CN1363519A - Process for preparing SAPO molecular sieve - Google Patents
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- CN1363519A CN1363519A CN 01135910 CN01135910A CN1363519A CN 1363519 A CN1363519 A CN 1363519A CN 01135910 CN01135910 CN 01135910 CN 01135910 A CN01135910 A CN 01135910A CN 1363519 A CN1363519 A CN 1363519A
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Abstract
A process for preparing SAPO molecular sieve by gas-phase transfer includes such steps as proportionally dissolving phosphoric acid, isoporpanol aluminium and silica sol in water, drying at 80 deg.C, grinding, loading it to upper part of reactor, adding the mixed solvent of H2O and volatile organic template agent to lower part of reactor, reacting at 150-185 deg.c for 2-5 days, and direct separation. Its advantages are less consumption of template agent and reuse of template agent.
Description
The present invention relates to a kind of preparation method of SAPO molecular sieve, specifically, the invention relates to the method that is equipped with the SAPO molecular sieve by the gas phase conversion legal system.
The SAPO molecular sieve is another big molecular sieve analog catalytic material except that sial type zeolite molecular sieve, they have been widely used in petrochemical complex and the petroleum refining process, especially have very high catalytic activity and selectivity in many reactions such as the isomerization of normal paraffin and methyl alcohol system hydrocarbon.The classical method for preparing the SAPO molecular sieve is a hydrothermal synthesis method, and promptly crystallization obtains in the high-temperature water hot system.By changing the kind of synthesis condition and template used dose, can much be had the SAPO molecular sieve of different structure.
Gas phase conversion method (the Vapour-Phase Transport that grew up in recent years, VPT) be the effective ways of preparation zeolite molecular sieve, its fundamental principle is at first to prepare molecular sieve precursor colloidal sol, become xerogel after this drying sol, to be placed in the container on special autoclave top, behind the gained xerogel porphyrize H
2The mixed solvent of O and volatility template joins the bottom of autoclave, and at high temperature the steam molecule of water and template and molecular sieve presoma glue interact, and can make amorphous dried glue be converted into the zeolite molecular sieve sample with certain crystallographic structure.Compare with the hydrothermal synthesis method of classics, resulting sieve sample of this process and mother liquor are directly isolating, can save numerous and diverse sepn process; Simultaneously the amount of required template reduces greatly, and organic formwork agent can reclaim and reuse easily, is a kind of easy, economy, environment-friendly method for preparing the molecular sieve catalytic material.This method successfully has been applied to the preparation of multiple zeolite molecular sieve and molecular screen membrane, but then rarely has report for the similar preparation method of SAPO molecular sieve.
The objective of the invention is to provide a kind of method of the SAPO of preparation molecular sieve by above-mentioned gas phase conversion method.
The method for preparing the SAPO molecular sieve among the present invention in turn includes the following steps: (1) with the precursor compound of phosphorus, aluminium and the silicon precursor colloidal sol that makes molecular sieve soluble in water, wherein the mol ratio of each raw material is under high degree of agitation:
Al
2O
3∶P
2O
5∶0.1-1.5SiO
2
(2) rising temperature of reaction to 80 ℃ behind the stirring reaction 2-5h at room temperature continues stirring reaction 8-16h.In the reaction process,, the viscosity of the evaporation system of moisture becomes dried glue greatly until at last along with becoming gradually;
(3) will be placed on reactor top behind the dried glue porphyrize of the gained powdered, add H at reactor bottom
2The mixed solvent of O and volatility organic amine template;
(4) with reactor sealing back 175 ℃ of constant temperature static crystallizations 2-5 days;
(5) autoclave is cooled to room temperature, then washing according to a conventional method, drying and roasting.
The precursor compound of said phosphorus is the ortho-phosphoric acid of weight 85% among the preparation method provided by the present invention.
The precursor compound of said aluminium is aluminum isopropylate, aluminium hydroxide or sodium aluminate among the preparation method provided by the present invention.
The precursor compound of said silicon is silicon sol, silicon gel or the positive tetraethyl orthosilicate of weight 30% among the preparation method provided by the present invention.
Said volatility organic amine template is di-n-propylamine, morpholine, quadrol, triethylamine, n-Butyl Amine 99 or hexanediamine among the preparation method provided by the present invention.
Said H among the preparation method provided by the present invention
2The volume ratio of O and volatility organic amine mixed solvent is 0.2-2.
Outstanding feature of the present invention is with molecular sieve presoma rubber powder end and H
2The mixed solvent of O and volatility organic amine template is placed on two portions up and down of reactor respectively, and both directly do not contact, at high temperature the H of reactor bottom
2The unformed dried glue precursor on the steam molecule of O and template mixed solvent and top interacts in closed reaction kettle, makes unformed dried glue progressively transform into the SAPO molecular sieve with ad hoc structure.Compare with traditional hydrothermal synthesis method, method of the present invention has following several advantage: 1) productive rate of molecular sieve is very high; 2) after crystallization was finished, sieve sample directly separated with liquid phase medium, thereby can save separating step numerous and diverse in the hydro-thermal building-up process; 3) template used dose amount is the 1/10-1/2 of hydrothermal synthesis method aequum in the method for the present invention, thereby can reduce the preparation cost of SAPO molecular sieve significantly, organic formwork agent can reclaim and reuse simultaneously, thereby is a kind of easy, economic, eco-friendly preparation method.
Fig. 1, Fig. 2, Fig. 3 are the X-ray diffractograms of the prepared sample of example 1, example 6 and example 7, measure on D/Max 2400 Rigaku diffractometers, and scanning electron microscope analysis carries out on JEOL 120 scanning electronic microscope.
The invention will be further described below by embodiment: embodiment 1
The 4.0g aluminum isopropylate is added to 15mlH
2Among the O, stir and to make its homodisperse, under high degree of agitation with the H of 1.35ml 85%
3PO
4Be added drop-wise in the aluminum isopropylate, add the silicon sol of 1.7ml 30% behind the stirring reaction 30min.The mole that wherein adds each component consists of:
Al
2O
3: P
2O
5: 0.5SiO
2Stirring reaction 2h under the room temperature, after, the temperature of reaction to 80 that raises gradually ℃ continues stirring reaction 8-16h.Along with the evaporation of moisture in the reaction process, the viscosity of system becomes greatly gradually, becomes dried glue until at last.With the dried glue grinding powder of gained, be placed in the container on the special autoclave of 500ml top, add 30mlH in autoclave base
2The mixed solvent of O and di-n-propylamine, both volume ratios are 1: 1.High pressure taken away the firewood under the cauldron be placed in the thermostat container temperature to 175 of rising thermostat container ℃, standing and reacting 5 days after the sealing.After at last autoclave being cooled to room temperature, with solid sample water thorough washing, filter the back at 100 ℃ of dry 8h.At last this molecular screen primary powder roasting 6h in 550 ℃ of air atmospheres is promptly got the SAPO molecular sieve.
The XRD spectra of gained sample by hydrothermal synthesis method gained SAPO-34 molecular sieve seemingly, is typical C HA structure in its crystalline phase and the document as shown in Figure 1.Scanning electronic microscope (SEM) is the result show, gained SAPO sieve sample is the small-particle of particle diameter between 0.2-0.5 μ m.
Embodiment 2-4
According to the method and the step of example 1, but the consumption of change silicon sol, the mole proportioning of each component is respectively in the precursor colloidal sol:
(2)Al
2O
3∶P
2O
5∶0.2SiO
2
(3)Al
2O
3∶P
2O
5∶0.8SiO
2
(4) Al
2O
3: P
2O
5: 1.0SiO
2Embodiment 5
According to the preparation method and the step of example 1, but replace di-n-propylamine as organic formwork agent with morpholine.XRD result shows that the gained sample also has the CHA crystalline structure of SAPO-34, but SEM result is different from example 1, be the square crystalline form of rule, and particle diameter is 1-3 μ m greater than example 1 gained sample.Embodiment 6
According to the preparation method and the step of example 1, but replace di-n-propylamine as organic formwork agent with triethylamine.XRD spectra by hydrothermal synthesis method gained SAPO-5 molecular sieve seemingly, has typical A FI structure in its diffraction mode and the document as shown in Figure 2.SEM result shows that this molecular sieve is the small-particle of 0.3-0.6 μ m.
Embodiment 7
According to the preparation method and the step of example 1, but replace di-n-propylamine as organic formwork agent with quadrol.XRD spectra as shown in Figure 3, its diffraction mode does not find corresponding structure in the XRD spectra of having reported of passing through the SAPO molecular sieve that hydrothermal synthesis method makes.SEM result shows that this molecular sieve is the tabular crystal of 0.5-2 μ m.
Claims (6)
1. the preparation method of a SAPO molecular sieve is characterized in that this method comprises that successively the following step poly-:
(1) under high degree of agitation with the precursor compound of phosphorus, aluminium and the silicon precursor colloidal sol that makes molecular sieve soluble in water, wherein the mol ratio of each raw material is:
Al
2O
3∶P
2O
5∶0.1-1.5SiO
2
(2) rising temperature of reaction to 80 ℃ behind the stirring reaction 2-5h at room temperature continues stirring reaction 8-16h.In the reaction process,, the viscosity of the evaporation system of moisture becomes dried glue greatly at last along with becoming gradually;
(3) will be placed on reactor top behind the dried glue porphyrize of the gained powdered, add H at reactor lower part
2The mixed solvent of O and volatility organic amine;
(4) with reactor sealing back 175 ℃ of constant temperature static crystallizations 2-5 days;
(5) with reactor cooling to room temperature, washing according to a conventional method, drying and roasting then, the SAPO molecular sieve.
2. according to the described preparation method of claim 1, the precursor compound that it is characterized in that phosphorus is the ortho-phosphoric acid of weight 85%.
3. according to the described preparation method of claim 1, the precursor compound that it is characterized in that aluminium is aluminum isopropylate, aluminium hydroxide or sodium aluminate.
4. according to the described preparation method of claim 1, the precursor compound that it is characterized in that silicon is silicon sol, silicon gel or the positive tetraethyl orthosilicate of weight 30%.
5. according to the described preparation method of claim 1, it is characterized in that the volatility organic amine is di-n-propylamine, morpholine, quadrol, triethylamine, n-Butyl Amine 99 or hexanediamine.
6. according to the described preparation method of claim 1, it is characterized in that H
2The volume ratio of O and volatility organic amine mixed solvent is 0.2-2.
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|---|---|---|---|
| CNB011359102A CN1191991C (en) | 2001-10-17 | 2001-10-17 | Process for preparing SAPO molecular sieve |
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|---|---|---|---|
| CNB011359102A CN1191991C (en) | 2001-10-17 | 2001-10-17 | Process for preparing SAPO molecular sieve |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314587C (en) * | 2005-04-14 | 2007-05-09 | 南京工业大学 | Process for prepareing SAPO-34 molecular siever |
| WO2008019592A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A method for utilizing mother liquor of synthesizing molecular sieve of silicoaluminum phosphate |
| CN100390056C (en) * | 2005-04-25 | 2008-05-28 | 中国科学院大连化学物理研究所 | Method for changing crystal structure of molecular sieve |
| CN101962196A (en) * | 2010-08-12 | 2011-02-02 | 南京工业大学 | Molecular sieve film and preparation method thereof |
| CN101284246B (en) * | 2008-04-24 | 2011-05-18 | 中国石油化工股份有限公司 | Catalyst for translating oxygen-containing compound into low carbon olefin hydrocarbon |
| CN101125665B (en) * | 2007-08-08 | 2011-07-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN102530987A (en) * | 2010-12-29 | 2012-07-04 | 中国科学院大连化学物理研究所 | Solvent thermal synthesis method of SAPO (silicoaluminophosphate) molecular sieve and catalyst prepared by SAPO molecular sieve |
| CN103172084A (en) * | 2013-04-11 | 2013-06-26 | 太原大成环能化工技术有限公司 | Solid phase preparation method of aluminosilicophosphate eutectic molecular sieve |
| CN103539154A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of SAPO (Si, Al, P, O)-56 molecular sieve |
| CN103936027A (en) * | 2014-04-04 | 2014-07-23 | 南京工业大学 | SAPO (silicoaluminophosphate)-34 zeolite material assembled by nanosheets and having controllable flower shape, as well as preparation method thereof |
| CN104556142A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of low-silicon SAPO-34 molecular sieve |
| CN105271303A (en) * | 2015-09-17 | 2016-01-27 | 中国石油大学(华东) | Preparing method of AEL structure rare earth substituted aluminum phosphate molecular sieve |
| CN105384178A (en) * | 2014-09-09 | 2016-03-09 | 中国石油化工股份有限公司 | Gas-phase synthesis method for SAPO-34 molecular sieve |
| CN106629770A (en) * | 2016-12-25 | 2017-05-10 | 复旦大学 | Synthesis method of microporous/mesoporous zeolite molecular sieve based on dry gel preparation |
| CN108147428A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of aluminium phosphate molecular sieve with CHA structure and preforming synthetic method |
| CN110040745A (en) * | 2019-05-21 | 2019-07-23 | 孔哲 | A kind of preparation method and applications of nanorod shaped SAPO-5 molecular sieve |
-
2001
- 2001-10-17 CN CNB011359102A patent/CN1191991C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314587C (en) * | 2005-04-14 | 2007-05-09 | 南京工业大学 | Process for prepareing SAPO-34 molecular siever |
| CN100390056C (en) * | 2005-04-25 | 2008-05-28 | 中国科学院大连化学物理研究所 | Method for changing crystal structure of molecular sieve |
| WO2008019592A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A method for utilizing mother liquor of synthesizing molecular sieve of silicoaluminum phosphate |
| CN101125665B (en) * | 2007-08-08 | 2011-07-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN101284246B (en) * | 2008-04-24 | 2011-05-18 | 中国石油化工股份有限公司 | Catalyst for translating oxygen-containing compound into low carbon olefin hydrocarbon |
| CN101962196B (en) * | 2010-08-12 | 2012-02-22 | 南京工业大学 | Molecular sieve film and preparation method thereof |
| CN101962196A (en) * | 2010-08-12 | 2011-02-02 | 南京工业大学 | Molecular sieve film and preparation method thereof |
| CN102530987A (en) * | 2010-12-29 | 2012-07-04 | 中国科学院大连化学物理研究所 | Solvent thermal synthesis method of SAPO (silicoaluminophosphate) molecular sieve and catalyst prepared by SAPO molecular sieve |
| CN103539154A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of SAPO (Si, Al, P, O)-56 molecular sieve |
| CN103172084A (en) * | 2013-04-11 | 2013-06-26 | 太原大成环能化工技术有限公司 | Solid phase preparation method of aluminosilicophosphate eutectic molecular sieve |
| CN103172084B (en) * | 2013-04-11 | 2015-03-11 | 太原大成环能化工技术有限公司 | Solid phase preparation method of aluminosilicophosphate eutectic molecular sieve |
| CN104556142B (en) * | 2013-10-25 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of preparation method of low silicon SAPO-34 molecular sieve |
| CN104556142A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of low-silicon SAPO-34 molecular sieve |
| CN103936027A (en) * | 2014-04-04 | 2014-07-23 | 南京工业大学 | SAPO (silicoaluminophosphate)-34 zeolite material assembled by nanosheets and having controllable flower shape, as well as preparation method thereof |
| CN103936027B (en) * | 2014-04-04 | 2015-12-30 | 南京工业大学 | Controlled SAPO-34 zeolitic material of colored shape of nanometer sheet assembling and preparation method thereof |
| CN105384178A (en) * | 2014-09-09 | 2016-03-09 | 中国石油化工股份有限公司 | Gas-phase synthesis method for SAPO-34 molecular sieve |
| CN105384178B (en) * | 2014-09-09 | 2017-12-15 | 中国石油化工股份有限公司 | The gas-phase synthesizing method of the molecular sieves of SAPO 34 |
| CN105271303A (en) * | 2015-09-17 | 2016-01-27 | 中国石油大学(华东) | Preparing method of AEL structure rare earth substituted aluminum phosphate molecular sieve |
| CN108147428A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of aluminium phosphate molecular sieve with CHA structure and preforming synthetic method |
| CN106629770A (en) * | 2016-12-25 | 2017-05-10 | 复旦大学 | Synthesis method of microporous/mesoporous zeolite molecular sieve based on dry gel preparation |
| CN110040745A (en) * | 2019-05-21 | 2019-07-23 | 孔哲 | A kind of preparation method and applications of nanorod shaped SAPO-5 molecular sieve |
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