CN101531377A - High-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34 - Google Patents
High-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34 Download PDFInfo
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- CN101531377A CN101531377A CN200810038742A CN200810038742A CN101531377A CN 101531377 A CN101531377 A CN 101531377A CN 200810038742 A CN200810038742 A CN 200810038742A CN 200810038742 A CN200810038742 A CN 200810038742A CN 101531377 A CN101531377 A CN 101531377A
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Abstract
The invention relates to a high-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34, the structural formula of which can be expressed by aR (SixAly Pz) O2, wherein x, y and z are respectively the mole fractions of Si, Al and P, and the template agent R is a nitrogen-containing organic compound of diethylamine and triethylamine or taking the diethylamine and the triethylamine as main material; the synthesis process is as follows: according to the molar volume of a molecular sieve: 0-500H2O, the template agent, silicon source, aluminum source, phosphorus source and water are respectively weighed and taken out; the materials are mixed and fully stirred so as to prepare gel; the gel is crystallized at the temperature of 250-350 DEG C for 0.1 to 12 hours; the gel is filtered after being crystallized completely, and then washed by water and dried while the drying can be implemented at the temperature of 25-120 DEG C. The method of the invention has short crystallization time, high product yield, small synthesis grain, and is simple and suitable for large-scale production and application.
Description
Technical field
The present invention relates to a kind of phosphorus aluminium silicon SAPO-34 and synthetic method thereof, be specifically related to a kind ofly be higher than under the conventional hydrothermal crystallizing temperature phosphorus aluminium silicon SAPO-34 fast and high-efficiency synthesis method.
Background technology
Synthetic phosphorus sial SAPO-34 molecular sieve is a kind ofly to be made up of phosphorus, silicon, aluminium and oxygen, has the molecular sieve of class chabazite structure.The SAPO-34 molecular sieve has elliposoidal basket structure that 8 yuan of annular distance mouths form and moderate acidity, shows excellent catalytic performance and come into one's own in methanol-to-olefins (MTO) technology.
European patent EP 0103117 discloses a kind of SAPO-34 molecular sieve hydrothermal synthesis method commonly used, and one of its technical characterstic is to have used tetraethyl ammonium hydroxide, Isopropylamine in the building-up process or be template with the mixture of tetraethyl ammonium hydroxide and di-n-propylamine.U.S. Pat 4440871 has reported that relevant SAPO-34 molecular sieve synthetic improves one's methods, but adopts identical more expensive tetraethyl ammonium hydroxide template.Because these template cost an arm and a leg, it is more limited to originate, and is difficult to large-scale production.
Having adopted cheap triethylamine among the Chinese patent CN1037334C is the method for the synthetic SAPO-34 molecular sieve of template, and synthesis temperature is for being lower than 225 ℃, and generated time is generally greater than 50 hours, and single template synthesizes crystal grain big (particle diameter is greater than 4 microns).Adopted the synthetic SAPO-34 of diethylamine template of another kind of cheapness among the Chinese patent CN1038125C, synthesis temperature is lower than 250 ℃, and crystallization time was greater than 45 hours, and it is also bigger that single template synthesizes the SAPO-34 particle diameter.When catalyzed reaction, the SAPO-34 particle diameter is too big, will reduce catalytic effect greatly.
Summary of the invention
The purpose of this invention is to provide simple, lower-cost SAPO-34 material of a kind of method and preparation method thereof, overcome that crystallization time is long in the prior art, efficiency of pcr product is low, the unmanageable shortcoming of particle diameter, expanded SAPO-34 preparation temperature scope.The key factor that the present invention is different from ordinary method just is to control crystallization temperature at 250～350 ℃, and crystallization time shortens greatly, and crystal grain is effectively controlled, and efficiency of pcr product can be more than 95% simultaneously.
A kind of high-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34, its structural formula can be used aR (Si
xAl
yP
z) O
2Expression, wherein x, y, z are respectively the molar fraction of Si, Al, P, x=0.01～0.98, y=0.01～0.85, z=0.01～0.80, and satisfy x+y+z=1; R is a template, and a is the mole number of template, and a=0.5～2.5 is characterized in that: template R is diethylamine, triethylamine or based on the itrogenous organic substance mixture of diethylamine, triethylamine; Crystallization temperature is 250～350 ℃; 0.1～12 hour crystallization time, the synthetic process is as described below:
(1) according to molecular sieve: 0～500H
2The molar weight of O takes by weighing template, silicon source, aluminium source, phosphorus source and water respectively;
(2), fully stir again and make gel with above-mentioned each mixing of materials;
(3) with gel in 250～350 ℃ of crystallization, the crystallization time is not shorter than 0.1 hour;
(4) the complete after-filtration of crystallization, again the washing, drying, drying can be carried out under 25～120 ℃ of conditions.
Described itrogenous organic substance mixture is tetraethyl ammonium hydroxide, TPAOH, tripropyl amine, TBAH, Tetramethylammonium hydroxide, Trimethylamine 99, n-Butyl Amine 99, isopropylamine, di-n-propylamine, diethanolamine, pyridine, pyrroles, quinoline.
Described silicon source can be silicon sol, active silica or positive silicon ester, and the aluminium source can be aluminum alkoxide, false thin nurse stone or activated alumina.
Described phosphorus source can be ortho-phosphoric acid, aluminum phosphate.
Described molecular sieve is applied to methyl alcohol as catalyzer or/and dimethyl ether conversion is the low-carbon alkene reaction, also can be used for vehicle exhaust and handles catalyzer or carrier.
Advantage of the present invention and positively effect are: synthetic method is simple, with low cost, and the control crystallization temperature is at 250～350 ℃, and crystallization time shortens greatly, synthetic crystal grain is little, and crystal grain is effectively controlled, simultaneously the efficiency of pcr product height, can be suitable for scale operation and application more than 95%.
Description of drawings
Fig. 1 is the XRD figure that embodiment 3 obtains the SAPO-34 sample;
Fig. 2 is the SEM figure that embodiment 3 obtains the SAPO-34 sample.
Embodiment
The invention will be further described below in conjunction with drawings and Examples, but present embodiment is not limited to the present invention, and every employing analog structure of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
Embodiment 1
Routine in molar ratio Al (OH)
3: 2H
3PO
4: 1SiO
2: 2R:500H
2O mixing pseudo-boehmite, phosphoric acid, white carbon black and diethylamine raw material.The 255 ℃ of heating 12 hours in baking oven of mixing and stirring, sealing back.Dry behind the suction filtration, 600 ℃ of roastings 24 hours under the air atmosphere can obtain the SAPO-34 material in retort furnace.Obtain 1～2 micron of SAPO-34 grain size, efficiency of pcr product is 95%.
Embodiment 2
Routine in molar ratio Al (OH)
3: 0.3H
3PO
4: 0.1SiO
2: 0.5R:10H
2The diethylamine of O mixing aluminum isopropylate, phosphoric acid, methyl silicate and 2:1 and triethylamine raw material.The 300 ℃ of heating 5 hours in baking oven of mixing and stirring, sealing back.Dry behind the suction filtration, 900 ℃ of roastings 12 hours under the air atmosphere can obtain the SAPO-34 material in retort furnace.Obtain 0.5～1.5 micron of SAPO-34 grain size, efficiency of pcr product is 99%.
Embodiment 3
Routine in molar ratio Al (OH)
3: 1H
3PO
4: 0.5SiO
2: 1R:100H
2The diethylamine of O mixing aluminum isopropylate, phosphoric acid, silicon sol and 4:1 and tetraethyl ammonium hydroxide raw material.The 350 ℃ of heating 0.2 hour in baking oven of sealing back.Dry behind the suction filtration, 400 ℃ of roastings 12 hours under the oxygen atmosphere can obtain the SAPO-34 material in retort furnace.Efficiency of pcr product is 99%.The XRD of the SAPO-34 that obtains and SEM such as attached illustrated in figures 1 and 2.As can be seen from Figure 1, the crystal that obtains is the SAPO-34 pure phase, no stray crystal.As can be seen from Figure 2,2～3 microns of the crystallographic dimensions that obtains are cubic bulk crystals, are typical SAPO-34 crystal morphology.
Claims (5)
1. high-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34, its structural formula can be used aR (Si
xAl
yP
z) O
2Expression, wherein x, y, z are respectively the molar fraction of Si, Al, P, x=0.01～0.98, y=0.01～0.85, z=0.01～0.80, and satisfy x+y+z=1; R is a template, and a is the mole number of template, and a=0.5～2.5 is characterized in that: template R is diethylamine, triethylamine or based on the itrogenous organic substance mixture of diethylamine, triethylamine; Crystallization temperature is 250～350 ℃; 0.1～12 hour crystallization time, the synthetic process is as described below:
(1) according to molecular sieve: 0～500H
2The molar weight of O takes by weighing template, silicon source, aluminium source, phosphorus source and water respectively;
(2), fully stir again and make gel with above-mentioned each mixing of materials;
(3) with gel in 250～350 ℃ of crystallization, the crystallization time is not shorter than 0.1 hour;
(4) the complete after-filtration of crystallization, again the washing, drying, drying can be carried out under 25～120 ℃ of conditions.
2. a kind of high-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34 according to claim 1 is characterized in that: described itrogenous organic substance mixture is tetraethyl ammonium hydroxide, TPAOH, tripropyl amine, TBAH, Tetramethylammonium hydroxide, Trimethylamine 99, n-Butyl Amine 99, isopropylamine, di-n-propylamine, diethanolamine, pyridine, pyrroles, quinoline.
3. a kind of high-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34 according to claim 1 is characterized in that: the silicon source can be silicon sol, active silica or positive silicon ester, and the aluminium source can be aluminum alkoxide, false thin nurse stone or activated alumina.
4. a kind of high-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34 according to claim 1 is characterized in that: the phosphorus source can be ortho-phosphoric acid, aluminum phosphate.
5. a kind of high-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34 according to claim 1, it is characterized in that: described molecular sieve is applied to methyl alcohol as catalyzer or/and dimethyl ether conversion is the low-carbon alkene reaction, also can be used for vehicle exhaust and handles catalyzer or carrier.
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| CN200810038742A CN101531377A (en) | 2008-06-10 | 2008-06-10 | High-temperature hydrothermal synthesis method of phosphorus Al-Si SAPO-34 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336413A (en) * | 2010-11-29 | 2012-02-01 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| CN102974392A (en) * | 2012-11-21 | 2013-03-20 | 西安近代化学研究所 | Mordenite/SAPO-34 composite molecular sieve amination catalyst and method for preparing same |
| CN104271240A (en) * | 2012-04-27 | 2015-01-07 | 赫多特普索化工设备公司 | Process for the direct synthesis of Cu-SAPO-34 |
| CN106044792A (en) * | 2016-05-31 | 2016-10-26 | 南开大学 | SAPO-34 molecular-sieve preparing method simultaneously using crystal microporous aluminum phosphite NKX-6 as phosphorus source and aluminum source |
| CN106082266A (en) * | 2016-05-31 | 2016-11-09 | 南开大学 | The method that two kinds of microporous crystals coordinate conversion to prepare SAPO 34 molecular sieve |
| CN107032364A (en) * | 2016-02-04 | 2017-08-11 | 中国科学院大连化学物理研究所 | A kind of silicoaluminophosphamolecular molecular sieves, its preparation method and application |
| CN107032363A (en) * | 2016-02-04 | 2017-08-11 | 中国科学院大连化学物理研究所 | The new SAPO molecular sieve of one class and its synthetic method |
| CN109179448A (en) * | 2018-08-15 | 2019-01-11 | 潍坊天晟新材料有限公司 | A kind of new method quickly preparing mesoporous small particle size SAPO-34 molecular sieve |
| US10532350B2 (en) | 2014-08-22 | 2020-01-14 | W.R. Grace & Co.-Conn | Method for synthesizing silicoaluminophosphate-34 molecular sieves using monoisopropanolamine |
| CN113354895A (en) * | 2021-05-10 | 2021-09-07 | 宁波聚才新材料科技有限公司 | High-temperature-resistant polypropylene composite material and preparation method thereof |
-
2008
- 2008-06-10 CN CN200810038742A patent/CN101531377A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336413A (en) * | 2010-11-29 | 2012-02-01 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| CN104271240B (en) * | 2012-04-27 | 2017-03-08 | 赫多特普索化工设备公司 | The direct synthesis technique of Cu SAPO 34 |
| CN104271240A (en) * | 2012-04-27 | 2015-01-07 | 赫多特普索化工设备公司 | Process for the direct synthesis of Cu-SAPO-34 |
| CN102974392A (en) * | 2012-11-21 | 2013-03-20 | 西安近代化学研究所 | Mordenite/SAPO-34 composite molecular sieve amination catalyst and method for preparing same |
| CN102974392B (en) * | 2012-11-21 | 2014-08-27 | 西安近代化学研究所 | Mordenite/SAPO-34 composite molecular sieve amination catalyst and method for preparing same |
| US10532350B2 (en) | 2014-08-22 | 2020-01-14 | W.R. Grace & Co.-Conn | Method for synthesizing silicoaluminophosphate-34 molecular sieves using monoisopropanolamine |
| CN107032363B (en) * | 2016-02-04 | 2019-08-02 | 中国科学院大连化学物理研究所 | A kind of novel SAPO molecular sieve and its synthetic method |
| CN107032364A (en) * | 2016-02-04 | 2017-08-11 | 中国科学院大连化学物理研究所 | A kind of silicoaluminophosphamolecular molecular sieves, its preparation method and application |
| CN107032363A (en) * | 2016-02-04 | 2017-08-11 | 中国科学院大连化学物理研究所 | The new SAPO molecular sieve of one class and its synthetic method |
| CN107032364B (en) * | 2016-02-04 | 2019-08-20 | 中国科学院大连化学物理研究所 | A kind of silicoaluminophosphamolecular molecular sieves, preparation method and application |
| CN106044792B (en) * | 2016-05-31 | 2018-03-09 | 南开大学 | A kind of crystalline microporous aluminium phosphite NKX 6 prepares the molecular sieve methods of SAPO 34 as phosphorus source and silicon source simultaneously |
| CN106082266A (en) * | 2016-05-31 | 2016-11-09 | 南开大学 | The method that two kinds of microporous crystals coordinate conversion to prepare SAPO 34 molecular sieve |
| CN106044792A (en) * | 2016-05-31 | 2016-10-26 | 南开大学 | SAPO-34 molecular-sieve preparing method simultaneously using crystal microporous aluminum phosphite NKX-6 as phosphorus source and aluminum source |
| CN109179448A (en) * | 2018-08-15 | 2019-01-11 | 潍坊天晟新材料有限公司 | A kind of new method quickly preparing mesoporous small particle size SAPO-34 molecular sieve |
| CN113354895A (en) * | 2021-05-10 | 2021-09-07 | 宁波聚才新材料科技有限公司 | High-temperature-resistant polypropylene composite material and preparation method thereof |
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