CN109896531A - A kind of preparation method of SAPO-11 molecular sieve - Google Patents
A kind of preparation method of SAPO-11 molecular sieve Download PDFInfo
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- CN109896531A CN109896531A CN201910321002.3A CN201910321002A CN109896531A CN 109896531 A CN109896531 A CN 109896531A CN 201910321002 A CN201910321002 A CN 201910321002A CN 109896531 A CN109896531 A CN 109896531A
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Abstract
The purpose of the present invention is to provide a kind of preparation methods of the SAPO-11 molecular sieve of high-crystallinity, the SAPO-11 molecular sieve has the structure feature of nanometer rods, without containing other mixed crystal in the SAPO-11 molecular sieve of this method preparation, purity with higher, this point is accomplished something difficult and so deserve praise in the synthesis that SAPO-n Series Molecules sieve, and the SAPO-11 molecular sieve of preparation also has very uniform topographic profile, this be conducive to it is subsequent metal-modified, to promote its whole catalytic performance.
Description
Technical field
The invention belongs to SAPO molecular sieve fields, and in particular to a kind of preparation method of SAPO-11 molecular sieve.
Background technique
SAPO-n Series Molecules sieve is a kind of important molecular sieve, according to the record of american documentation literature US4440871,
It is to develop to obtain after introducing Si element on the basis of 1984 in AIPO molecular sieve by lok et al..The introducing of adjoint element silicon,
So that the skeleton of the molecular sieve analog shows elecrtonegativity, so that carrying out ion load to it becomes possible.People usually press
According to SAPO-n Series Molecules sieve framework mesoporous diameter size, be divided into micropore (SAPO-16,20,25), aperture (SAPO-17,34,
44,47), the types such as mesoporous (SAPO-11,31,41) and macropore (SAPO-5,36,37,40).
Each type of molecular sieve all has oneself unique application field, such as the common SAPO-34 of people, has very
Good MTO catalytic performance；SAPO-5 is usually used in cracking reaction, alkylated reaction etc.；SAPO-11 is usually used in n-butene isomery and length
In chain n-alkane hydro-refining isomery reaction.
The synthetic method of SAPO-n molecular sieve is substantially all similar, and the main distinction is the accurate control to response parameter.Greatly
Range for, synthetic method all mainly includes hydrothermal synthesis method, microwave process for synthesizing, two-phase synthesis method, gas phase crystallization method, molten
Agent thermal synthesis method, ultrasonic or solid-phase synthesis etc.；Specifically, for each specific molecular sieve,
Synthetic method is again there is ever-changing, although as being all hydrothermal synthesis method, raw material used in every kind of molecular sieve is different
(including silicon source, silicon source, phosphorus source, template etc.), crystallization parameter are different, and the result being likely to be obtained is all entirely different, this is namely
Easily there is the reason of mixed crystal phenomenon when synthesizing SAPO-n molecular sieve.
The purpose of the present invention is to provide a kind of preparation method of the SAPO-11 molecular sieve of high-crystallinity, which divides
Sub- sifter device has the structure feature of nanometer rods.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of the SAPO-11 molecular sieve of high-crystallinity, which divides
Sub- sifter device has the structure feature of nanometer rods, and other mixed crystal are not contained in the SAPO-11 molecular sieve of this method preparation, are had higher
Purity, this point in the synthesis that SAPO-n Series Molecules sieve accomplish something difficult and so deserve praise, and prepare SAPO-11 molecular sieve also have very
Uniform topographic profile, this be conducive to it is subsequent metal-modified, to promote its whole catalytic performance.
The preparation method of SAPO-11 molecular sieve provided by the invention, comprises the steps of:
1) first silicon source, silicon source, phosphoric acid, template and deionized water are mixed in proportion, obtains pre- crystallization liquid；
2) pre- crystallization liquid is placed in microwave reactor and carries out initial reaction；
3) by after microwave reaction solution take out, then add suitable water, with maintain H2O/SiO2 40-70 it
Between, and adjust the pH of reaction solution in 5.4-6.0 or so, then, then the mixed solution is transferred in hydrothermal reaction kettle, by one
After the reaction fixed time, reaction kettle is taken out, conventional centrifugation, washing are carried out to product；
4) the SAPO-11 molecular sieve after above-mentioned washing is calcined at 500-600 DEG C 5-10h, can be obtained with nanometer rods
The SAPO-11 molecular sieve of type.
Silicon source used in the present invention is boehmite, and silicon source is silica solution, and template is diethylamine and diisopropylamine
Mixture, by its volume ratio 1:0.1-0.2 mix.
Preferably, in step 1), silicon source used, silicon source, the molar ratio of phosphoric acid, template and deionized water are as follows: 1:1.2-
2.0:1.2-1.8:1.1-1.5:40-70；In step 2, the microwave power used is 550-700W, and the microwave crystallization time is 10-
30min；In step 3), the hydrothermal reaction condition is to react 12-24h at 160-200 DEG C.
According to the inventors knowledge, by the way that compared with prior art, the present invention achieves a series of advantageous effects:
1) by changing the type of template, especially with the template that diethylamine and diisopropylamine mix, height has been prepared
The SAPO-11 molecular sieve of crystallinity；
2) the SAPO-11 molecular sieve prepared by has uniform nano bar-shape structure；
3) by the change to reaction condition, the SAPO-11 molecular sieve without containing mixed crystal has been prepared.
Detailed description of the invention
Fig. 1 SAPO-11 molecular sieve scanning electron micrograph prepared by the present invention；
The graph of pore diameter distribution of Fig. 2 SAPO-11 molecular sieve prepared by the present invention.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
A kind of preparation method of SAPO-11 molecular sieve, comprises the steps of:
1) first silicon source, silicon source, phosphoric acid, template and deionized water are mixed in proportion, obtains pre- crystallization liquid；
2) pre- crystallization liquid is placed in microwave reactor and carries out initial reaction；
3) by after microwave reaction solution take out, then add suitable water, with maintain H2O/SiO2 40-70 it
Between, and adjust the pH of reaction solution in 5.4-6.0 or so, then, then the mixed solution is transferred in hydrothermal reaction kettle, by one
After the reaction fixed time, reaction kettle is taken out, conventional centrifugation, washing are carried out to product；
4) the SAPO-11 molecular sieve after above-mentioned washing is calcined at 500-600 DEG C 5-10h, can be obtained with nanometer rods
The SAPO-11 molecular sieve of type.
Silicon source used in the present invention is boehmite, and silicon source is silica solution, and template is diethylamine and diisopropylamine
Mixture, by its volume ratio 1:0.1-0.2 mix.
Preferably, in step 1), silicon source used, silicon source, the molar ratio of phosphoric acid, template and deionized water are as follows: 1:1.2-
2.0:1.2-1.8:1.1-1.5:40-70；In step 2, the microwave power used is 550-700W, and the microwave crystallization time is 10-
30min；In step 3), the hydrothermal reaction condition is to react 12-24h at 160-200 DEG C.
Fig. 1 is the SEM photograph of SAPO-11 molecular sieve prepared by the present invention under different multiplying；Fig. 2 is implementation of the present invention
The graph of pore diameter distribution of the SAPO-11 molecular sieve of example 1-5 preparation.
Embodiment 1
The ratio that molar ratio according to silicon source, silicon source, phosphoric acid, template and deionized water is 1:1.2:1.2:1.1:40 first weighs
And configure pre- crystallization liquid, wherein the volume ratio of diethylamine and diisopropylamine is 1:0.1；Then the pre- crystallization liquid is transferred to micro-
In wave reactor, radioreaction 10min, is then taken out at 600W, adds suitable deionized water, maintains H2O/SiO2=40,
And pH=5.5 of reaction system are adjusted, later, which is transferred in hydrothermal reaction kettle, reacts 20h at 180 DEG C,
After reaction, after being centrifuged, washing, which is calcined to 6h in 550 DEG C of sintering furnace and obtains SAPO-11 points
Son sieve.
Embodiment 2
The ratio that molar ratio according to silicon source, silicon source, phosphoric acid, template and deionized water is 1:1.5:1.3:1.2:45 first weighs
And configure pre- crystallization liquid, wherein the volume ratio of diethylamine and diisopropylamine is 1:0.1；Then the pre- crystallization liquid is transferred to micro-
In wave reactor, radioreaction 10min, is then taken out at 600W, adds suitable deionized water, maintains H2O/SiO2=45,
And pH=5.5 of reaction system are adjusted, later, which is transferred in hydrothermal reaction kettle, reacts 20h at 180 DEG C,
After reaction, after being centrifuged, washing, which is calcined to 6h in 550 DEG C of sintering furnace and obtains SAPO-11 points
Son sieve.
Embodiment 3
The ratio that molar ratio according to silicon source, silicon source, phosphoric acid, template and deionized water is 1:1.8:1.5:1.5:60 first weighs
And configure pre- crystallization liquid, wherein the volume ratio of diethylamine and diisopropylamine is 1:0.1；Then the pre- crystallization liquid is transferred to micro-
In wave reactor, radioreaction 10min, is then taken out at 600W, adds suitable deionized water, maintains H2O/SiO2=60,
And pH=5.5 of reaction system are adjusted, later, which is transferred in hydrothermal reaction kettle, reacts 20h at 180 DEG C,
After reaction, after being centrifuged, washing, which is calcined to 6h in 550 DEG C of sintering furnace and obtains SAPO-11 points
Son sieve.
Embodiment 4
The ratio that molar ratio according to silicon source, silicon source, phosphoric acid, template and deionized water is 1:1.2:1.2:1.1:40 first weighs
And configure pre- crystallization liquid, wherein the volume ratio of diethylamine and diisopropylamine is 1:0.15；Then the pre- crystallization liquid is transferred to micro-
In wave reactor, radioreaction 10min, is then taken out at 600W, adds suitable deionized water, maintains H2O/SiO2=40,
And pH=5.5 of reaction system are adjusted, later, which is transferred in hydrothermal reaction kettle, reacts 20h at 180 DEG C,
After reaction, after being centrifuged, washing, which is calcined to 6h in 550 DEG C of sintering furnace and obtains SAPO-11 points
Son sieve.
Embodiment 5
The ratio that molar ratio according to silicon source, silicon source, phosphoric acid, template and deionized water is 1:1.2:1.2:1.1:40 first weighs
And configure pre- crystallization liquid, wherein the volume ratio of diethylamine and diisopropylamine is 1:0.1；Then the pre- crystallization liquid is transferred to micro-
In wave reactor, radioreaction 6min, is then taken out at 700W, adds suitable deionized water, maintains H2O/SiO2=40,
And pH=5.5 of reaction system are adjusted, later, which is transferred in hydrothermal reaction kettle, reacts 20h at 180 DEG C,
After reaction, after being centrifuged, washing, which is calcined to 6h in 550 DEG C of sintering furnace and obtains SAPO-11 points
Son sieve.
Comparative example 1
The ratio that molar ratio according to silicon source, silicon source, phosphoric acid, template and deionized water is 1:1.2:1.2:1.1:40 first weighs
And configure pre- crystallization liquid, wherein the volume ratio of di-n-propylamine and diisopropylamine is 1:0.1；Then the pre- crystallization liquid is transferred to
In microwave reactor, radioreaction 10min, is then taken out at 600W, adds suitable deionized water, maintain H2O/SiO2=
40, and pH=5.5 of reaction system are adjusted, later, which is transferred in hydrothermal reaction kettle, is reacted at 180 DEG C
The molecular screen primary powder after being centrifuged, washing, 6h is calcined in 550 DEG C of sintering furnace and obtains SAPO- by 20h after reaction
11 molecular sieves, but the SAPO-11 molecular sieve is not nano-rod shaped.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
Claims (7)
1. a kind of preparation method of SAPO-11 molecular sieve, which is characterized in that comprise the steps of:
1) first silicon source, silicon source, phosphoric acid, template and deionized water are mixed in proportion, obtains pre- crystallization liquid；
2) pre- crystallization liquid is placed in microwave reactor and carries out initial reaction；
3) by after microwave reaction solution take out, then add suitable water, with maintain H2O/SiO2 40-70 it
Between, and adjust the pH of reaction solution in 5.4-6.0 or so, then, then the mixed solution is transferred in hydrothermal reaction kettle, by one
After the reaction fixed time, reaction kettle is taken out, conventional centrifugation, washing are carried out to product；
4) the SAPO-11 molecular sieve after above-mentioned washing is calcined at 500-600 DEG C 5-10h, can be obtained with nanometer rods
The SAPO-11 molecular sieve of type.
2. a kind of preparation method of SAPO-11 molecular sieve according to claim 1, it is characterised in that: silicon source used is
Boehmite, silicon source are silica solution.
3. a kind of preparation method of SAPO-11 molecular sieve according to claim 1, it is characterised in that: template used
For the mixture of diethylamine and diisopropylamine, mixed by its volume ratio 1:0.1-0.2.
4. a kind of preparation method of SAPO-11 molecular sieve according to claim 1, it is characterised in that: used in step 1)
Silicon source, silicon source, the molar ratio of phosphoric acid, template and deionized water are as follows: 1:1.2-2.0:1.2-1.8:1.1-1.5:40-70.
5. a kind of preparation method of SAPO-11 molecular sieve according to claim 1, it is characterised in that: in step 2, use
Microwave power be 550-700W, the microwave crystallization time be 10-30min.
6. a kind of preparation method of SAPO-11 molecular sieve according to claim 1, it is characterised in that: described in step 3)
Hydrothermal reaction condition be 160-200 DEG C at react 12-24h.
7. a kind of nano-rod shaped SAPO-11 molecular sieve prepared by any one of claim 1-6 the method.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100119736A1 (en) * | 2008-10-07 | 2010-05-13 | The Regents Of The University Of California | Ambient pressure synthesis of zeolite films and their application as corrosion resistant coatings |
| CN102746102A (en) * | 2012-07-26 | 2012-10-24 | 黑龙江大学 | Preparation method of 2,6-DiMethylnaphthalene (DMN) by using SAPO-11 molecular sieve |
| CN103408031A (en) * | 2013-08-23 | 2013-11-27 | 黑龙江大学 | Microwave heating synthesis method of SAPO (Silicoaluminophosphate)-41 molecular sieve |
| CN103523795A (en) * | 2013-11-07 | 2014-01-22 | 黑龙江大学 | Method for preparing SAPO-11 molecular sieve |
| 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 |
| CN106809862A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method and its molecular sieve for preparing multi-stage porous SAPO-11 molecular sieves |
-
2019
- 2019-04-21 CN CN201910321002.3A patent/CN109896531A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100119736A1 (en) * | 2008-10-07 | 2010-05-13 | The Regents Of The University Of California | Ambient pressure synthesis of zeolite films and their application as corrosion resistant coatings |
| CN102746102A (en) * | 2012-07-26 | 2012-10-24 | 黑龙江大学 | Preparation method of 2,6-DiMethylnaphthalene (DMN) by using SAPO-11 molecular sieve |
| CN103408031A (en) * | 2013-08-23 | 2013-11-27 | 黑龙江大学 | Microwave heating synthesis method of SAPO (Silicoaluminophosphate)-41 molecular sieve |
| 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 |
| CN103523795A (en) * | 2013-11-07 | 2014-01-22 | 黑龙江大学 | Method for preparing SAPO-11 molecular sieve |
| CN106809862A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method and its molecular sieve for preparing multi-stage porous SAPO-11 molecular sieves |
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