CN102372290A - Synthetic method of SAPO-5 and SAPO-34 symbiotic molecular sieves - Google Patents
Synthetic method of SAPO-5 and SAPO-34 symbiotic molecular sieves Download PDFInfo
- Publication number
- CN102372290A CN102372290A CN2010102619111A CN201010261911A CN102372290A CN 102372290 A CN102372290 A CN 102372290A CN 2010102619111 A CN2010102619111 A CN 2010102619111A CN 201010261911 A CN201010261911 A CN 201010261911A CN 102372290 A CN102372290 A CN 102372290A
- Authority
- CN
- China
- Prior art keywords
- sapo
- molecular sieve
- coexisting molecular
- source
- compound method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a synthetic method of SAPO-5 and SAPO-34 symbiotic molecular sieves and mainly solves the problems of single aperture and low activity of a porous material synthesized by the prior art. The synthetic method provided by the invention comprises the following steps of: using a phosphor source, an aluminium source, a silicon source and an organic template as raw materials, mixing the raw materials according to a certain proportion to form a mixed solution, and carrying out hydrothermal crystallization to obtain a series of SAPO-5 and SAPO-34 symbiotic molecular sieves. The synthesized symbiotic molecular sieves have the following molar ratio: AlO3: P2O5: SiO2: R: H2O=1: 0.2-1-2: 0.1-2.0: 0.5-2.5: 20-100, wherein R is the organic template. The technical scheme provided by the invention greatly solves the problems, and can be used in the industrial production of low carbon olefin prepared by methanol.
Description
Technical field
The present invention relates to the compound method of a kind of SAPO-5 and SAPO-34 coexisting molecular sieve.
Background technology
1984, people such as Lok at first introduced AlPO with Si
4In the series molecular sieve; Synthesize one type of new silicon aluminium phosphate (SAPO-n) molecular sieve, this molecular sieve analog comprises 13 kinds of three-dimensional microporous framework structures that are made up of tetrahedron, and wherein some belongs to novel texture; Some then with conventional zeolite facies seemingly; Have from the pore passage structure of six-ring to twelve-ring, therefore the aperture can adapt to the requirement of different size molecular adsorption and diffusion between 0.3～0.8nm.Silicoaluminophosphamolecular molecular sieves (SAPO-n) is by SiO
2, AlO
2 -And PO
2 +Three kinds of microporous type crystal that tetrahedron element constitutes, wherein n represents the crystals with different structure.The structure kind of SAPO series is a lot, can be divided into wide aperture structure (like SAPO-5), intermediate pore size structure (like SAPO-11), small-bore structure (like SAPO-34) and very low pore size structure (like SAPO-20) etc. according to pore size.The SAPO of suitable pore structure has the excellent shape selectivity of selecting.SAPO-n can be used in many hydrocarbon conversion reactions as catalyzer, like the alkylation of the alkylation of cracking, hydrogenation cracking, aromatics and isomerizing, branched paraffin and isomerizing, polymerization, reformation, hydrogenation, transalkylation reaction, dealkylation, hydration etc.; As sorbent material, SAPO-n can come separating mixture according to bulk of molecule is different with polar.
The SAPO-5 molecular sieve belongs to AFI type molecular sieve; The one-dimensional linear and the channel system that do not cross one another of the twelve-ring that its skeleton alternately is made up of two tetra-atomic rings and six-ring belong to the wide aperture molecular sieve, and the crystalline structure of SAPO-34 are similar to Chabazite-type (CHA); Its basic structural unit is two six-rings; These pairs six-ring links to each other through the part tetra-atomic ring, has formed to have the three-dimensional open-framework that is octatomic ring to the maximum, belongs to the small-bore molecular sieve.
Methyl alcohol is important chemical material, is again the raw material of potential vehicle fuel and fuel cell, so the exploration of the research of methyl alcohol synthesis catalytic mechanism and raw catalyst and new catalytic process comes into one's own in the world always.Wherein, Methanol conversion system light olefin process has meaning of the utmost importance; Because ethene, propylene are the crucial intermediates of synthetic detergent, plastics, fiber and all kinds of chemical materialss; It is to be the product of upstream raw material with " triolefin " " triphen " that the organic chemicals of today can be traced back to more than 90%, and wherein be with ethene upstream raw material account for 40%.It is very high that the SAPO-34 molecular sieve of small-bore structure is selected the shape selectivity; Have outstanding thermostability and hydrothermal stability simultaneously, make that its application prospect is very extensive, in methanol conversion inhibition and generation preparing low carbon olefin hydrocarbon (MTO); Because its pore size is about 0.43nm, only to C
1～C
4Hydro carbons have the shape of selecting selectivity, use it can make that as catalyzer most products of methanol conversion are low-carbon alkenes, no aromatics and side chain isomer generate, and have improved the transformation efficiency and the productive rate of MTO process.And wide-aperture SAPO-5 molecular sieve is in shape selective catalysis, fractionation by adsorption, photochemical transformation field, nonlinear optical material preparation, made of carbon nanotubes, atmospheric pollution.Fields such as improvement and support of the catalyst have very big application potential.
USP 4440871 discloses the preparation method of multiple silicoaluminophosphamolecular molecular sieves.Adopt silicon source, phosphorus source, aluminium source and organic formwork agent to produce the preparation method of SAPO-34 molecular sieve, the crystallization time of this method is long, reaches more than 150 hours even 320 hours.
Chinese patent CN1088483 discloses the method for the synthetic SAPO-34 molecular sieves of one or more cheap organic formwork agents, and this method is used for synthesizing the SAPO-34 molecular sieve of big crystal grain.
Chinese patent CN101293660 discloses the compound method of the synthetic SAPO-34 molecular sieve of a kind of order of addition(of ingredients), but the order of addition(of ingredients) operation is too complicated.
It is the method for the synthetic SAPO-5 molecular sieve of template with the diethylamine that Chinese patent 101302015A discloses a kind of, and this method cost is lower.
It is the method for synthetic SAPO-11 of template and SAPO-34 with the diethylamine that Chinese patent 10144350 discloses a kind of, this kind method characteristics be can the control template agent amount come to synthesize respectively SAPO-11 and SAPO-34 molecular sieve
The SAPO molecular sieve is as active ingredient; In the entire synthesis process of catalyzer, play important effect; And the application of SAPO-5 and SAPO-34 molecular sieve very extensively, and on this basis, the coexisting molecular sieve that synthesizes them is in the hope of obtaining better application and better development space.
Summary of the invention
Technical problem to be solved by this invention is single, the active not high problem of synthetic aperture of porous material in the prior art.The preparation method of a kind of coexisting molecular sieve SAPO-5 and SAPO-34 is provided, and this molecular sieve has multi-stage artery structure, active higher characteristics.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: the compound method of a kind of SAPO-5 and SAPO-34 coexisting molecular sieve; With phosphorus source, aluminium source, silicon source and template is raw material; Through synthetic a series of SAPO-5 of proportioning raw materials and SAPO-34 coexisting molecular sieve in the control synthesized gel rubber, it is characterized in that the mixture for preparing has following mole and forms: AlO
3: P
2O
5: SiO
2: R: H
2O=1: 0.2～1-2: 0.1～2.0: 0.5～2.5: 20～100 (wherein R is an organic formwork agent).
In the technique scheme, contain two kinds of Symbionts of SAPO-5 and SAPO-34 in the coexisting molecular sieve at least mutually, wherein in the coexisting molecular sieve by weight percentage the content of SAPO-34 molecular sieve be 50%～98%.The temperature preferable range of hydrothermal crystallizing is 100～220 ℃, and the crystallization time preferable range is 2～160 hours, and crystallization pressure is himself pressure; Said aluminium source is at least a in aluminium salt, aluminate, aluminum isopropylate, activated alumina, pseudobochmite or the pseudo-boehmite; Said silicon source is at least a in silicon sol, water glass, active silica or the positive silicon ester; Said phosphorus source is at least a in ortho-phosphoric acid, phosphoric acid salt or the phosphorous oxides.Organic formwork agent is at least a of tetraethyl-oxyammonia, diethylamine, triethylamine, morpholine.
The present invention has adopted and has been fit to two kinds of template that thing is grown mutually simultaneously, and the proportioning raw materials in the crystallization liquid that control is fit to grow is regulated the crystallization temperature that related thing is grown mutually; Under hydrothermal condition; In the environment that is fit to their growth, generated this coexisting molecular sieve,, contained multistage pore canal because the surface of coexisting molecular sieve has than big difference with interface, acidity and specific surface and the simple mutually mechanical blended of thing; So catalytic performance is preferably arranged; Can be used for the reaction of preparing light olefins from methanol, propene yield can reach 40%, has obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
12.7g phosphoric acid (is contained H
3PO
485%) mixes with the 36g deionized water, under agitation add triethylamine 6.6g, add the 10.5g silicon sol after stirring again and (contain SiO
225%), adds 7.2g pseudo-boehmite powder at last, after thorough mixing is even, with sealing in this mixture immigration synthesis reactor.Crystallization is 24 hours under 200 ℃ and self pressure, and the solid matter with deionized water washing promptly obtains SAPO-5 and SAPO-34 coexisting molecular sieve to neutral at 100 ℃ of air dryings.Use the XRD diffraction can know that quantitatively the SAPO-5 weight percentage is 40.8% in the coexisting molecular sieve, the SAPO-34 weight percentage is 59.2%.
[embodiment 2]
In embodiment 1, only the amount with phosphoric acid changes 8.6g into, and all the other compositions and operational condition are constant, and product is SAPO-5 and SAPO-34 coexisting molecular sieve.Use the XRD diffraction can know that quantitatively the SAPO-5 weight percentage is 45.6% in the coexisting molecular sieve, the SAPO-34 weight percentage is 54.4%.
[embodiment 3]
In embodiment 1, only the amount with triethylamine changes 8.5g into, and all the other compositions and operational condition are constant, and product is SAPO-5 and SAPO-34 coexisting molecular sieve.Use the XRD diffraction can know that quantitatively the SAPO-5 weight percentage is 338% in the coexisting molecular sieve, the SAPO-34 weight percentage is 66.2%.
[embodiment 4]
127g phosphoric acid (is contained H
3PO
485%) mixes with the 45g deionized water, under agitation add the mixed templates of triethylamine 5.1g and 3.7g diethylamine successively, add the 5.0g silicon sol after stirring again and (contain SiO
230%), the last 7.2g pseudo-boehmite powder that slowly adds, be stirred well to fully evenly after, this gel moved in synthesis reactor seal.Crystallization is 32 hours under 190 ℃ and self pressure, and the solid matter with deionized water washing is to neutral, and at 100 ℃ of air dryings, products therefrom is SAPO-5 and SAPO-34 coexisting molecular sieve.Use the XRD diffraction can know that quantitatively the SAPO-5 weight percentage is 19.7% in the coexisting molecular sieve, the SAPO-34 weight percentage is 80.3%.
[embodiment 5]
In embodiment 4, only the amount with silicon sol changes 4.2g into, and all the other compositions and operational condition are constant, and its product is SAPO-5 and SAPO-34 coexisting molecular sieve.Use the XRD diffraction can know that quantitatively the SAPO-5 weight percentage is 31.1% in the coexisting molecular sieve, the SAPO-34 weight percentage is 68.9%.
[embodiment 6]
In embodiment 4, only the amount with triethylamine in the mixed templates changes 9.2g into, and the add-on of diethylamine changes 0.7g into, and all the other compositions and operational condition are constant, and its product is SAPO-5 and SAPO-34 coexisting molecular sieve.Use the XRD diffraction can know that quantitatively the SAPO-5 weight percentage is 13.5% in the coexisting molecular sieve, the SAPO-34 weight percentage is 86.5%.
Claims (5)
1. the compound method of SAPO-5 and SAPO-34 coexisting molecular sieve; With phosphorus source, aluminium source, silicon source and template is raw material; Through synthetic a series of SAPO-5 of proportioning raw materials and SAPO-34 coexisting molecular sieve in the control synthesized gel rubber, it is characterized in that the mixture for preparing has following mole and forms: AlO
3: P
2O
5: SiO
2: R: H
2O=1: 0.2～1-2: 0.1～2.0: 0.5～2.5: 20～100 (wherein R is an organic formwork agent).
2. the compound method of SAPO-5 according to claim 1 and SAPO-34 coexisting molecular sieve; It is characterized in that containing at least in the coexisting molecular sieve two kinds of Symbionts of SAPO-5 and SAPO-34 mutually, wherein in the coexisting molecular sieve by weight percentage the content of SAPO-34 molecular sieve be 50%～98%.
3. the compound method of SAPO-5 according to claim 1 and SAPO-34 coexisting molecular sieve is characterized in that said aluminium source is at least a in aluminium salt, aluminate, aluminum isopropylate, activated alumina, pseudobochmite or the pseudo-boehmite; Said silicon source is at least a in silicon sol, water glass, active silica or the positive silicon ester; Said phosphorus source is at least a in ortho-phosphoric acid, phosphoric acid salt or the phosphorous oxides.
4. the compound method of SAPO-5 according to claim 1 and SAPO-34 coexisting molecular sieve is characterized in that organic formwork agent is selected from least a of tetraethyl-oxyammonia, diethylamine, triethylamine, morpholine.
5. the compound method of SAPO-5 according to claim 1 and SAPO-34 coexisting molecular sieve is characterized in that the temperature of hydrothermal crystallizing is controlled at 100～220 ℃, and crystallization time is 2～160 hours, and crystallization pressure is himself pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102619111A CN102372290A (en) | 2010-08-23 | 2010-08-23 | Synthetic method of SAPO-5 and SAPO-34 symbiotic molecular sieves |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102619111A CN102372290A (en) | 2010-08-23 | 2010-08-23 | Synthetic method of SAPO-5 and SAPO-34 symbiotic molecular sieves |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102372290A true CN102372290A (en) | 2012-03-14 |
Family
ID=45791604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102619111A Pending CN102372290A (en) | 2010-08-23 | 2010-08-23 | Synthetic method of SAPO-5 and SAPO-34 symbiotic molecular sieves |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102372290A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011195A (en) * | 2012-12-18 | 2013-04-03 | 吉林大学 | One-step preparation method for hydrogen type multistage pore molecular sieve with SAPO-5 and SAPO-34 symbiosis |
| CN103833047A (en) * | 2014-03-28 | 2014-06-04 | 神华集团有限责任公司 | SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same |
| CN104326483A (en) * | 2014-10-13 | 2015-02-04 | 天津众智科技有限公司 | Low-silicon composite molecular sieve, and synthetic method and application thereof |
| CN105642342A (en) * | 2014-12-02 | 2016-06-08 | 神华集团有限责任公司 | SAPO-5/SAPO-34 composite molecular sieve, preparation method and application thereof |
| CN105728032A (en) * | 2014-12-10 | 2016-07-06 | 神华集团有限责任公司 | Preparation method of composite molecular sieve, and prepared composite molecular sieve and application thereof |
| CN104671256B (en) * | 2013-11-29 | 2016-08-24 | 神华集团有限责任公司 | Preparation method of SAPO-5/SAPO-34 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound |
| CN106115735A (en) * | 2016-06-15 | 2016-11-16 | 南开大学 | AlPO434 with SAPO 34 composite molecular sieves and synthetic method thereof |
| CN106185982A (en) * | 2014-12-19 | 2016-12-07 | 神华集团有限责任公司 | A kind of SAPO-5 content is SAPO5/SAPO34 composite molecular screen, its preparation method and the application thereof of 70%-90% |
| CN106608634A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method of cocrystallization molecular sieve integral material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060293547A1 (en) * | 2005-06-24 | 2006-12-28 | Mertens Machteld M | Process for manufacture of silicoaluminophosphate molecular sieves |
| CN101808740A (en) * | 2007-07-31 | 2010-08-18 | 道达尔石油化学产品研究弗吕公司 | Mixtures of molecular sieves comprising meapo, their use in conversion of organics to olefins |
-
2010
- 2010-08-23 CN CN2010102619111A patent/CN102372290A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060293547A1 (en) * | 2005-06-24 | 2006-12-28 | Mertens Machteld M | Process for manufacture of silicoaluminophosphate molecular sieves |
| CN101808740A (en) * | 2007-07-31 | 2010-08-18 | 道达尔石油化学产品研究弗吕公司 | Mixtures of molecular sieves comprising meapo, their use in conversion of organics to olefins |
Non-Patent Citations (1)
| Title |
|---|
| 叶丽萍 等: "SAPO-34分子筛的合成及其对甲醇制低碳烯烃反应的催化性能", 《华东理工大学学报(自然科学版)》, vol. 36, no. 1, 15 February 2010 (2010-02-15), pages 6 - 13 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011195A (en) * | 2012-12-18 | 2013-04-03 | 吉林大学 | One-step preparation method for hydrogen type multistage pore molecular sieve with SAPO-5 and SAPO-34 symbiosis |
| CN104671256B (en) * | 2013-11-29 | 2016-08-24 | 神华集团有限责任公司 | Preparation method of SAPO-5/SAPO-34 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound |
| CN103833047A (en) * | 2014-03-28 | 2014-06-04 | 神华集团有限责任公司 | SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same |
| CN104326483A (en) * | 2014-10-13 | 2015-02-04 | 天津众智科技有限公司 | Low-silicon composite molecular sieve, and synthetic method and application thereof |
| CN105642342B (en) * | 2014-12-02 | 2018-09-14 | 国家能源投资集团有限责任公司 | SAPO-5/SAPO-34 composite molecular screens, and preparation method thereof, and its application |
| CN105642342A (en) * | 2014-12-02 | 2016-06-08 | 神华集团有限责任公司 | SAPO-5/SAPO-34 composite molecular sieve, preparation method and application thereof |
| CN105728032A (en) * | 2014-12-10 | 2016-07-06 | 神华集团有限责任公司 | Preparation method of composite molecular sieve, and prepared composite molecular sieve and application thereof |
| CN105728032B (en) * | 2014-12-10 | 2019-06-18 | 国家能源投资集团有限责任公司 | The preparation method of composite molecular screen and composite molecular screen obtained and its application |
| CN106185982A (en) * | 2014-12-19 | 2016-12-07 | 神华集团有限责任公司 | A kind of SAPO-5 content is SAPO5/SAPO34 composite molecular screen, its preparation method and the application thereof of 70%-90% |
| CN106185982B (en) * | 2014-12-19 | 2019-04-02 | 国家能源投资集团有限责任公司 | SAPO5/SAPO34 composite molecular screen, preparation method and its application that a kind of SAPO-5 content is 70%-90% |
| CN106608634B (en) * | 2015-10-22 | 2018-07-17 | 中国石油化工股份有限公司 | The preparation method of cocrystallization molecular sieve integral material |
| CN106608634A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Preparation method of cocrystallization molecular sieve integral material |
| CN106115735A (en) * | 2016-06-15 | 2016-11-16 | 南开大学 | AlPO434 with SAPO 34 composite molecular sieves and synthetic method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102372290A (en) | Synthetic method of SAPO-5 and SAPO-34 symbiotic molecular sieves | |
| CN101555022B (en) | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve | |
| CN101195492B (en) | Method for synthesizing SAPO-11 and SAPO-34 molecular sieve with diethylamine as template agent | |
| CN102372291A (en) | Preparation method of SAPO-18 / SAPO-34 intergrowth molecular sieve | |
| CN103011195B (en) | One-step preparation method for hydrogen type multistage pore molecular sieve with SAPO-5 and SAPO-34 symbiosis | |
| CN102530988B (en) | Method for preparing SAPO-11 molecular sieve and application of SAPO-11 molecular sieve | |
| CN104828842A (en) | Preparation method of SAPO-5 and SAPO-34 symbiotic composite molecular sieve | |
| CN103030158B (en) | Synthetic method of SAPO-44 molecular sieve modified by rare earth metals | |
| CN101503201B (en) | Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst | |
| CN101195491A (en) | Method for hoisting degree of silicon entering SAPO-34 molecular sieve framework in synthesized gel rubber | |
| CN101508446A (en) | Production process of regulating and controlling SAPO-11 molecular sieve bore diameter | |
| CN1182034C (en) | Method for preparing aluminium silicophosphate molecular sieve | |
| CN108928830A (en) | Molecular sieve SCM-17, its preparation method and use | |
| CN101284673A (en) | Process for preparing SAPO molecular sieve | |
| CN103878016A (en) | Composite molecular sieve catalyst for MTP (methanol to propylene) as well as application thereof | |
| CN111115655B (en) | Eutectic nano molecular sieve, preparation method and application thereof | |
| CN102372289B (en) | Synthetic method of SAPO (Silicoaluminophosphate)-11 molecular sieve | |
| CN101580248B (en) | Aluminosilicophosphate molecular sieve SAPO-34 and preparation method thereof | |
| CN108314056B (en) | Method for selectively synthesizing SAPO-15 and SAPO-34 molecular sieves | |
| CN103030155B (en) | Synthesis method of silicoaluminophosphate (SAPO)-44 molecular sieve | |
| CN103030154B (en) | Synthesis method of silicoaluminophosphate (SAPO)-5 and SAPO-44 symbiotic molecular sieve | |
| CN1359753A (en) | Metal aluminophosphate molecular sieve and method for converting methanol to olefin with same | |
| CN101293660A (en) | Synthesizing method for high-performance SAPO molecular sieve | |
| CN103285915A (en) | Preparation method of palladium catalyst loaded on silicoaluminophosphate (SAPO)-11 molecular sieve carrier | |
| CN104174433B (en) | A kind of n-butene isomerization catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120314 |