing cost.
The invention provides a complete molecular sieve preforming synthesis method, which can simultaneously achieve the aims of simplifying the preparation process of a molecular sieve catalyst and an adsorbent and improving the content of the molecular sieve in a formed body. The invention particularly provides a preformed synthesis method aiming at a heteroatom metal aluminum phosphate molecular sieve with an AFO structure.
Disclosure of Invention
The invention aims to simplify the process flow of preparing molecular sieve catalysts and adsorbents, directly prepare pure molecular sieve materials with expected shapes and provide a pre-forming synthesis method of heteroatom metal aluminum phosphate molecular sieves with AFO structures.
The scheme for solving the technical problems is as follows:
a method for synthesizing a heteroatomic metalloaluminophosphate molecular sieve having an AFO structure identified by the International Zeolite Association, comprising: the synthetic gel is processed and molded according to the expected shape, and then is directly crystallized to obtain the molded molecular sieve with the shape consistent with the shape of the molded gel, which comprises the following steps,
(1) mixing an aluminum source, a phosphorus source, a metal source, a fluorine source, an organic amine, an ionic liquid and water according to the proportion of Al2O3:P2O5:MeO:F-Organic amine, ionic liquid, H2O =1: 0.2-5: 0.002-6: 0.01-9: 0.01-10: 0.005-5: 2-100, and mixing to obtain gel,
(2) processing the gel obtained in step (1) into a formed gel with a desired shape, properly aging the gel or treating the gel at a temperature of not more than 110 ℃, removing a part of water in the gel to obtain a plastic solid, and then forming and processing.
(3) And (3) placing the formed gel prepared in the step (2) in a closed container, and crystallizing at 100-260 ℃ for 10 min-10 d to obtain the formed molecular sieve with the AFO topological structure.
The preparation method of the gel adopts the conventional operation method in the field, for example, under the conditions of certain temperature and strong stirring, the aluminum source, the phosphorus source, the metal source, the fluorine source, the organic amine and the ionic liquid are added into deionized water according to a certain proportion and mixed to obtain the uniformly mixed aqueous gel containing the aluminum source, the phosphorus source, the metal source, the fluorine source, the organic amine and the ionic liquid.
The gel forming according to the present invention is a conventional operation in the art, such as strip extrusion, compression molding, oil column molding, rotational molding, spray molding, granulation, and the shape of the formed gel may be spherical, strip, cylindrical, honeycomb, clover, external gear without holes, quincunx, porous quincunx, seven-hole spherical, non-hole spherical, seven-ribbed wheel, four-hole, four-leaf butterfly, etc. The specific adopted shape and size are selected and determined according to the requirements of actual use conditions. The gel of the invention can be pretreated in a certain form before the molding operation, so as to improve the plasticity of the gel and ensure the convenient operation of the molding process. For example, the gel may be suitably aged or treated at a temperature not exceeding 110 ℃ to remove a part of water in the gel to obtain a plastic solid, which is then molded.
The molar ratio of the aluminum source, the phosphorus source, the metal source, the fluorine source, the organic amine, the ionic liquid and the water is preferably Al2O3:P2O5A metal source F-Organic amine, ionic liquid, H2O=1: 0.4~2.0 : 0.002~1: 0.02~2.0 : 0.1~6.0 : 0.01~3.0 : 25~60。
The gel synthesized by the invention needs to be added with ionic liquid, and one or more than two ionic liquids can be added. The anion of the ionic liquid added may be
、
、
、
、
、
One or more than two of the above; the cation being an alkyl-substituted imidazolium ion
Alkyl substituted pyridinium ions
Alkyl quaternary ammonium salt ion
R is C1-C16 alkyl.
The organic amine is one or more than two of 2-methylimidazole, pyridine and 1-methylpiperidine.
The aluminum source is one or more than two of pseudo-boehmite, activated alumina, aluminum hydroxide, aluminum isopropoxide and aluminum sulfate or aluminum nitrate.
The phosphorus source is one or more than two of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and triammonium phosphate.
The fluorine source is one or more than two of hydrofluoric acid, sodium fluoride and ammonium fluoride.
In the crystallization process, the preferable crystallization temperature is 110-220 ℃, and the preferable crystallization time is 30 min-7 d. The crystallization process is carried out by placing the shaped gel in a pressure-bearing container as is conventional in the art, which may be pre-filled with a quantity of water, but it is not necessary to bring the water into direct contact with the shaped gel. The crystallization process employs heating means conventional in the art, such as oil bath heating, oven heating, and microwave heating.
After crystallization, the formed product does not need to be filtered and washed. The crystallized product retains the same shape and size of the formed gel, and is completely composed of molecular sieve, and the framework structure of the molecular sieve is AFO structure confirmed by International Zeolite Association. And (3) crushing the crystallized product, and performing powder X-ray diffraction, wherein the positions and relative strengths of diffraction peaks are as follows:
| position (degree) | Relative strength and weakness |
| 6.85±0.2 | High strength |
| 9.72±0.2 | High strength |
| 13.72±0.2 | High strength |
| 18.26±0.2 | Medium and high grade |
| 20.64±0.2 | Weak (weak) |
| 21.26±0.2 | High strength |
| 22.20±0.2 | High strength |
| 22.91±0.2 | Medium and high grade |
| 25.84±0.2 | Medium and high grade |
| 29.46±0.2 | Medium and high grade |
To aid in understanding the present invention, the following defines the term "preformed". The terms defined herein have the meanings commonly understood by those of ordinary skill in the art to which the invention pertains.
Unless otherwise indicated, "preforming" as used herein refers to a process or step of pre-processing a gel used to synthesize a molecular sieve into a shaped gel having a shape, size, and mechanical strength by compression, extrusion, tumbling, spraying, and the like.
In summary, the invention provides a preformed synthesis method of a heteroatom metal aluminum phosphate molecular sieve with an AFO structure, which has the following advantages:
the shape and size of the molecular sieve prepared by the method are selected and determined according to the requirements of actual use conditions, and the requirements of different reaction devices are met. In the method, the gel is pretreated in a certain form before the molding operation, so that the plasticity of the gel is improved, and the convenient operation of the molding process is ensured. The gel may be suitably aged or otherwise treated at a temperature not exceeding 110 ℃ to remove a portion of the water from the gel to provide a malleable solid which may then be shaped and processed. The method crystallizes the formed gel, and the product can be formed after the crystallization is finished without filtration and washing; the method directly obtains the formed molecular sieve, avoids the filtering and washing steps in the conventional molecular sieve production process, and has low waste liquid discharge and environmental friendliness. The crystallized product retains the same shape and size of the shaped gel, the shaped body is completely composed of molecular sieve, and the framework structure of the molecular sieve is AFO structure confirmed by International Zeolite Association. The method adopts one-step preparation of the formed molecular sieve, simplifies the preparation process of the catalyst or the adsorbent, and the formed body is completely composed of the molecular sieve, so that the content of the molecular sieve in the catalyst or the adsorbent per unit volume is increased, and the catalytic activity and the adsorption capacity of the catalyst or the adsorbent can be improved.
Drawings
FIG. 1 is an XRD pattern of a sample of example 1 of the present invention.
FIG. 2 is a photograph of a cylindrical bar AFO type heteroatomic aluminophosphate molecular sieve prepared by the preformation method of example 1 of the present invention.
FIG. 3 is a photograph of a clover-shaped AFO type heteroatomic aluminophosphate molecular sieve prepared by the pre-forming method of example 2 of the present invention.
Detailed Description
The present invention is described in detail below by way of examples, but the method of the present invention is not limited thereto, and the scope of the present invention is not limited thereto.
Table 1 examples 1 to 8 of the present invention and synthesis conditions.
Example 1
17.35g of pseudoboehmite (78.6wt% Al)2O3) Placing the mixture into a 250ml beaker, adding 95.39g of deionized water, stirring the mixture for 30 minutes at room temperature, adding 33.90g of phosphoric acid with the concentration of 85wt%, stirring the mixture for 3 hours at room temperature, adding 1.72g of magnesium acetate, stirring the mixture for 30 minutes, adding 1.34g of hydrofluoric acid with the concentration of 40wt%, continuing stirring the mixture for 30 minutes, adding 11.10g of 2-methylimidazole, stirring the mixture for 30 minutes, adding 28.09g of 1-ethyl-3-methylimidazole bromide ionic liquid, stirring the mixture until the mixture is uniformly treated at 90 ℃, and extruding the mixture into a cylindrical strip shape. And (3) filling the formed cylindrical strip-shaped gel into a crystallization kettle with a polytetrafluoroethylene kettle liner, and crystallizing for 3 days at 200 ℃.
And cooling the crystallization kettle to room temperature after crystallization is finished to obtain the formed molecular sieve. The formed molecular sieve is ground into powder and analyzed by XRD spectrogram, the molecular sieve is MgAPO-41, as shown in figure 1, and figure 2 is a real picture of the formed molecular sieve of the embodiment.
Example 2
17.35g of pseudoboehmite (78.6wt% Al)2O3) Placing into a 250ml beaker, adding 129.23g deionized water, stirring for 30 minutes at room temperature, adding 53.08g phosphoric acid with 85wt% concentration and 6.152g ammonium dihydrogen phosphate with 99% purity, stirring for 3 hours at room temperature, adding 0.025g magnesium chloride, stirring for 30 minutes, adding 0.14g hydrofluoric acid with 40wt% concentration, stirring for 30 minutes, adding 31.71g pyridine and 32.92g 2-methylimidazole (2-mim), stirring for 30 minutes, adding 0.31g N-butylpyridineacetate ionic liquid, stirring the mixture, and stirringProcessing at 100 deg.C, and extruding into clover strip. And (3) filling the formed clover strip-shaped gel into a crystallization kettle with a polytetrafluoroethylene kettle liner, and crystallizing for 7 days at 220 ℃.
And cooling the crystallization kettle to room temperature after crystallization is finished to obtain the formed molecular sieve. Grinding the formed molecular sieve into powder, and analyzing by an XRD spectrogram, wherein the molecular sieve is MgAPO-41. FIG. 3 is a photograph of a MgAPO-41 molecular sieve in this example.
Example 3
17.35g of pseudoboehmite (78.6wt% Al)2O3) Placing the mixture into a 250ml beaker, adding 44.23g of deionized water, stirring the mixture for 30 minutes at room temperature, adding 12.33g of phosphoric acid with the concentration of 85wt%, stirring the mixture for 3 hours at room temperature, adding 34.27g of magnesium nitrate, stirring the mixture for 30 minutes, adding 12.03g of hydrofluoric acid with the concentration of 40wt% and 1.00g of ammonium fluoride with the purity of 99%, stirring the mixture for 30 minutes, adding 1.34g of 1-methylpiperidine, stirring the mixture for 30 minutes, adding 45.31g of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and 38.31g of 1-ethyl-3-methylimidazolium bromide ionic liquid, stirring the mixture until the mixture is treated uniformly at 75 ℃ and rolling the mixture into balls. And (3) filling the molded spherical gel into a crystallization kettle with a polytetrafluoroethylene kettle liner, and crystallizing for 30 minutes at 220 ℃.
And cooling the crystallization kettle to room temperature after crystallization is finished to obtain the formed molecular sieve. Grinding the formed molecular sieve into powder, and analyzing by an XRD spectrogram, wherein the molecular sieve is MgAPO-41.
Example 4
17.35g of pseudoboehmite (78.6wt% Al)2O3) Placing the mixture into a 250ml beaker, adding 32.03g of deionized water, stirring the mixture for 30 minutes at room temperature, adding 12.33g of phosphoric acid with the concentration of 85wt%, stirring the mixture for 3 hours at room temperature, adding 0.06g of magnesium acetate, stirring the mixture for 30 minutes, adding 13.37g of hydrofluoric acid with the concentration of 40wt%, continuing stirring the mixture for 30 minutes, adding 2-methylimidazole, stirring the mixture for 30 minutes, adding 0.22g of tetraethylammonium chloride ionic liquid, stirring the mixture until the mixture is uniformly treated at 75 ℃, and extruding the mixture into a honeycomb shape. And (3) putting the formed honeycomb-shaped gel block into a crystallization kettle with a polytetrafluoroethylene kettle liner, and crystallizing for 30min at 220 ℃.
And cooling the crystallization kettle to room temperature after crystallization is finished to obtain the formed molecular sieve. Grinding the formed molecular sieve into powder, and analyzing by an XRD spectrogram, wherein the molecular sieve is MgAPO-41.
Example 5
14.74g of pseudo-boehmite (78.6wt% Al)2O3) And 4.09g of 99% pure aluminum isopropoxide in a 250ml beaker, 103.37g of deionized water was added, stirring was carried out at room temperature for 30 minutes, 12.33g of 85wt% phosphoric acid was added, after stirring was carried out at room temperature for 3 hours, 0.06g of magnesium acetate was added, stirring was carried out for 30 minutes, 0.14g of 40wt% hydrofluoric acid was added, after further stirring was carried out for 30 minutes, 1.10g of 2-methylimidazole was added, after stirring was carried out for 30 minutes, 0.14g of ethylammonium nitrate ionic liquid was added, the above mixture was stirred until it was uniformly treated at 80 ℃, and spherical particles were prepared by an oil column molding method. And (3) putting the formed gel into a crystallization kettle with a polytetrafluoroethylene kettle liner, and crystallizing for 7 days at 110 ℃.
And cooling the crystallization kettle to room temperature after crystallization is finished to obtain the formed molecular sieve. Grinding the formed molecular sieve into powder, and analyzing by an XRD spectrogram, wherein the molecular sieve is MgAPO-41.
Example 6
17.35g of pseudoboehmite (78.6wt% Al)2O3) Placing the mixture into a 250ml beaker, adding 95.39g of deionized water, stirring the mixture for 30 minutes at room temperature, adding 33.90g of phosphoric acid with the concentration of 85wt%, stirring the mixture for 3 hours at room temperature, adding 1.47g of zinc acetate, stirring the mixture for 30 minutes, adding 1.34g of hydrofluoric acid with the concentration of 40wt%, continuing stirring the mixture for 30 minutes, adding 11.10g of 2-methylimidazole, stirring the mixture for 30 minutes, adding 28.09g of 1-ethyl-3-methylimidazole bromide ionic liquid, stirring the mixture uniformly, treating the mixture at 90 ℃, and extruding the mixture into clover strips. And (3) putting the formed clover strip-shaped gel into a crystallization kettle with a polytetrafluoroethylene kettle liner, and crystallizing for 3 days at 210 ℃.
And cooling the crystallization kettle to room temperature after crystallization is finished to obtain the formed molecular sieve. Grinding the formed molecular sieve into powder, and analyzing by an XRD spectrogram, wherein the molecular sieve is ZnAPO-41.
Example 7
17.35g of pseudo-boehmiteStone (78.6wt% Al)2O3) Placing the mixture into a 250ml beaker, adding 95.39g of deionized water, stirring the mixture for 30 minutes at room temperature, adding 33.90g of phosphoric acid with the concentration of 85wt%, stirring the mixture for 3 hours at room temperature, adding 2.00g of cobalt acetate, stirring the mixture for 30 minutes, adding 1.34g of hydrofluoric acid with the concentration of 40wt%, continuing stirring the mixture for 30 minutes, adding 11.10g of 2-methylimidazole, stirring the mixture for 30 minutes, adding 28.09g of 1-ethyl-3-methylimidazole bromide ionic liquid, stirring the mixture until the mixture is uniformly treated at 90 ℃, and extruding the mixture into a cylindrical strip shape. And (3) filling the formed cylindrical strip-shaped gel into a crystallization kettle with a polytetrafluoroethylene kettle liner, and crystallizing for 3 days at 210 ℃.
And cooling the crystallization kettle to room temperature after crystallization is finished to obtain the formed molecular sieve. Grinding the formed molecular sieve into powder, and analyzing by an XRD spectrogram, wherein the molecular sieve is CoAPO-41.
Example 8
17.35g of pseudoboehmite (78.6wt% Al)2O3) Placing the mixture into a 250ml beaker, adding 95.39g of deionized water, stirring the mixture for 30 minutes at room temperature, adding 33.90g of phosphoric acid with the concentration of 85wt%, stirring the mixture for 3 hours at room temperature, adding 1.97g of manganese acetate, stirring the mixture for 30 minutes, adding 1.34g of hydrofluoric acid with the concentration of 40wt%, continuing stirring the mixture for 30 minutes, adding 11.10g of 2-methylimidazole, stirring the mixture for 30 minutes, adding 28.09g of 1-ethyl-3-methylimidazole bromide ionic liquid, stirring the mixture until the mixture is uniformly treated at 90 ℃, and extruding the mixture into a cylindrical strip shape. And (3) filling the formed cylindrical strip-shaped gel into a crystallization kettle with a polytetrafluoroethylene kettle liner, and crystallizing for 3 days at 210 ℃.
And cooling the crystallization kettle to room temperature after crystallization is finished to obtain the formed molecular sieve. Grinding the formed molecular sieve into powder, and analyzing by an XRD spectrogram, wherein the molecular sieve is MnAPO-41.
Table 2 shows the XRD diffraction peak positions and relative intensities of the samples of examples 1-8 of the present invention.
As can be seen from the above table, the pure phase AFO type heteroatom metalloaluminophosphate molecular sieve can be prepared within the reaction condition range stated in the method.
Claims (2)
1. A preformed synthesis method of a heteroatom metalloaluminophosphate molecular sieve with an AFO structure is characterized by comprising the following steps:
(1) uniformly mixing an aluminum source, a phosphorus source, a metal source, a fluorine source, organic amine, ionic liquid and water to obtain gel, wherein Al in the gel2O3:P2O5:MeO:F-Organic amine, ionic liquid, H2The molar ratio of O is 1: 0.4-2.0: 0.002-1: 0.02-2.0: 0.1-6.0: 0.01-3.0: 25-60;
(2) pretreating the gel prepared in the step (1) and then processing the gel into a formed gel with a required shape, wherein the pretreatment adopts gel aging or gel treatment at the temperature of not more than 110 ℃;
(3) placing the formed gel prepared in the step (2) in a closed container, wherein the crystallization temperature is 110-220 ℃, and the crystallization time is 30 min-7 d, so as to obtain a formed molecular sieve with an AFO topological structure;
me of the MeO is magnesium, cobalt, zinc, manganese or nickel; the anion in the ionic liquid is
、
、
、
、
、
Wherein the cation is alkyl-substituted imidazolium
Alkyl-substituted pyridinium ions
Alkyl quaternary ammonium salt ionWherein R is C1-C16 alkyl; the organic amine is one or more than two of 2-methylimidazole, pyridine and 1-methylpiperidine;
the metal source is one or more than two of magnesium acetate, magnesium chloride, magnesium nitrate, cobalt acetate, cobalt carbonate, cobalt sulfate, zinc acetate, zinc chloride, zinc nitrate, manganese acetate, manganese chloride, manganese sulfate, nickel acetate, nickel nitrate and nickel oxide; the aluminum source is one or more than two of pseudo-boehmite, activated alumina, aluminum hydroxide, aluminum isopropoxide, aluminum sulfate or aluminum nitrate; the phosphorus source is one or more than two of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and triammonium phosphate; the fluorine source is one or more than two of hydrofluoric acid, ammonium fluoride and sodium fluoride.
2. The preformed synthesis method of the heteroatom metalloaluminophosphate molecular sieve having an AFO structure according to claim 1, characterized in that: the shape of the formed gel is spherical, strip-shaped, cylindrical, honeycomb-shaped, clover-shaped, external gear-shaped, nonporous external gear-shaped, quincunx, porous quincunx, seven-hole spherical, nonporous spherical, seven-rib wheel-shaped, four-hole or four-leaf butterfly.
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| US6768036B2 (en) * | 2001-12-31 | 2004-07-27 | Exxonmobil Chemical Patents Inc. | Method for adding heat to a reactor system used to convert oxygenates to olefins |
| CN100497172C (en) * | 2005-08-31 | 2009-06-10 | 中国石油化工股份有限公司 | Metal modified AFO structure silicon aluminum phosphate molecular sieve and application thereof |
| CN1850606A (en) * | 2006-06-07 | 2006-10-25 | 中国科学院大连化学物理研究所 | Method for preparing AlPO4 or SAPO molecular sieve |
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