CN101195491A - Method for hoisting degree of silicon entering SAPO-34 molecular sieve framework in synthesized gel rubber - Google Patents
Method for hoisting degree of silicon entering SAPO-34 molecular sieve framework in synthesized gel rubber Download PDFInfo
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- CN101195491A CN101195491A CNA2006101443498A CN200610144349A CN101195491A CN 101195491 A CN101195491 A CN 101195491A CN A2006101443498 A CNA2006101443498 A CN A2006101443498A CN 200610144349 A CN200610144349 A CN 200610144349A CN 101195491 A CN101195491 A CN 101195491A
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Abstract
The invention discloses a process for increasing the degree that silicon in synthetic gel enters the framework of SAPO-34 molecular sieve. The invention is characterized in that diethyl amine is taken as template agent, and simultaneously a specific silicon volume regulator is added to the synthetic gel, thereby achieving the purpose of effectively increasing silicon content of the framework of SAPO-34 molecular sieve. The molecular sieve synthesized by the process of the invention can be used for various acid catalytic reactions, such as the reaction of the conversion of oxygenated compounds to light olefins.
Description
Technical field
The present invention relates to a kind ofly promote that silicon enters SAPO-34 framework of molecular sieve degree methods and the application of this molecular sieve in acid catalyzed reaction in the synthesized gel rubber.
Background technology
1984, U.S. combinating carbide company (UCC) developed silicon aluminium phosphate series SAPO molecular sieve (USP 4440871).This molecular sieve is a class crystalline silicoaluminophosphate salt, and its three-dimensional framework structure is by PO
2 +, AlO
2 -And SiO
2Tetrahedron constitutes.Wherein SAPO-34 is the class chabazite structure, and the main aperture road is made of eight annulus, and the aperture is 0.38nm * 0.38nm.The SAPO-34 molecular sieve is because its proper acidic and pore passage structure, presents excellent catalytic performance and receive much attention in MTO (preparing low carbon olefinic hydrocarbon with methanol) reaction.The initial synthetic used template of SAPO-34 is expensive tetraethyl ammonium hydroxide and Isopropylamine, uses relatively inexpensive morpholine, triethylamine also to synthesize well-crystallized's SAPO-34 molecular sieve afterwards.Chinese patent CNP 1096496 has reported that with diethylamine be the synthetic SAPO-34 molecular sieve of template.
Silicone content in the SAPO molecular sieve is the key factor of its acidity of decision (acid site density and intensity).Along with the increase of silicone content in the framework of molecular sieve, its acid amount and strength of acid also increase gradually.Generally the modulation to the SAPO acidic zeolite is to realize by the silicon amount that changes in the synthesized gel rubber.In addition, same feed molar proportioning, different types of template might influence the silicone content in the final sintetics.By discovering, use diethylamine to be template, in synthesized gel rubber, add specific silicon amount conditioning agent simultaneously, can reach the purpose of silicone content in effective lifting SAPO-34 framework of molecular sieve.Research about this respect yet there are no the open source literature report.
Summary of the invention
The invention provides that silicon enters SAPO-34 framework of molecular sieve degree methods in a kind of lifting synthesized gel rubber, it uses diethylamine to be template, in synthesized gel rubber, add specific silicon amount conditioning agent simultaneously, reach the purpose of silicone content in effective lifting SAPO-34 framework of molecular sieve.
The synthetic method of molecular sieve provided by the invention, its used template is a diethylamine, silicon amount conditioning agent is one or more the mixture in ammoniacal liquor, triethylamine, tetraethyl ammonium hydroxide, beautiful jade, tripropyl amine, Isopropylamine or the Tri N-Propyl Amine.Used phosphorus source is one or more the mixture in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides; The aluminium source is a kind of or any several mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite or the pseudo-boehmite; The silicon source is a kind of or any several mixture in silicon sol, water glass, active silica or the positive silicon ester.
Each proportioning raw materials of preparation SAPO-34 molecular sieve (by the oxide molecule ratio) is in the synthetic method of the present invention: SiO
2/ Al
2O
3=0.01～10;
P
2O
5/Al
2O
3＝0.5～1.5；
H
2O/Al
2O
3＝10～100；
DEA/Al
2O
3=0.05～10 (DEA is a diethylamine);
R/DEA=0～10 (R is a silicon amount conditioning agent).
The crystallization temperature of synthesized gel rubber is 150～220 ℃; Crystallization time is no less than 1 hour, and the best is 6～120 hours.Crystallization pressure is its autogenous pressure or nitrogen, air or the rare gas element etc. that charge into 0.01～1MPa.
Silicon enters SAPO-34 molecular sieve degree methods in the lifting synthesized gel rubber provided by the invention, and concrete preparation process is as follows:
(1) synthesized gel rubber preparation: at first aluminium source material is mixed with deionized water, under agitation phosphoric acid and deionized water solution are added, add silicon-containing material after stirring, add template and silicon amount conditioning agent after continuing to stir again, promptly become the gel for the treatment of crystallization after fully stirring.
(2) gel that obtains in (1) is packed into reactor sealing is warmed up to 150～220 ℃, and crystallization is no less than 1 hour, and the best is 6～120 hours.
(3) solid crystallized product is separated with mother liquor, to neutral, behind 100 ℃ of air dryings, obtain molecular screen primary powder with deionized water wash.
(4) molecular screen primary powder roasting in 550～700 ℃ of air is no less than 3 hours, promptly gets the molecular sieve active catalyst.
Adopting silicone content (mol ratio Si/ (Si+Al+P)) in present method synthetic SAPO-34 molecular sieve is 1.0～2.0 times of silicone content in the synthesized gel rubber.
Adopt present method institute synthetic molecular sieve to react as converting oxygen-containing compound to low-carbon olefins as the catalyzer of various acid catalyzed reactions.
Description of drawings
Fig. 1: the embodiment of the invention 1,2,3,4 and Comparative Examples 1,2 in the XRD spectra of sample.
Embodiment
Below by embodiment in detail the present invention is described in detail.
With synthesized gel rubber ratio 3.0 diethylamine: 0.6SiO
2: P
2O
5: Al
2O
3: 50H
2O measures raw material, and pseudo-boehmite (is contained Al
2O
373%) powder dissolution adds phosphoric acid successively under stirring and (contains H in deionized water
3PO
485%) and silicon sol (contain SiO
228%).Add diethylamine at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 48 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing promptly obtains SAPO-34 molecular sieve (being numbered DEA-1) to neutral at 100 ℃ of air dryings, and its XRD analysis as shown in Figure 1.
With synthesized gel rubber molar ratio (3.0 diethylamine+0.5 tripropyl amine): 0.6SiO
2: P
2O
5: Al
2O
3: 50H
2O measures raw material, and pseudo-boehmite (is contained Al
2O
373%) powder dissolution adds phosphoric acid successively under stirring and (contains H in deionized water
3PO
485%) and silicon sol (contain SiO
228%).Add diethylamine and tripropyl amine at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 48 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing promptly obtains SAPO-34 molecular sieve (being numbered DEA-2) to neutral at 100 ℃ of air dryings, and its XRD analysis as shown in Figure 1.
With synthesized gel rubber ratio (3.0 diethylamine+1.0 tripropyl amines): 0.6SiO
2: P
2O
5: Al
2O
3: 50H
2O measures raw material, and pseudo-boehmite (is contained Al
2O
373%) powder dissolution adds phosphoric acid successively under stirring and (contains H in deionized water
3PO
485%) and silicon sol (contain SiO
228%).Add diethylamine and tripropyl amine at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 24 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing promptly obtains SAPO-34 molecular sieve (being numbered DEA-3) to neutral at 100 ℃ of air dryings, and its XRD analysis as shown in Figure 1.
With synthesized gel rubber ratio (3.0 diethylamine+1.0 ammoniacal liquor): 0.6SiO
2: P
2O
5: Al
2O
3: 50H
2O (DEA is a template) measures raw material, and pseudo-boehmite (is contained Al
2O
373%) powder dissolution adds phosphoric acid successively under stirring and (contains H in deionized water
3PO
485%) and the 4.27g silicon sol (contain SiO
228%).Add diethylamine at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 24 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and at 100 ℃ of air dryings, the products therefrom XRD spectra is shown in Fig. 1, is SAPO-34 molecular sieve (being numbered DEA-4).
Comparative Examples 1
With synthesized gel rubber molar ratio 3.0 triethylamines: 0.6SiO
2: P
2O
5: Al
2O
3: 50H
2O measures raw material, and pseudo-boehmite (is contained Al
2O
373%) powder dissolution adds phosphoric acid successively under stirring and (contains H in deionized water
3PO
485%) and silicon sol (contain SiO
228%).Add triethylamine at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 48 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing promptly obtains SAPO-34 molecular sieve (being numbered TEA-1) to neutral at 100 ℃ of air dryings, and its XRD analysis as shown in Figure 1.
Comparative Examples 2
With synthesized gel rubber molar ratio 2.0 tetraethyl ammonium hydroxides: 0.6SiO
2: P
2O
5: Al
2O
3: 50H
2O measures raw material, and pseudo-boehmite (is contained Al
2O
373%) powder dissolution adds phosphoric acid successively under stirring and (contains H in deionized water
3PO
485%) and silicon sol (contain SiO
228%).Add triethylamine at last, after mixing, will seal in this mixture immigration stainless steel synthesis reactor.Crystallization is 48 hours under 200 ℃ and autogenous pressure, and the solid matter with deionized water washing promptly obtains SAPO-34 molecular sieve (being numbered TEAOH-1) to neutral at 100 ℃ of air dryings, and its XRD analysis as shown in Figure 1.
Embodiment 5
With embodiment 1,2,3,4 and Comparative Examples 1,2 in the sample that obtains carry out ultimate analysis (XRF), its Si, Al, P analytical results are listed in table 1.
Table 1 SAPO-34 molecular sieve elementary composition
Embodiment 6 (catalyzed reaction)
With resulting SAPO-34 sample among the embodiment 2 in 550 ℃ of following bubbling air roastings 4 hours.Then compressing tablet, be crushed to 20～40 orders.Take by weighing the 2.50g sample fixed-bed reactor of packing into, carry out methanol-to-olefins reaction (MTO) reaction evaluating.40wt% methyl alcohol, the pump charging, weight space velocity WHSV is 4.0h
-1, temperature of reaction is 450 ℃, and reaction product is analyzed by online gas-chromatography, and concrete outcome sees Table 2.
Table 2 methanol conversion system olefine reaction result
Claims (12)
1. one kind promotes that silicon enters SAPO-34 framework of molecular sieve degree methods in the synthesized gel rubber, it is characterized in that: use diethylamine to be template, in synthesized gel rubber, add specific silicon amount conditioning agent simultaneously, to reach the purpose of silicone content in effective lifting SAPO-34 framework of molecular sieve; Its step is as follows:
(1) at first aluminium source material is mixed with deionized water, under agitation phosphoric acid and deionized water solution are added, the back that stirs adds silicon-containing material, adds template and silicon amount conditioning agent after continuing to stir again, promptly becomes the gel for the treatment of crystallization after fully stirring;
(2) crystallization is carried out in the gel that obtains in (1) is packed into reactor sealing;
(3) solid crystallized product is separated with mother liquor, to neutral, behind air drying, obtain molecular screen primary powder with deionized water wash;
(4) with molecular screen primary powder roasting in air, promptly get the molecular sieve active catalyst.
2. in accordance with the method for claim 1, it is characterized in that: the silicone content in the synthetic SAPO-34 molecular sieve, Si/ (Si+Al+P) meter in molar ratio is 1.0～2.0 times of silicone content in the synthesized gel rubber.
3. in accordance with the method for claim 1, it is characterized in that: each used proportioning raw materials, by the oxide molecule ratio, for:
SiO
2/Al
2O
3＝0.01～10；
P
2O
5/Al
2O
3＝0.5～1.5；
H
2O/Al
2O
3＝10～100；
DEA/Al
2O
3=0.05～10, wherein DEA is a diethylamine;
R/DEA=0～10, wherein R is a silicon amount conditioning agent.
4. according to claim 1 and 3 described methods, it is characterized in that: the synthetic used silicon amount conditioning agent of hydro-thermal is one or more the mixture in ammoniacal liquor, triethylamine, tetraethyl ammonium hydroxide, beautiful jade, tripropyl amine, Isopropylamine or the Tri N-Propyl Amine.
5. according to claim 1 and 3 described methods, it is characterized in that: the synthetic used phosphorus source of hydro-thermal is a kind of or any several mixture in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides; Used aluminium source is a kind of or any several mixture in aluminium salt, aluminate, activated alumina, aluminum alkoxide, false boehmite or the pseudo-boehmite; Used silicon source is a kind of or any several mixture in silicon sol, water glass, active silica or the positive silicon ester.
6. in accordance with the method for claim 1, it is characterized in that: described synthesized gel rubber, its crystallization temperature are 150～220 ℃.
7. in accordance with the method for claim 1, it is characterized in that: described synthesized gel rubber, its crystallization time is no less than 1 hour.
8. in accordance with the method for claim 1, it is characterized in that: described synthesized gel rubber, its crystallization pressure are its autogenous pressure or nitrogen, air or the rare gas element that charges into 0.01～1MPa.
9. it is characterized in that in accordance with the method for claim 3: described
DEA/Al
2O
3=1～5, wherein DEA is a diethylamine;
R/DEA=0～5, wherein R is a silicon amount conditioning agent.
10. in accordance with the method for claim 1, it is characterized in that: described synthesized gel rubber, its crystallization time are 6～120 hours.
11. in accordance with the method for claim 1, it is characterized in that: in described (4) step, with molecular screen primary powder roasting in air, its temperature is 550～700 ℃, and roasting time is no less than 3 hours.
12. in accordance with the method for claim 1, it is characterized in that: the synthetic molecular sieve comprises the catalyzer of methanol conversion system olefine reaction as the catalyzer of acid catalyzed reaction.
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Cited By (9)
| 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 |
| CN102795640A (en) * | 2012-09-13 | 2012-11-28 | 南开大学 | Method for synthesizing SAPO-34 molecular sieve by using piperazidine as template |
| CN103663484A (en) * | 2012-09-26 | 2014-03-26 | 中国科学院大连化学物理研究所 | Method for quickly synthesizing SAPO(silicoaluminophosphate)-34 molecular sieve and catalyst prepared from molecular sieve |
| CN103818927A (en) * | 2014-02-20 | 2014-05-28 | 无锡威孚环保催化剂有限公司 | One-step method for synthesizing copper-containing CHA type molecular sieve with high hydro-thermal stability |
| WO2014089738A1 (en) * | 2012-12-10 | 2014-06-19 | 中国科学院大连化学物理研究所 | Sapo-34 zeolite having n-methyldiethanolamine as templating agent and synthesis method for the zeolite |
| CN104108726A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Silicoaluminophosphate molecular sieve with high silica-alumina ratio and CHA structure, and synthetic method thereof |
| CN108097304A (en) * | 2017-12-13 | 2018-06-01 | 山东齐鲁华信高科有限公司 | The preparation method of Cu-SAPO-34 molecular sieve catalysts |
| CN105936511B (en) * | 2016-02-22 | 2018-06-12 | 山东齐鲁华信高科有限公司 | A kind of preparation method of high activity SAPO-34 molecular sieves |
| CN113912080A (en) * | 2021-11-08 | 2022-01-11 | 吉林大学 | SAPO-14 molecular sieve, and preparation method and application thereof |
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2006
- 2006-12-04 CN CNA2006101443498A patent/CN101195491A/en active Pending
Cited By (11)
| 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 |
| CN102795640A (en) * | 2012-09-13 | 2012-11-28 | 南开大学 | Method for synthesizing SAPO-34 molecular sieve by using piperazidine as template |
| CN103663484A (en) * | 2012-09-26 | 2014-03-26 | 中国科学院大连化学物理研究所 | Method for quickly synthesizing SAPO(silicoaluminophosphate)-34 molecular sieve and catalyst prepared from molecular sieve |
| CN103663484B (en) * | 2012-09-26 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for quickly synthesizing SAPO(silicoaluminophosphate)-34 molecular sieve and catalyst prepared from molecular sieve |
| WO2014089738A1 (en) * | 2012-12-10 | 2014-06-19 | 中国科学院大连化学物理研究所 | Sapo-34 zeolite having n-methyldiethanolamine as templating agent and synthesis method for the zeolite |
| CN104108726A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Silicoaluminophosphate molecular sieve with high silica-alumina ratio and CHA structure, and synthetic method thereof |
| CN103818927A (en) * | 2014-02-20 | 2014-05-28 | 无锡威孚环保催化剂有限公司 | One-step method for synthesizing copper-containing CHA type molecular sieve with high hydro-thermal stability |
| CN103818927B (en) * | 2014-02-20 | 2016-05-18 | 无锡威孚环保催化剂有限公司 | The method of the synthetic high hydrothermal stability cupric CHA type molecular sieve of one-step method |
| CN105936511B (en) * | 2016-02-22 | 2018-06-12 | 山东齐鲁华信高科有限公司 | A kind of preparation method of high activity SAPO-34 molecular sieves |
| CN108097304A (en) * | 2017-12-13 | 2018-06-01 | 山东齐鲁华信高科有限公司 | The preparation method of Cu-SAPO-34 molecular sieve catalysts |
| CN113912080A (en) * | 2021-11-08 | 2022-01-11 | 吉林大学 | SAPO-14 molecular sieve, and preparation method and application thereof |
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Open date: 20080611 |