CN102372291A - Preparation method of SAPO-18 / SAPO-34 intergrowth molecular sieve - Google Patents
Preparation method of SAPO-18 / SAPO-34 intergrowth molecular sieve Download PDFInfo
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- CN102372291A CN102372291A CN2010102619361A CN201010261936A CN102372291A CN 102372291 A CN102372291 A CN 102372291A CN 2010102619361 A CN2010102619361 A CN 2010102619361A CN 201010261936 A CN201010261936 A CN 201010261936A CN 102372291 A CN102372291 A CN 102372291A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The invention relates to a preparation method of a SAPO-18 and SAPO-34 intergrowth molecular sieve, and mainly solves problems of single aperture and low activity of a porous material synthesized by a prior art. According to the invention, raw materials of phosphor source, aluminium source, silicon source and organic template in a certain proportion are mixed into a solution and treated with a hydrothermal crystallization to obtain the SAPO-18 and SAPO-34 intergrowth molecular sieve. The synthesized intergrowth molecular sieve has a molar composition that AlO3:P2O5:SiO2:R:H2O equals to 1:0.2-2.0:0-1.5:0.5-3.0:30-120 (R represents the organic template). The above technical scheme well solves the problems and can be used in industrial production of producing low carbon olefin from methanol.
Description
Technical field
The present invention relates to the preparation method of a kind of SAPO-18 and SAPO-34 coexisting molecular sieve.
Background technology
The serial molecular sieve of silicon aluminium phosphate (SAPO) is a kind of novel molecular sieve of U.S. combinating carbide company (UCC) in exploitation in 1984, is by SiO
2, AlO
2 -, PO
2 +Three kinds of microporous type crystal that tetrahedron element constitutes.Wherein, The crystalline structure of SAPO-34 is similar to Chabazite-type (CHA), and SAPO-18 is the molecular sieve that has with the AEI structure of the microcosmic pore passage structure of CHA similar, and its basic structural unit is two six-rings; Its orifice diameter is 0.43nm, belongs to pore zeolite.
Low-carbon alkene plays a part very important as the starting material of synthetic detergent, plastics, fiber and all kinds of chemical materialss in modern times in the petrochemical complex industry.Traditional low-carbon alkene is through petroleum cracking production, and along with the worsening shortages of petroleum resources, the various countries scientist is carrying out seeking the work of oil replacement resource just in full preparation.Wherein a kind of important alternative source is to be similar to materials such as alcoholic acid oxide compound, particularly methyl alcohol, dme and ethanol.In these a series of work, received the generally attention of researcher with the work of low-carbon alkenes such as methanol decomposition synthesizing ethylene.Because SAPO-18 and SAPO-34 have special pore passage structure and proton is acid, when methanol to olefins reaction, the gaseous product of methanol conversion has only C
1～C
5Hydro carbons, its aperture forms bigger diffusional resistance to macromole, has C only
2And C
3Hydro carbons can diffuse out outside the crystal at an easy rate, makes this kind molecular sieve in the reaction of preparing light olefins from methanol, show obvious superiority, and selectivity of light olefin is high, C
5Above product and side chain isomer are seldom.
USP 2002/0165090A1 and Chinese patent CN101076401A disclose first symbiosis of a kind of CHA of comprising framework types and AEI framework types and the silicoaluminophosphamolecular molecular sieve of second coexisting phase, mainly the ratio through assay determination AEI and CHA.
USP 9815496A1 discloses the silicoaluminophosphamolecular molecular sieve of a kind of RUW-19, and this kind molecular sieve is an AEI/CHA mixed phase compsn, and understands the characteristic of these materials through analytical table.
In the reaction of preparing light olefins from methanol; SAPO-34 shows ethene and propylene than more excellent product selectivity; But in reaction process, form coke fast easily and make rapid catalyst deactivation; Mixed catalyst of the present invention makes catalyst deactivation slack-off, thereby has increased life of catalyst owing to SAPO-34 molecular sieve and the symbiosis of SAPO-18 molecular sieve.The present invention uses the tetraethyl-oxyammonia to be template, under the condition of conventional synthesis of molecular sieve, mainly synthesizes through proportioning raw materials in the control synthesized gel rubber and prepares SAPO-18 and SAPO-34 coexisting molecular sieve.
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-18 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 preparation method of a kind of SAPO-18 and SAPO-34 coexisting molecular sieve.With phosphorus source, aluminium source, silicon source and organic formwork agent is raw material, through the coexisting molecular sieve of synthetic SAPO-18 of proportioning raw materials and SAPO-34 in the control synthesized gel rubber, it is characterized in that the synthetic coexisting molecular sieve for preparing has following mole and forms: AlO
3: P
2O
5: SiO
2: R: H
2O=1: 0.2～2.0: 0～1.5: 0.5～3.0: 30～120 (R is an organic formwork agent).
In the technique scheme, contain two kinds of Symbionts of SAPO-18 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 40%～98%.Said phosphorus source is at least a in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides; 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.Organic formwork agent is an organic amine tetraethyl-oxyammonia, and the crystallization temperature preferable range is 150～200 ℃, and the crystallization time preferable range is 18～160 hours.
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, 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; Contain multistage pore canal; So catalytic performance is preferably arranged, can be used for the reaction of preparing light olefins from methanol, ethene and propene yield can reach more than 80%; Life-span can reach 120min, has obtained better technical effect.
Further specify method of the present invention through embodiment below, but be not limited to these examples.
Embodiment
[embodiment 1]
5.7 gram pseudo-boehmite powder dissolutions in the 36ml deionized water, are stirred, under agitation add phosphoric acid (85% aqueous solution), after stirring, add the 0.6g silicon sol again and (contain SiO
230%).Add template tetraethyl-oxyammonia 23.5g at last, stir up to processing even gel, this mixture moves in synthesis reactor and seals, and crystallization is 48 hours under 180 ℃ and autogenous pressure.Solid is separated from mother liquor, and solid promptly obtains SAPO-18 and SAPO-34 coexisting molecular sieve at 100 ℃ of air dryings with deionized water wash for several times.Use the XRD diffraction can know that quantitatively the SAPO-18 weight percentage is 35.8% in the coexisting molecular sieve, the SAPO-34 weight percentage is 64.2%.
[embodiment 2]
In embodiment 1, only the amount with silicon sol changes 0.8g into, and all the other compositions and operational condition are constant, and products therefrom is SAPO-18 and SAPO-34 coexisting molecular sieve.Use the XRD diffraction can know that quantitatively the SAPO-18 weight percentage is 30.7% in the coexisting molecular sieve, the SAPO-34 weight percentage is 69.3%.
[embodiment 3]
In embodiment 1, only the amount with the tetraethyl-oxyammonia changes 28.2g into, and all the other compositions and operational condition are constant, and product is SAPO-18 and SAPO-34 coexisting molecular sieve.Use the XRD diffraction can know that quantitatively the SAPO-18 weight percentage is 31.6% in the coexisting molecular sieve, the SAPO-34 weight percentage is 68.4%.
[embodiment 4]
The 23.2g aluminum isopropylate is added in the beaker, add deionized water 30.2g again, stir, under agitation add phosphoric acid (85% aqueous solution) 11.1g, add the 1.5g silicon sol again and (contain SiO
230%), add 28.3g template tetraethyl-oxyammonia at last and stir, this gel is moved in reaction kettle, crystallization is 36 hours under 175 ℃ and autogenous pressure.The solid matter with deionized water washing promptly obtains SAPO-18 and SAPO-34 coexisting molecular sieve to neutral at 100 ℃ of air dryings.Use the XRD diffraction can know that quantitatively the SAPO-18 weight percentage is 18.8% in the coexisting molecular sieve, the SAPO-34 weight percentage is 81.2%.
[embodiment 5]
In embodiment 4, only the amount with phosphoric acid changes 8.8g into, and all the other compositions and operational condition are constant, and product is SAPO-18 and SAPO-34 coexisting molecular sieve.Use the XRD diffraction can know that quantitatively the SAPO-18 weight percentage is 21.6% in the coexisting molecular sieve, the SAPO-34 weight percentage is 78.4%.
[embodiment 6]
With resulting sample among the embodiment 1 in 550 ℃ of following bubbling air roastings 4 hours.Then compressing tablet, be crushed to 20～40 orders.Take by weighing the 2.0g sample fixed-bed reactor of packing into, carry out the reaction for preparing light olefins from methanol evaluation.Pure methanol pump charging, weight space velocity are 6.0h
-1, temperature of reaction is 460 ℃, and reaction product is analyzed by gc, and the selectivity of low-carbon alkene in the reaction product (ethene+propylene) is up to 80%, life-span 120min.
Claims (6)
1. the preparation method of SAPO-18 and SAPO-34 coexisting molecular sieve.With phosphorus source, aluminium source, silicon source and organic formwork agent is raw material, through the coexisting molecular sieve of synthetic SAPO-18 of proportioning raw materials and SAPO-34 in the control synthesized gel rubber, it is characterized in that the synthetic coexisting molecular sieve for preparing has following mole and forms: AlO
3: P
2O
5: SiO
2: R: H
2O=1: 02～2.0: 0～1.5: 0.5～3.0: 30～120 (R is an organic formwork agent).
2. the preparation method of SAPO-18 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-18 and SAPO-34 mutually, wherein in the coexisting molecular sieve by weight percentage the content of SAPO-34 molecular sieve be 40%～98%.
3. the preparation method of SAPO-18 according to claim 1 and SAPO-34 coexisting molecular sieve is characterized in that said phosphorus source is at least a in ortho-phosphoric acid, phosphoric acid salt, Organophosphorous compounds or the phosphorous oxides; 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.
4. the preparation method of SAPO-18 according to claim 1 and SAPO-34 coexisting molecular sieve is characterized in that said organic formwork agent is an organic amine tetraethyl-oxyammonia.
5. the preparation method of SAPO-18 according to claim 1 and SAPO-34 coexisting molecular sieve is characterized in that its crystallization temperature is 150～200 ℃, and crystallization time is 18～160 hours.
6. the preparation method of SAPO-18 according to claim 1 and SAPO-34 coexisting molecular sieve is characterized in that: the synthetic molecular sieve comprises the methanol-to-olefins reaction catalyst for reaction as the catalyzer of acid catalyzed reaction.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633279A (en) * | 2012-04-17 | 2012-08-15 | 清华大学 | Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof |
| CN103263947A (en) * | 2013-06-03 | 2013-08-28 | 神华集团有限责任公司 | Composite molecular sieve for preparing catalyst for producing light olefins from organic oxygen-containing compound, and preparation method thereof |
| CN103418431A (en) * | 2013-08-28 | 2013-12-04 | 神华集团有限责任公司 | SAPO-34/SAPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound and preparation method thereof |
| CN103878018A (en) * | 2014-01-22 | 2014-06-25 | 山西大学 | Method for synthesizing small grain SAPO-18/SAPO-34 eutectic molecular sieve |
| CN105174286A (en) * | 2015-08-17 | 2015-12-23 | 久泰能源科技有限公司 | Preparation method for high-proportion AEI/CHA eutectic molecular sieve |
| CN105819466A (en) * | 2016-03-04 | 2016-08-03 | 中国石油天然气股份有限公司 | SAPO-18/SAPO-34 eutectic molecular sieve, and preparation method and application thereof |
| CN108128782A (en) * | 2017-12-20 | 2018-06-08 | 卓悦环保新材料（上海）有限公司 | A kind of synthetic method of low silicon SAPO-34 molecular sieves |
| CN111115655A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Eutectic nano molecular sieve, preparation method and application thereof |
| CN111744547A (en) * | 2020-06-29 | 2020-10-09 | 华中科技大学 | Eutectic catalyst and preparation and application thereof by solid-state ion exchange method |
| CN112619697A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve |
| CN112756011A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application |
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| CN1227159C (en) * | 2001-03-01 | 2005-11-16 | 埃克森美孚化学专利公司 | Silicoaluminophosphate molecular sieve |
| 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 CN2010102619361A patent/CN102372291A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227159C (en) * | 2001-03-01 | 2005-11-16 | 埃克森美孚化学专利公司 | Silicoaluminophosphate molecular sieve |
| 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 |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633279A (en) * | 2012-04-17 | 2012-08-15 | 清华大学 | Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof |
| CN103263947A (en) * | 2013-06-03 | 2013-08-28 | 神华集团有限责任公司 | Composite molecular sieve for preparing catalyst for producing light olefins from organic oxygen-containing compound, and preparation method thereof |
| CN103418431A (en) * | 2013-08-28 | 2013-12-04 | 神华集团有限责任公司 | SAPO-34/SAPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound and preparation method thereof |
| CN103418431B (en) * | 2013-08-28 | 2015-11-04 | 神华集团有限责任公司 | SAPO-34/SAPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound and preparation method thereof |
| CN103878018B (en) * | 2014-01-22 | 2016-07-06 | 山西大学 | A kind of synthetic method of little crystal grain SAPO-18/SAPO-34 eutectic molecular sieve |
| CN103878018A (en) * | 2014-01-22 | 2014-06-25 | 山西大学 | Method for synthesizing small grain SAPO-18/SAPO-34 eutectic molecular sieve |
| CN105174286B (en) * | 2015-08-17 | 2017-12-22 | 久泰能源科技有限公司 | A kind of preparation method of the eutectic molecular sieves of AEI/CHA at high proportion |
| CN105174286A (en) * | 2015-08-17 | 2015-12-23 | 久泰能源科技有限公司 | Preparation method for high-proportion AEI/CHA eutectic molecular sieve |
| CN105819466A (en) * | 2016-03-04 | 2016-08-03 | 中国石油天然气股份有限公司 | SAPO-18/SAPO-34 eutectic molecular sieve, and preparation method and application thereof |
| CN108128782A (en) * | 2017-12-20 | 2018-06-08 | 卓悦环保新材料（上海）有限公司 | A kind of synthetic method of low silicon SAPO-34 molecular sieves |
| CN111115655A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Eutectic nano molecular sieve, preparation method and application thereof |
| CN112619697A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve |
| CN112619697B (en) * | 2019-09-24 | 2023-08-04 | 中国石油化工股份有限公司 | Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve |
| CN112756011A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application |
| CN111744547A (en) * | 2020-06-29 | 2020-10-09 | 华中科技大学 | Eutectic catalyst and preparation and application thereof by solid-state ion exchange method |
| CN111744547B (en) * | 2020-06-29 | 2021-10-15 | 华中科技大学 | Eutectic catalyst and preparation and application thereof by solid-state ion exchange method |
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Application publication date: 20120314 |