CN101229921B - Method for synthesizing SAPO-46 silicoaluminophosphate molecular sieve - Google Patents
Method for synthesizing SAPO-46 silicoaluminophosphate molecular sieve Download PDFInfo
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- CN101229921B CN101229921B CN2007101501869A CN200710150186A CN101229921B CN 101229921 B CN101229921 B CN 101229921B CN 2007101501869 A CN2007101501869 A CN 2007101501869A CN 200710150186 A CN200710150186 A CN 200710150186A CN 101229921 B CN101229921 B CN 101229921B
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Abstract
The invention provides a synthesizing method of SAPO-46 silicon aluminum phosphate molecular sieve Which takes Phosphorous acid-phosphoric acid as phosphorous source and di-n-propylamine as template. Silicon source, aluminum source, the phosphorous source, organic template, the silicon source and the water are prepared into the synthesis colloid according to the mole proportion that Al2O3: H3PO3:H3PO4: R : SiO2 : H2O is equal to 0.8-1.2:0.5-2.0:2.5-1.0:2.0-8.0:0.40-2.0:50-150; then, hydrothermal crystallization is carried out for the colloid under 180-200 DGE C and autogenous pressure for 3-5 days; the obtained substance is washed by water, separated, dried at the room temperature of 60-80 DGE C to obtain the finished product. The method of the invention uses convenient method to synthesize SAPO-46 molecular sieve products with high crystallinity in which thermal stability is remarkably higher than the products synthesized by the current method.
Description
Technical field
The present invention relates to the synthetic method of aluminium silicophosphate molecular sieve, specifically is a kind of synthetic method of SAPO-46 aluminium silicophosphate molecular sieve.Do in the system in phosphorus source containing phosphorous acid, make synthetic SAPO-46 aluminium silicophosphate molecular sieve under the template condition with di-n-propylamine di-n-propylammine (DPA).
Background technology
Aluminium silicophosphate molecular sieve SAPO-46 skeleton is made of Si, P, Al, O element, have three-dimensional octatomic ring (free diameter 0.4 nanometer) and twelve-ring (free diameter 0.7 nanometer) opening, and cross one another straight hole road system, belong to hexagonal system, unit cell dimension is a=1.33, the c=2.69 nanometer.Connect owing in the skeleton structure of SAPO-46, exist Si-O-Al, thereby it is acid that this molecular sieve is produced.Because the acidity of pore passage structure of its uniqueness and suitable medium tenacity makes them show higher activity in catalysis methanol/toluene system dimethylbenzene alkylated reaction.
Up to the present less about the synthetic bibliographical information of SAPO-46, only several pieces of documents (J.Chem.Soc., Chem.Commun., 1994,1527-1528) (J.Chem.Soc., Faraday Trans., 1995,91,1045-1050) reported the synthetic of SAPO-46 molecular sieve.Adopting pseudo-boehmite is the aluminium source, and phosphoric acid is the phosphorus source, and silicon sol is the silicon source, and di-n-propylamine di-n-propylammine (DPA) is an organic formwork agent.The main deficiency of this method is that the synthetic SAPO-46 of institute molecular sieve thermostability is lower, is unfavorable for removing organic formwork agent, and the application in the Industrial Catalysis reaction.And required crystallization time is longer, and complex steps generally was the initial stage 150 ℃ of crystallization 96 hours, and further 180 ℃ of crystallization 120 hours, products therefrom degree of crystallinity was also relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of SAPO-46 aluminium silicophosphate molecular sieve to make synthetic method in the system in phosphorus source containing phosphorous acid.It is the method that a kind of usefulness synthesizes the SAPO-46 aluminium silicophosphate molecular sieve of high-crystallinity easy within a short period of time.The thermostability of products therefrom is apparently higher than existing method synthetic SAPO-46 molecular sieve, synthetic in employed template can under 650 ℃, remove fully and SAPO-46 framework of molecular sieve structure still can remain intact, help its application in catalyzed reaction.
The present invention is through following step: silicon source, aluminium source, phosphorus source, organic formwork agent and water or aluminium source, phosphorus source, organic formwork agent and water are mixed make synthetic colloid earlier, the temperature when becoming glue is 25～50 ℃.Should synthesize colloid hydrothermal crystallizing 3～5 days under 150～220 ℃ and autogenous pressure then, collection, washing and 60-80 ℃ is drying to obtain product.
Silicon of the present invention source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, the phosphorus source is with H
3PO
3With H
3PO
4The mixture meter, organic formwork agent is represented with R.Reaction mass is according to synthetic colloid: the Al of following mole proportioning
2O
3: H
3PO
3: H
3PO
4: R: SiO
2: H
2O=0.8～1.5: 0.2～2.0: 2.8～1.0: 1.0～8.0: 0.30～2.0: 20～150.
In the inventive method, said phosphorus source is that the mixing acid of phosphorous acid and phosphoric acid is as the phosphorus source; The aluminium source is the salt of pseudo-boehmite, aluminum isopropylate and aluminium; The silicon source is the aerogel (fume silica) of silicon sol, silicon; Organic formwork agent is a di-n-propylamine.
In the inventive method, the nitration mixture of preferred phosphorous acid and phosphoric acid is that aluminium source, silicon sol are the silicon source as phosphorus source, pseudo-boehmite; Di-n-propylamine is a template.
In the inventive method, the addition sequence of said phosphorus source, aluminium source, silicon source and organic formwork agent is the order adding according to aluminium source, phosphorus source, organic formwork agent, silicon source.
In the inventive method, preferably will synthesize colloid hydrothermal crystallizing 3～5 days hours under 150～220 ℃ and autogenous pressure, and collect then, wash and 60～80 ℃ of oven dry promptly get product.
The invention has the beneficial effects as follows: the silicon source of being adopted in the synthetic method of SAPO-46 molecular sieve provided by the present invention, aluminium source, phosphorus source and organic formwork agent are all determined according to existing technical specification, the present invention has no particular limits it, can synthesize degree of crystallinity, thermostability apparently higher than existing methods SAPO-46 molecular sieve with step comparatively easily.
The present invention is further described below in conjunction with accompanying drawing and embodiment.
Description of drawings
Fig. 1 is the XRD of the product SAPO-46 of 1 of the embodiment of the invention.
Fig. 2 is the XRD after the product SAPO-46 roast 550 of 1 of the embodiment of the invention is spent
Fig. 3 is the embodiment of the invention 1 a digit microscope photo
Embodiment
At 25 ℃, with 20 ml waters dissolving, 1.8 gram phosphorous acid, drip 2.4 milliliters of 85% phosphoric acid, this mixed acid aqueous solution is poured in the 4.2 gram pseudo-boehmite pressed powders again, stirred 45 minutes rapidly, and then add 12.2 milliliters of di-n-propylamines while stirring, drip 1.6 milliliters of silicon sol again, and then stir and moved into to even back in 2 hours in the stainless steel cauldron in 200 ℃ of crystallization 72 hours, collect then, wash and 60～80 ℃ of oven dry, promptly get product.
At 25 ℃, with 30 ml waters dissolving, 1.8 gram phosphorous acid, drip 2.4 milliliters of 85% phosphoric acid, this mixed acid aqueous solution is poured in the 5.4 gram aluminum isopropylate pressed powders again, stirred 50 minutes rapidly, and then add 10 milliliters of di-n-propylamines while stirring, drip 1.5 milliliters of silicon sol again, and then stir and moved into to even back in 2 hours in the stainless steel cauldron in 190 ℃ of crystallization 80 hours, collect then, wash and 60～80 ℃ of oven dry, promptly get product.
At 25 ℃, with 40 ml waters dissolving, 1.5 gram phosphorous acid, drip 2.1 milliliters of 85% phosphoric acid, this mixed acid aqueous solution is poured in the 3.3 gram pseudo-boehmite pressed powders again, stirred 30 minutes rapidly, and then add 8.4 milliliters of di-n-propylamines while stirring, drip 1.3 milliliters of silicon sol again, and then stir and moved into to even back in 2 hours in the stainless steel cauldron in 210 ℃ of crystallization 72 hours, collect then, wash and 60～80 ℃ of oven dry, promptly get product.
Embodiment 4
At 25 ℃, with 10 ml waters dissolving, 1.8 gram phosphorous acid, drip 85% phosphatase 11 .6 milliliter, this mixed acid aqueous solution is poured in the 3.8 gram pseudo-boehmite pressed powders again, stirred rapidly 45 minutes, and then add 10 milliliters of di-n-propylamines while stirring, drip 1.4 milliliters of silicon sol again, add 10 milliliters in water then, restir 2 hours to even back moves in the stainless steel cauldron in 160 ℃ of crystallization 90 hours, collect then, wash and 60～80 ℃ of oven dry, promptly get product.
At 25 ℃, with 10 ml waters dissolving, 1.4 gram phosphorous acid, drip 2.0 milliliters of 85% phosphoric acid, this mixed acid aqueous solution is poured in the 4.3 gram aluminum isopropylate pressed powders again, stirred rapidly 50 minutes, and then add 7.6 milliliters of di-n-propylamines while stirring, drip 1.8 milliliters of silicon sol again, add 10 milliliters in water then, restir 2 hours to even back moves in the stainless steel cauldron in 170 ℃ of crystallization 72 hours, collect then, wash and 60～80 ℃ of oven dry, promptly get product.
Embodiment 6
At 25 ℃, with 20 ml waters dissolving, 1.8 gram phosphorous acid, drip 2.4 milliliters of 85% phosphoric acid, this mixed acid aqueous solution is poured in the 3.6 gram pseudo-boehmite pressed powders again, stirred 30 minutes rapidly, and then add 5.0 milliliters of di-n-propylamines while stirring, drip 1.5 milliliters of silicon sol again, stir then and moved into to even back in 2 hours in the stainless steel cauldron, collect then, wash and 60～80 ℃ of oven dry, promptly get product in 185 ℃ of crystallization 72 hours.
Embodiment 7
At 25 ℃, with 10 ml waters dissolving, 1.8 gram phosphorous acid, drip 85% phosphatase 11 .5 milliliter, this mixed acid aqueous solution is poured in the 3.0 gram pseudo-boehmite pressed powders again, stirred rapidly 45 minutes, and then add 16 milliliters of di-n-propylamines while stirring, drip 3.6 milliliters of silicon sol again, add 10 milliliters in water then, restir 2 hours to even back moves in the stainless steel cauldron in 170 ℃ of crystallization 76 hours, collect then, wash and 60～80 ℃ of oven dry, promptly get product.
Claims (7)
1. the synthetic method of an aluminium silicophosphate molecular sieve SAPO-46 is characterized in that the phosphorus source that will contain phosphorous acid combines with the di-n-propylamine template and prepares high thermal stability SAPO-46 aluminium silicophosphate molecular sieve;
It is through following step: aluminium source, phosphorus source, organic formwork agent, silicon source and water are mixed make synthetic colloid earlier, temperature when becoming glue is 25～50 ℃, should synthesize colloid hydrothermal crystallizing 3～5 days under 180～200 ℃ and autogenous pressure then, collect then, wash and 60～80 ℃ of oven dry, promptly get product;
The addition sequence of wherein said phosphorus source, aluminium source, silicon source and organic formwork agent is that the order according to the order in the order in aluminium source, phosphorus source, organic formwork agent, silicon source or aluminium source, organic formwork agent, phosphorus source, silicon source or phosphorus source, organic formwork agent, aluminium source, silicon source adds.
2. according to the synthetic method of the described SAPO-46 aluminium silicophosphate molecular sieve of claim 1, it is characterized in that described synthetic colloidal material mole proportioning is: Al
2O
3: H
3PO
3: H
3PO
4: organic formwork agent: SiO
2: H
2O=0.8～1.2: 0.5～2.0: 2.5～1.0: 2.5～5.0: 0.4～0.8: 30～100.
3. according to the synthetic method of the described SAPO-46 aluminium silicophosphate molecular sieve of claim 1, it is characterized in that described phosphorus source is phosphorous acid and phosphoric acid mixing acid; The aluminium source is the salt of pseudo-boehmite, aluminum isopropylate and aluminium; The silicon source is the aerogel of silicon sol, silicon; Organic formwork agent is a di-n-propylamine.
4. according to the synthetic method of the described SAPO-46 aluminium silicophosphate molecular sieve of claim 1, it is characterized in that described phosphorus source is the nitration mixture of phosphorous acid and phosphoric acid.
5. according to the synthetic method of the described SAPO-46 aluminium silicophosphate molecular sieve of claim 1, it is characterized in that described aluminium source is a pseudo-boehmite.
6. according to the synthetic method of the described SAPO-46 aluminium silicophosphate molecular sieve of claim 1, it is characterized in that described silicon source is a silicon sol.
7. according to the synthetic method of the described SAPO-46 aluminium silicophosphate molecular sieve of claim 1, it is characterized in that described template is a di-n-propylamine.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456502A (en) * | 2003-03-27 | 2003-11-19 | 中国石油化工股份有限公司 | Preparation of silicon aluminum phosphoric molecular sieves and preparation thereof |
| US6710218B1 (en) * | 1997-10-02 | 2004-03-23 | Casale Chemicals Sa | Catalytic process for the preparation of light olefins from methanol in fluidized bed reactor |
| CN1830783A (en) * | 2006-03-23 | 2006-09-13 | 南开大学 | Synthesis method of silicon aluminium phosphate molecular sieve |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6710218B1 (en) * | 1997-10-02 | 2004-03-23 | Casale Chemicals Sa | Catalytic process for the preparation of light olefins from methanol in fluidized bed reactor |
| CN1456502A (en) * | 2003-03-27 | 2003-11-19 | 中国石油化工股份有限公司 | Preparation of silicon aluminum phosphoric molecular sieves and preparation thereof |
| CN1830783A (en) * | 2006-03-23 | 2006-09-13 | 南开大学 | Synthesis method of silicon aluminium phosphate molecular sieve |
Non-Patent Citations (4)
| Title |
|---|
| 毛海立.磷酸硅铝分子筛（SAPO-n）的合成及应用简介.黔南民族师范学院学报 6.2001,(6),51-53. |
| 毛海立.磷酸硅铝分子筛(SAPO-n)的合成及应用简介.黔南民族师范学院学报 6.2001,(6),51-53. * |
| 陈会慧等.过氧化氢和磷酸对以亚磷酸作磷源合成SAPO-41和AlPO-41的影响.催化学报28 6.2007,28(6),501-503. |
| 陈会慧等.过氧化氢和磷酸对以亚磷酸作磷源合成SAPO-41和AlPO-41的影响.催化学报28 6.2007,28(6),501-503. * |
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