CN101302015A - Method for synthesizing SAPO-5 with diethylamine as a template and recovering template - Google Patents
Method for synthesizing SAPO-5 with diethylamine as a template and recovering template Download PDFInfo
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- CN101302015A CN101302015A CNA2008100435328A CN200810043532A CN101302015A CN 101302015 A CN101302015 A CN 101302015A CN A2008100435328 A CNA2008100435328 A CN A2008100435328A CN 200810043532 A CN200810043532 A CN 200810043532A CN 101302015 A CN101302015 A CN 101302015A
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- diethylamine
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Abstract
The invention provides a method for synthesizing SAPO-5 by using diethylamine as template and recovering the template of the SAPO-5. The structural formula of the SAPO-5 is represented by aR x (SixAlyPz)O2, wherein, the x, y and z are a molar fraction of Si, a molar fraction of Al and a molar fraction of P respectively, and meet a relation of x+y+z =1; the R is the template; and the a is the mole number of the template, and a is between 0.5 and 2.5. The invention is characterized in that: the template adopts the diethylamine or mixture of nitrogenous organic substances mainly containing the diethylamine ; and the method comprises the following steps of: weighing the template, a silicon source, an aluminium source, a phosphorus source and water according to the mole amount of H2O on a molecular sieve with meshes between 0 and 500; preparing gel through sufficiently mixing and stirring the materials; crystallizing the gel at a temperature of between 160 and 350 DEG C with a reaction time not shorter than 0.1 hour; filtering, washing and drying after complete crystallization, and performing drying under a temperature of between 25 and 120 DEG C; heating up the gel to a temperature not higher than 250 DEG C after molecular sieve synthesis, and condensing and volatilizing diethylamine template which can be reused. The method has the advantages of simple preparation method, low cost and high product yield.
Description
Technical field
The present invention relates to a kind of novel environment friendly synthetic method of SAPO-5 molecular sieve, specifically having provided a kind of is the synthetic and template recovery method of phosphorus aluminium silicon SAPO-5 molecular sieve of main template with diethylamine under comparatively high temps.
Background technology
Phosphorus sial SAPO-5 molecular sieve is made up of phosphorus, silicon, aluminium and oxygen.The SAPO-5 molecular sieve has 12 yuan of ring straight hole roads, and moderate acidity and higher thermostability have special performance at aspects such as catalysis, absorption, assemblings and come into one's own.
The synthetic use organic formwork agent that needs of SAPO-5 molecular sieve comprises triethylamine, tripropyl amine, different tripropyl amine etc.These template molecule sizes and SAPO-5 duct size 0.73nm have better coupling, thereby help the synthetic of SAPO-5 as template.Because these template sizes are bigger, after synthesizing the SAPO-5 structure, the template in the SAPO-5 duct must could thoroughly be removed behind oxidizing fire under the high-temperature roasting condition but simultaneously.This has just caused template to recycle, and also causes the synthetic cost of SAPO-5 higher.The low-cost synthetic recovery method that reaches template of SAPO-5 molecular sieve at present, at home and abroad there is no relevant report and patent application.
Summary of the invention
The purpose of this invention is to provide simple, lower-cost SAPO-5 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 irretrievable shortcoming of template, expanded SAPO-5 preparation temperature scope.The key factor that the present invention is different from ordinary method just is that the diethylamine with less molecular dimension is the master module agent, in big may command crystallization temperature scope, synthesizes the SAPO-5 crystal, and diethylamine template is wherein recycled.
Diethylamine is synthetic SAPO-5 of template and template recovery method, and 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, a=0.5～2.5; It is characterized in that: template adopts diethylamine, or based on the itrogenous organic substance mixture of diethylamine, specifically building-up process and template recovery method are as follows:
(1) according to molecular sieve: 0～500H
2The molar weight of O takes by weighing template, silicon source, aluminium source, phosphorus source and water;
(2), fully stir again and make gel with above-mentioned each mixing of materials;
(3) with gel in 160～350 ℃ 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;
(5) molecular sieve can not be higher than 250 ℃ of heating down after synthesizing, and condensation volatilizes the diethylamine template, can reuse the diethylamine template.
Described silicon source can be silicon sol, active silica or positive silicon ester; Described aluminium source can be aluminum alkoxide, false thin nurse stone or activated alumina; Described phosphorus source can be ortho-phosphoric acid, aluminum phosphate.
Employed template be diethylamine or with the diethylamine be main and following any one or more composition mixture: triethylamine, tripropyl amine, tetraethyl ammonium hydroxide, TPAOH, TBAH, Tetramethylammonium hydroxide, Trimethylamine 99, n-Butyl Amine 99, isopropylamine, di-n-propylamine, diethanolamine, pyridine, pyrroles, quinoline etc.
The storage that the low cost S APO-5 material that the present invention obtains is mainly used in cracking catalyst, gas separates with mixed gas.
Advantage of the present invention and positively effect are: crystallization time is short, efficiency of pcr product is high, template is recyclable, and the preparation method is simple, with low cost.
Description of drawings
Fig. 1 is the XRD figure that embodiment 3 obtains the SAPO-5 sample;
Fig. 2 is the SEM figure that embodiment 3 obtains the SAPO-5 sample;
Embodiment
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 345 ℃ of heating 0.2 hour 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-5 material in retort furnace.Obtain 4～10 microns of SAPO-5 grain sizes, efficiency of pcr product is 99%.After reclaiming diethylamine under 250 ℃, with containing the diethylamine template hardly in the infrared experiment demonstration SAPO-5 duct.
Embodiment 2
Routine in molar ratio Al (OH)
3: 0.5H
3PO
4: 0.1SiO
2: 0.5R: 10H
2The diethylamine and the triethylamine raw material of O mixing aluminum isopropylate, phosphoric acid, tetraethoxy and 8: 1.The 165 ℃ of heating 48 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-5 material in retort furnace.Obtain 0.5～5 micron of SAPO-5 grain size, efficiency of pcr product is 65%.Behind 250 ℃ of following recovery part diethylamine, with also containing the minute quantity template in the infrared experiment demonstration SAPO-5 duct.
Embodiment 3
Routine in molar ratio Al (OH)
3: 1H
3PO
4: 0.5SiO
2: 1R: 100H
2The diethylamine and the tetraethyl ammonium hydroxide raw material of O mixing aluminum isopropylate, phosphoric acid, silicon sol and 16: 1.The 300 ℃ of heating 2 hours in baking oven of sealing back.Dry behind the suction filtration, 400 ℃ of roastings 12 hours under the oxygen atmosphere can obtain the SAPO-5 material in retort furnace.Obtain 1～3 micron of SAPO-5 grain size, efficiency of pcr product is 98%.The XRD of the SAPO-5 that obtains and SEM such as attached illustrated in figures 1 and 2.Behind 250 ℃ of following recovery part diethylamine, with also containing the minute quantity template in the infrared experiment demonstration SAPO-5 duct.
Claims (3)
1. diethylamine is synthetic SAPO-5 of template and template recovery method, and 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, a=0.5～2.5; It is characterized in that: template adopts diethylamine, or based on the itrogenous organic substance mixture of diethylamine, specifically building-up process and template recovery method are as follows:
(1) according to molecular sieve: 0～500H
2The molar weight of O takes by weighing template, silicon source, aluminium source, phosphorus source and water;
(2), fully stir again and make gel with above-mentioned each mixing of materials;
(3) with gel in 160～350 ℃ of crystallization, the crystallization time is not shorter than 0.1 hour;
(4) the complete after-filtration of crystallization, washing, drying, drying can be carried out under 25～120 ℃ of conditions.
(5) after molecular sieve synthesizes, can not be higher than 250 ℃ of heating down, condensation volatilizes the diethylamine template, can reuse the diethylamine template.
2. be synthetic SAPO-5 of template and template recovery method by the described diethylamine of claim 1, it is characterized in that: described silicon source can be silicon sol, active silica or positive silicon ester; Described aluminium source can be aluminum alkoxide, false thin nurse stone or activated alumina; Described phosphorus source can be ortho-phosphoric acid, aluminum phosphate.
3. be synthetic SAPO-5 of template and template recovery method by the described diethylamine of claim 1, it is characterized in that: employed template be diethylamine or with the diethylamine be main and following any one or more composition mixture: triethylamine, tripropyl amine, tetraethyl ammonium hydroxide, TPAOH, TBAH, Tetramethylammonium hydroxide, Trimethylamine 99, n-Butyl Amine 99, isopropylamine, di-n-propylamine, diethanolamine, pyridine, pyrroles, quinoline etc.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100435328A CN101302015A (en) | 2008-06-20 | 2008-06-20 | Method for synthesizing SAPO-5 with diethylamine as a template and recovering template |
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|---|---|---|---|
| CNA2008100435328A CN101302015A (en) | 2008-06-20 | 2008-06-20 | Method for synthesizing SAPO-5 with diethylamine as a template and recovering template |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993095A (en) * | 2010-10-28 | 2011-03-30 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
| CN101734684B (en) * | 2008-11-26 | 2011-11-09 | 中国科学院过程工程研究所 | Method for preparing SAPO-5 molecular sieve from kaoline |
| CN102372287A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | SAPO (Silicoaluminophosphate)-5 molecular sieve and production method thereof |
| CN102389833A (en) * | 2011-09-23 | 2012-03-28 | 辽阳华程化工有限公司 | Catalyst for preparing low-carbon olefin from light dydrocarbon and methanol mixtures |
| CN102424399A (en) * | 2011-09-05 | 2012-04-25 | 中国科学院过程工程研究所 | Preparation process for aluminosilicophosphate molecular sieve |
| CN102657955A (en) * | 2012-05-23 | 2012-09-12 | 安徽淮化股份有限公司 | Method for recycling template agent in improved methanol to propylene catalyst production process |
| CN103030154A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Synthesis method of silicoaluminophosphate (SAPO)-5 and SAPO-44 symbiotic molecular sieve |
| CN105110348A (en) * | 2010-12-29 | 2015-12-02 | 中国科学院大连化学物理研究所 | Solvothermal synthesis method of SAPO molecular sieve and catalyst using same |
| CN103787370B (en) * | 2013-12-31 | 2016-04-13 | 中国天辰工程有限公司 | The recovery method of template in a kind of molecular sieve process |
| CN108910913A (en) * | 2018-08-30 | 2018-11-30 | 南京大学 | A kind of two-dimensional ultrathin SAPO-5 molecular sieve sheeting and preparation method thereof |
-
2008
- 2008-06-20 CN CNA2008100435328A patent/CN101302015A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734684B (en) * | 2008-11-26 | 2011-11-09 | 中国科学院过程工程研究所 | Method for preparing SAPO-5 molecular sieve from kaoline |
| CN102372287A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | SAPO (Silicoaluminophosphate)-5 molecular sieve and production method thereof |
| CN102372287B (en) * | 2010-08-23 | 2013-01-09 | 中国石油化工股份有限公司 | SAPO (Silicoaluminophosphate)-5 molecular sieve and production method thereof |
| CN101993095A (en) * | 2010-10-28 | 2011-03-30 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
| CN101993095B (en) * | 2010-10-28 | 2012-06-27 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
| CN105110348A (en) * | 2010-12-29 | 2015-12-02 | 中国科学院大连化学物理研究所 | Solvothermal synthesis method of SAPO molecular sieve and catalyst using same |
| CN102424399B (en) * | 2011-09-05 | 2014-04-02 | 中国科学院过程工程研究所 | Preparation process for aluminosilicophosphate molecular sieve |
| CN102424399A (en) * | 2011-09-05 | 2012-04-25 | 中国科学院过程工程研究所 | Preparation process for aluminosilicophosphate molecular sieve |
| CN102389833A (en) * | 2011-09-23 | 2012-03-28 | 辽阳华程化工有限公司 | Catalyst for preparing low-carbon olefin from light dydrocarbon and methanol mixtures |
| CN103030154A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Synthesis method of silicoaluminophosphate (SAPO)-5 and SAPO-44 symbiotic molecular sieve |
| CN102657955A (en) * | 2012-05-23 | 2012-09-12 | 安徽淮化股份有限公司 | Method for recycling template agent in improved methanol to propylene catalyst production process |
| CN103787370B (en) * | 2013-12-31 | 2016-04-13 | 中国天辰工程有限公司 | The recovery method of template in a kind of molecular sieve process |
| CN108910913A (en) * | 2018-08-30 | 2018-11-30 | 南京大学 | A kind of two-dimensional ultrathin SAPO-5 molecular sieve sheeting and preparation method thereof |
| CN108910913B (en) * | 2018-08-30 | 2021-09-28 | 南京大学 | Two-dimensional ultrathin SAPO-5 molecular sieve sheet material and preparation method thereof |
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Open date: 20081112 |