CN102786063A - Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure - Google Patents
Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure Download PDFInfo
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Abstract
The invention provides a method for synthesizing a silicoaluminophosphate molecular sieve SAPO-11 at normal pressure. The method is characterized in that the main process comprises the following steps of 1) preparation of eutectic mixture: fully grinding and mixing quaternary ammonium salt and organic acid or organic alcohol in a mortar with a mol ratio of 0.1 to 1.0; placing the mixture in a beaker, heating the beaker at a temperature of 80-180 DEG C to melt the mixture into transparent liquid, so as to obtain the eutectic mixture; 2) preparation of crystallization reaction mixture: adding phosphorus source, silicon source, mineralizing agent, template agent and aluminum source into the molten eutectic mixture in sequence, uniformly stirring the mixture at a mixing temperature range from 80 to 150 DEG C to form a reaction mixture; 3) crystallizing the reaction mixture prepared by step 2); and 4) water cooling the reactant reacted in step 3) to a room temperature, washing and separating the mixture, and drying and baking the washed and separated mixture, wherein the washed filtrate is recovered after rotary evaporation.
Description
Technical field
The invention belongs to inorganic synthetic field, relate to a kind of compound method of molecular sieve; More precisely relate to the ion thermal synthesis method of a kind of aluminium silicophosphate molecular sieve (SAPO-11) in eutectic mixture.
Background technology
Aluminium phosphate molecular sieve is after Si-Al molecular sieve, and U.S. combinating carbide company is at the molecular sieve of new generation (USP4310440) of early eighties exploitation in last century.AlPO
4-11 molecular sieves (the matrix topology code name is AEL) contain one dimension ten-ring straight hole pore passage structure, and the aperture is oval, and size is 0.39 * 0.63 nm.Aluminium silicophosphate SAPO (MAPO) molecular sieve that silicon (or other metal heteroatom M) is introduced; Skeleton has acidic site; Therefore expanded the purposes of this molecular sieve, particularly in the alkane hygrogenating isomerization reaction, the SAPO-11 molecular sieve that has supported precious metal has excellent catalytic performance.US 4440871, and US 4701485, and US 4943424, and US 4960504, and US 5208005, and US 5817595, CN 1155519C, and patents such as CN 1174919 have been announced the hydrothermal synthesis method of SAPO-11 molecular sieve.Need in high-tension apparatus, carry out because hydro-thermal is synthetic, exist potential dangerous, and facility investment is high, inconvenient operation.
Recently, Morris professor's people from research group reported use ionic liquid as the ion process for thermosynthesizing of solvent and the synthetic microporous aluminium phosphate molecular sieve of template (
Nature430,1012-1016 (2004)).Compare with the hydro-thermal of routine is synthetic, the ion thermal synthesis can be carried out under normal pressure, and this mainly is because ionic liquid has insignificant saturated vapor pressure.Therefore, use common round-bottomed flask or open beaker just can carry out building-up reactions.Tian Zhijian researcher's research group has introduced organic amine as extra compositional variable in the ion thermal synthesis, but modulation response path and crystallization product (
J. Am. Chem. Soc.128,7432-7433 (2006)).
But ionic liquid is not very convenient synthetic, and price is higher; Eutectic mixture and ionic liquid have close character, also can be used as molecular sieve synthetic solvent, and preparation is convenient and more cheap.Compound method of the present invention adopts eutectic mixture as solvent, and introducing organic amine simultaneously is that template is carried out the synthetic of SAPO-11 molecular sieve under normal pressure.
Summary of the invention
The compound method that the purpose of this invention is to provide a kind of molecular sieve; More precisely be that adopting the eutectic mixture close with ionic liquid character is the ion thermal synthesis method of solvent about the compound method of a kind of matrix topology code name aluminium silicophosphate molecular sieve (SAPO-11) that is AEL.
The present invention is the method for synthesizing silicon aluminum orthophosphate molecular sieve SAPO-11 under a kind of normal pressure, it is characterized in that, main processes comprises:
1) preparation of eutectic mixture
With quaternary ammonium salt and organic acid or organic alcohol abundant ground and mixed in mortar, place beaker then 80～180
oC heating down makes it to be melted into transparent liquid, makes eutectic mixture;
Described quaternary ammonium salt is one or more in etamon chloride, 4-propyl bromide, Tetrabutyl amonium bromide, the choline chloride 60;
Described organic acid/organic alcohol is Hydrocerol A, one or more in the tetramethylolmethane,
Quaternary ammonium salt and organic acid in the described eutectic mixture/organic pure blended molar ratio is 0.1 ~ 10; Optimizing molar ratio is 0.2 ~ 8;
2) preparation of crystallization mixture
Phosphorus source, silicon source, mineralizer and template, aluminium source are joined in the eutectic mixture of fusing successively, in 80～150 ° of C blend temperature range, or in 105 ~ 140 ° of more excellent C blend temperature range; Stir, form reaction mixture;
Described phosphorus source be in the phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate of mass concentration 50 ~ 85% one or more;
Described silicon source is one or more in silicon sol, water glass, tetraethoxy, WHITE CARBON BLACK, superfine silicon dioxide powder and the silicic acid;
Described mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride or the water of mass concentration 20-40%;
Described organic amine template is a di-n-propylamine, Diisopropylamine, n-Butyl Amine 99, triethylamine, triethyl tetramine, diethyl triamine, Tributylamine, one or more in diethylamine or the hexamethyl time tetramine;
Described aluminium source is one or more in aluminum isopropylate, aluminum chloride, the pseudo-boehmite;
With Al in the aluminium source
2O
3The content meter, the mol ratio in quaternary ammonium salt cationic and aluminium source is 2.0 ~ 40 in the eutectic mixture; More excellent mol ratio is 3 ~ 20;
The mol ratio in phosphorus source and aluminium source is 0.6 ~ 3.0; More excellent mol ratio is 0.9 ~ 1.1;
The mol ratio in silicon source and aluminium source is 0.05 ~ 0.6; More excellent mol ratio is 0.15 ~ 0.5;
The mol ratio in mineralizer and aluminium source is 0.1 ~ 1.2; More excellent mol ratio is 0.6 ~ 0.8;
The mol ratio in template and aluminium source is 0.1 ~ 5.0; More excellent mol ratio is 0.3 ~ 3.0;
3) with step 2) preparation reaction mixture uncovered crystallization in glassware; Or in the teflon-lined stainless steel cauldron airtight crystallization, crystallization temperature is 130 ~ 220 ° of C, crystallization time is more than 10 minutes; More excellent crystallization temperature is 150 ~ 190 ° of C, and more excellent crystallization time is 2 ~ 12 hours;
4) the reacted reactants water of step 3) is chilled to room temperature, behind deionized water repetitive scrubbing sample, separates the white powder that obtains after the oven dry roasting of back and be said aluminium silicophosphate molecular sieve; Recycle after receiving the filtrating rotary evaporation after washing.
The analysis of institute of the present invention synthetic aluminium silicophosphate molecular sieve product is carried out on Japan's Rigaku x-ray powder diffraction instrument of science (40kV/200mA) and Rigaku x-ray fluorescence analyzer (40kV/40mA).
The present invention finds; In ion thermal synthesis molecular sieve process; The effect of the following aspects has been played in the introducing of organic amine: the gel that a) changes crystallization is formed, and this influences the interaction of gel species, and then influences nucleation, crystallization and the growth of molecular sieve crystal; B) change solvent properties, like viscosity, surface tension, polarity and conductivity; C) the pH value of change system, organic amine is to have different pK
bOrganic bases of value, and the synthetic environment that phosphoric acid exists is a tart; D) species that play structure-directing effect in the crystallization process have been changed.So the present invention is intended to the synthetic middle organic amine of introducing of the hot method of ion and plays structure-directing effect, avoids consuming the solvent of synthetic system, through synthetic target molecule sieves of key elements such as control reaction ratio, temperature, times.
The invention discloses the ion process for thermosynthesizing of a kind of microporous aluminophosphates molecular sieve SAPO-11.The present invention has overcome the shortcoming of the synthetic SAPO-11 molecular sieve of traditional hydrothermal method: process needs condition of high voltage and produces a large amount of waste liquids.It synthesizes under normal pressure and carries out, and organic amine is easy to separate with eutectic mixture and can reuses environmental friendliness.
Description of drawings
Fig. 1 is the XRD spectra of 1 synthetic AEL of embodiment of the invention type aluminium phosphate molecular sieve.
Fig. 2 is the SEM electromicroscopic photograph of 1 synthetic AEL of embodiment of the invention type aluminium phosphate molecular sieve.
Embodiment
Embodiment 1
Take by weighing 20.0 gram tetramethylolmethanes and 40.0 respectively and restrain Tetrabutyl amonium bromides, ground and mixed is placed in the 150mL beaker, and heating makes its fusing on hot-plate, and evenly stirs until forming transparent liquid, gets eutectic mixture.3.89 gram phosphoric acid are dropped in the eutectic mixture, stir, add 7.1 gram (30.0%) acidic silicasols then, add 0.50 gram hydrofluoric acid (40.0%) again, 3.1 gram di-n-propylamines are added in the eutectic mixture, stir; Aluminium source 2.85 Keshans east aluminium powder is slowly added in the above-mentioned mixed solution, continue to stir gained mixed sols half a hour; Above-mentioned mixed sols is moved in 150 milliliters of round-bottomed flasks, adopt the heating jacket heating, magnetic agitation connects the prolong water-cooled, in 180 on the flask
oC crystallization 12 hours.With the reactant cool to room temperature, add 50 ml deionized water and stir then, after the supersound washing reactant is filtered, obtain the white solid powder, triplicate.Place 110 ° of C baking ovens to dry in the final white powder, through the XRD test, this white powder is SAPO-11 (AEL topological framework) molecular sieve, and the fluorometric analysis result is following: Al
2O
3, 49.2%; P
2O
5, 42.6%; SiO
2, 7.84%.
With embodiment 1 is benchmark, and following examples have only part steps and crystallization condition to change, but all can obtain the SAPO-11 product of different crystallinity, for simplicity, is summarized as follows.
Concrete steps and synthesis condition are similar to embodiment 1, but crystallization temperature is 160,170,180,190
oC, crystallization time are 24 hours.
Embodiment 6
Concrete steps and synthesis condition are similar to embodiment 1, process but eutectic mixture restrains Tetrabutyl amonium bromides by 15 gram tetramethylolmethanes and 45, and crystallization carries out in 150 milliliters of static reaction stills, and constant temperature 180 in the rotary oven
oC crystallization 12 hours.
Embodiment 7
Concrete steps and synthesis condition are similar to embodiment 1, process but eutectic mixture restrains Tetrabutyl amonium bromides by 15 gram tetramethylolmethanes and 45, and the phosphoric acid add-on is 4.32 grams, and the hydrofluoric acid add-on is 0.35 gram, and the time is 36 hours.
Embodiment 8
Concrete steps and synthesis condition are similar to embodiment 1, but the phosphoric acid add-on is 4.10 grams, and the hydrofluoric acid add-on is 0.20 gram, and the time is 48 hours.
Embodiment 9
Concrete steps and synthesis condition are similar to embodiment 1, process but eutectic mixture restrains Tetrabutyl amonium bromides by 25 gram tetramethylolmethanes and 35, and the phosphoric acid add-on is 4.10 grams, and template is 4.1 gram diethylamine, and crystallization temperature is 190 ° of C.Crystallization time is 4 hours.
Concrete steps and synthesis condition are similar to embodiment 1, but the phosphoric acid add-on is 3.89 grams, and template is diethyl triamine 4.5 grams.
Embodiment 11
Concrete steps and synthesis condition are similar to embodiment 1, but the aluminium source is 3.52 gram SB powder (Sasol company, pseudo-boehmite, 74.0%), and template is di-n-propylamine 3.1 grams.
Embodiment 12
Concrete steps and synthesis condition are similar to embodiment 1, but the aluminium source is 7.66 gram aluminum isopropylates, and template is diethylamine 3.1 grams.
Embodiment 13
Concrete steps and synthesis condition are similar to embodiment 1, process but eutectic mixture restrains choline chloride 60s by 30 gram tetramethylolmethanes and 30, and the silicon source is tetraethoxy 7.5 grams, and crystallization temperature is 170 ° of C, and crystallization time is 48 hours.
Embodiment 14～16
Concrete steps and synthesis condition are similar to embodiment 1, but template is diethylamine 4.1 grams, and the silicon sol add-on is respectively 3.6 grams among the embodiment 14～16,5.7 grams and 10.6 grams.
Claims (2)
1. the method for synthesizing silicon aluminum orthophosphate molecular sieve SAPO-11 under the normal pressure is characterized in that main processes comprises:
1) preparation of eutectic mixture
With quaternary ammonium salt and organic acid or organic alcohol abundant ground and mixed in mortar, place beaker then 80～180
oC heating down makes it to be melted into transparent liquid, makes eutectic mixture;
Described quaternary ammonium salt is one or more in etamon chloride, 4-propyl bromide, Tetrabutyl amonium bromide, the choline chloride 60;
Described organic acid/organic alcohol is Hydrocerol A, one or more in the tetramethylolmethane,
Quaternary ammonium salt and organic acid in the described eutectic mixture/organic pure blended molar ratio is 0.1 ~ 10;
2) preparation of crystallization mixture
Phosphorus source, silicon source, mineralizer and template, aluminium source are joined in the eutectic mixture of fusing successively, in 80～150 ° of C blend temperature range, stir, form reaction mixture;
Described phosphorus source be in the phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate of mass concentration 50 ~ 85% one or more;
Described silicon source is one or more in silicon sol, water glass, tetraethoxy, WHITE CARBON BLACK, superfine silicon dioxide powder and the silicic acid;
Described mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride or the water of mass concentration 20-40%;
Described organic amine template is a di-n-propylamine, Diisopropylamine, n-Butyl Amine 99, triethylamine, triethyl tetramine, diethyl triamine, Tributylamine, one or more in diethylamine or the hexamethyl time tetramine;
Described aluminium source is one or more in aluminum isopropylate, aluminum chloride, the pseudo-boehmite;
With Al in the aluminium source
2O
3The content meter, the mol ratio in quaternary ammonium salt cationic and aluminium source is 2.0 ~ 40 in the eutectic mixture;
The mol ratio in phosphorus source and aluminium source is 0.6 ~ 3.0;
The mol ratio in silicon source and aluminium source is 0.05 ~ 0.6;
The mol ratio in mineralizer and aluminium source is 0.1 ~ 1.2;
The mol ratio in template and aluminium source is 0.1 ~ 5.0;
3) with step 2) preparation reaction mixture uncovered crystallization in glassware; Or in the teflon-lined stainless steel cauldron airtight crystallization, crystallization temperature is 130 ~ 220 ° of C, crystallization time is more than 10 minutes;
4) the reacted reactants water of step 3) is chilled to room temperature, behind deionized water repetitive scrubbing sample, separates the white powder that obtains after the oven dry roasting of back and be said aluminium silicophosphate molecular sieve; Recycle after receiving the filtrating rotary evaporation after washing.
2. according to the described method of claim 1, it is characterized in that main processes comprises:
1) preparation of eutectic mixture
With quaternary ammonium salt and organic acid or organic alcohol abundant ground and mixed in mortar, place beaker then 80～180
oC heating down makes it to be melted into transparent liquid, makes eutectic mixture;
Described quaternary ammonium salt is one or more in etamon chloride, 4-propyl bromide, the Tetrabutyl amonium bromide;
Described organic acid/organic alcohol is Hydrocerol A, one or more in the tetramethylolmethane,
Quaternary ammonium salt and organic acid in the described eutectic mixture/organic pure blended molar ratio is 0.2 ~ 8;
2) preparation of crystallization mixture
Phosphorus source, silicon source, mineralizer and template, aluminium source are joined in the eutectic mixture of fusing successively, in 105 ~ 140 ° of C blend temperature range; Stir, form reaction mixture;
Described phosphorus source be in the phosphoric acid, ammonium phosphate of mass concentration 50 ~ 85% one or more;
Described silicon source is one or more in silicon sol, water glass, tetraethoxy, WHITE CARBON BLACK, the superfine silicon dioxide powder;
Described mineralizer is the Neutral ammonium fluoride of mass concentration 20-40% or in the water one or more;
Described organic amine template is a di-n-propylamine, Diisopropylamine, n-Butyl Amine 99, triethylamine, triethyl tetramine, diethyl triamine, Tributylamine, one or more in the diethylamine;
Described aluminium source is one or more in aluminum isopropylate, aluminum chloride, the pseudo-boehmite;
With Al in the aluminium source
2O
3The content meter, the mol ratio in quaternary ammonium salt cationic and aluminium source is 3 ~ 20 in the eutectic mixture;
The mol ratio in phosphorus source and aluminium source is 0.9 ~ 1.1;
The mol ratio in silicon source and aluminium source is 0.15 ~ 0.5;
The mol ratio in mineralizer and aluminium source is 0.6 ~ 0.8;
The mol ratio in template and aluminium source is 0.3 ~ 3.0;
3) with step 2) preparation reaction mixture airtight crystallization in the teflon-lined stainless steel cauldron, crystallization temperature is 150 ~ 190 ° of C, crystallization time is 2 ~ 12 hours.
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| CN103539146A (en) * | 2013-10-28 | 2014-01-29 | 中国海洋石油总公司 | Ion hot method for continuously synthesizing SAPO-11 molecular sieves |
| CN103553076A (en) * | 2013-10-28 | 2014-02-05 | 中国海洋石油总公司 | Method for continuously producing silicoaluminophosphate (SAPO-5) molecular sieve |
| CN103979574A (en) * | 2014-06-05 | 2014-08-13 | 郑州大学 | Method for synthesizing molecular sieve by using solid phase |
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| CN103553076A (en) * | 2013-10-28 | 2014-02-05 | 中国海洋石油总公司 | Method for continuously producing silicoaluminophosphate (SAPO-5) molecular sieve |
| CN103539146B (en) * | 2013-10-28 | 2015-06-24 | 中国海洋石油总公司 | Ion hot method for continuously synthesizing SAPO-11 molecular sieves |
| CN103539146A (en) * | 2013-10-28 | 2014-01-29 | 中国海洋石油总公司 | Ion hot method for continuously synthesizing SAPO-11 molecular sieves |
| CN103979574B (en) * | 2014-06-05 | 2016-03-30 | 郑州大学 | The method of solid phase synthesis molecular sieve |
| CN103979574A (en) * | 2014-06-05 | 2014-08-13 | 郑州大学 | Method for synthesizing molecular sieve by using solid phase |
| CN104722331B (en) * | 2014-12-13 | 2017-02-01 | 济南大学 | Preparation method of Cu-SAPO-44 microporous molecular sieve and application thereof as NH3-SCR catalyst |
| CN104722331A (en) * | 2014-12-13 | 2015-06-24 | 济南大学 | Preparation method of Cu-SAPO-44 microporous molecular sieve and application thereof as NH3-SCR catalyst |
| CN105753006B (en) * | 2014-12-17 | 2018-09-25 | 中国科学院大连化学物理研究所 | A kind of preparation of AEL structure multi-stage porous silicoaluminophosphamolecular molecular sieves and molecular sieve |
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| CN106366005A (en) * | 2016-08-08 | 2017-02-01 | 河南工业大学 | Method for preparing eutectic solvent through ball milling |
| CN108017068B (en) * | 2016-11-03 | 2021-01-22 | 神华集团有限责任公司 | SAPO-11 molecular sieve and preparation method thereof, and hydroisomerization catalyst and preparation method thereof |
| CN108017068A (en) * | 2016-11-03 | 2018-05-11 | 神华集团有限责任公司 | A kind of SAPO-11 molecular sieves and preparation method thereof and hydroisomerization catalyst and preparation method thereof |
| CN110372005A (en) * | 2019-07-03 | 2019-10-25 | 常州大学 | A method of multi-stage porous aluminium phosphate molecular sieve is synthesized using fluorine ion |
| CN110372005B (en) * | 2019-07-03 | 2022-10-28 | 常州大学 | Method for synthesizing hierarchical pore aluminum phosphate molecular sieve by using fluorine ions |
| CN112456512A (en) * | 2020-12-10 | 2021-03-09 | 聊城大学 | AEL structure hierarchical pore integral silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN112456512B (en) * | 2020-12-10 | 2023-03-21 | 聊城大学 | AEL structure hierarchical pore integral silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN113353948A (en) * | 2021-07-07 | 2021-09-07 | 厦门大学 | SAPO-11 molecular sieve, and preparation method and application thereof |
| CN113353948B (en) * | 2021-07-07 | 2022-05-17 | 厦门大学 | SAPO-11 molecular sieve, and preparation method and application thereof |
| CN114835138A (en) * | 2022-03-17 | 2022-08-02 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
| CN114835138B (en) * | 2022-03-17 | 2024-04-19 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
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