CN102372288A - Method for preparing SAPO-34 molecular sieve - Google Patents

Method for preparing SAPO-34 molecular sieve Download PDF

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CN102372288A
CN102372288A CN2010102618513A CN201010261851A CN102372288A CN 102372288 A CN102372288 A CN 102372288A CN 2010102618513 A CN2010102618513 A CN 2010102618513A CN 201010261851 A CN201010261851 A CN 201010261851A CN 102372288 A CN102372288 A CN 102372288A
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sapo
molecular sieve
solution
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organic amine
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CN102372288B (en
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王伟
刘红星
陆贤
方敬东
赵昱
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method for preparing a SAPO-34 molecular sieve, which aims at solving the problems that the SAPO-34 molecular sieve prepared by a vapor phase method has low crystallization degree, poor reaction activity when being used for preparing low olefins by methanol and fast coking rate. According to the invention, a precursor compound of aluminum, silicon and phosphor, fluoride and an organic template are prepared to dry glue and placed at the upper part of a reaction vessel, a mixed solution of water and organic amine is placed at the lower part of the reaction vessel, and the SAPO-34 molecular sieve is prepared under the reaction condition with 140-220 DEG C of crystallization temperature. The technical scheme of the method for preparing the SAPO-34 molecular sieve solves the problems better, and is used for preparing low olefins by methanol in industrial production.

Description

The preparation method of SAPO-34 molecular sieve
Technical field
The present invention relates to a kind of preparation method of SAPO-34 molecular sieve, specifically, the invention relates to the method for preparing the SAPO-34 molecular sieve through vapor phase process.
Background technology
U.S. Union Carbide Corp had developed a series of silicoaluminophosphamolecular molecular sieves in 1984, and wherein the SAPO-34 molecular sieve has similar phosphorus zeolite type structure, belongs to pore zeolite, can be used as sorbent material, catalyzer and support of the catalyst.In methane producing light olefins (MTO) reaction, shown good catalytic activity, selectivity of light olefin is up to more than 90%, and the therein ethylene selectivity can reach more than 50%, C 5Above product amount is considerably less.The classical method for preparing SAPO-34 is hydro-thermal synthetic (USP4440871, CN 1037334C, CN 1038125C, CN 1048428C), i.e. crystallization and obtaining in the high-temperature water hot system.Hydrothermal Preparation molecular sieve process more complicated needs to use a large amount of organic formwork agents, and need from mother liquor, isolate zeolite product at last.
Vapor phase process is as a kind of method of preparation molecular sieve, and at zeolite molecular sieve, particularly there has been deep research ZSM-5 molecular sieve aspect, but aspect phosphate aluminium molecular sieve synthetic, reports less at present.So-called vapor phase process is meant in building-up process; At first be prepared into dried glue to the synthetic presoma of molecular sieve under certain condition; Place reaction kettle top to dried glue then, the mixing solutions that adds a certain amount of organic amine and water in the reaction kettle bottom simultaneously is as template, and dried glue does not contact with liquid phase part.Compare with traditional hydro-thermal is synthetic; Vapor phase process can reduce the usage quantity of organic formwork agent greatly; Saved the isolating numerous and diverse step of product and mother liquor, organic formwork agent easy recovery and recycling are a kind of friendly methods of easy economic environment for preparing molecular sieve.
Also use vapor phase process to prepare the SAPO-34 molecular sieve just like CN1363519A at present, but it only uses organic formwork agent at liquid phase part, percent crystallinity is relatively poor.CN1693202 prepares at dried glue and drops into template in the process, but through experimental verification, the SAPO-34 molecular sieve crystallinity of this kind method preparation improves not obvious, and activity is relatively poor when using it for methanol to olefins reaction, and coking rate is very fast.
Summary of the invention
Technical problem to be solved by this invention be overcome report in the document in the past to utilize vapor phase process to prepare SAPO-34 molecular sieve relative crystallinity lower; The problem that activity is low when being used for methanol-to-olefins reaction, coking rate is fast provides a kind of preparation method of new SAPO-34 molecular sieve.This method has the SAPO-34 molecular sieve relative crystallinity height that makes, active high, the slow characteristics of coking rate when being used for methanol-to-olefins reaction.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of preparation method of SAPO-34 molecular sieve in turn includes the following steps:
(a) with the precursor compound of phosphorus, aluminium, the silicon solution I that gets soluble in water, adding organic amine and fluorochemical get solution II in solution I, the mol ratio of each material in the solution II are consisted of: Al 2O 3: a SiO 2: bP 2O 5: cH 2O: d organic amine: the e fluorochemical, wherein the span of a is 0.05～2, and the span of b is 0.05～2, and the span of c is 10～200, and the span of d is 0～10, the span of e is 0.03～0.6;
(b) with solution II elevated temperature to 70～90 ℃ colloid, then colloid is warming up to 100～160 ℃ and obtains dried glue;
(c) dried glue is placed reaction kettle upper gaseous phase position; With mass ratio 0.1～4: 1 the water and the mixture of organic amine place liquid phase position, reaction kettle bottom, crystallization temperature be under 140～220 ℃ of conditions organic amine steam and the reaction of dried glue 12～72 hours the SAPO-34 molecular sieve.
In the technique scheme, the fluorochemical preferred version is a hydrofluoric acid; The presoma preferred version of phosphorus is an ortho-phosphoric acid, and more preferably scheme is the ortho-phosphoric acid of quality 85%; The presoma preferred version of aluminium is selected from activated alumina, pseudo-boehmite or aluminum isopropylate; The presoma preferred version of silicon is a silicon sol, and more preferably scheme is the silicon sol of quality 30～40%; The organic amine preferred version is selected from least a in triethylamine, tetraethyl-oxyammonia or the morphine quinoline.The precursor compound of phosphorus, aluminium, silicon soluble in water solution I, at room temperature stir after 1～3 hour add organic amine, fluorochemical gets solution II.After 12～24 hours elevated temperature to 80～90 ℃ in stirring at room for solution II in the step (b), continue then to stir 3～5 hours colloid.Temperature with solution II in the step (b) rises to 120～140 ℃, obtains dried glue after 12～24 hours.
The crystallization temperature preferable range of reaction kettle is 160～200 ℃ in the technique scheme.
The present invention is through being incorporated into fluorochemical in the synthetic SAPO-34 molecular sieve of vapor phase process; Improved the relative crystallinity of molecular sieve; Activity was improved when it was used for methanol-to-olefins reaction as catalyzer, coking rate also is reduced, and had obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
Embodiment
[comparative example 1]
Under the state that stirs, the phosphoric acid of 23g 85% and the silicon sol of 28.2g silicone content 30% are dropped in the 94g deionized water, add the 14.6g aluminum oxide behind the thorough mixing again.
At room temperature stir after 2 hours and add TEAOH, the mol ratio that add each component this moment is Al 2O 3: P 2O 5: 1.25SiO 2: 75H 2O: TEAOH.
At room temperature continue to stir after 24 hours gradually elevated temperature to 80 ℃, continue to stir 3-5 hour, along with the evaporation of moisture in the reaction process, the viscosity of system becomes greatly gradually, is colloidal.Colloid is dropped into baking oven, and 120 ℃ of heating are more than 12 hours, and moisture evaporates fully, becomes dried glue.
With dried glue grind into powder, to get the dried glue of 6.5g and place reaction kettle top, the reaction kettle bottom is the mixing solutions of 7.5g triethylamine and 15g water.Reaction kettle sealing back is 180 ℃ of following crystallization 48 hours, cooling back products therefrom thorough washing, filters the back 120 ℃ of dryings 5 hours, and 550 ℃ of roastings promptly got the SAPO-34 molecular sieve in 6 hours, stipulated that its percent crystallinity is 100%.
[comparative example 2]
According to each Step By Condition of comparative example 1, but the template triethylamine of reaction kettle bottom is changed to the morphine woods, the percent crystallinity that obtains SAPO-34 at last is 125.1%.
[embodiment 1]
Under the state that stirs, the phosphoric acid of 23g 85% and the silicon sol of 28.2g silicone content 30% are dropped in the 94g deionized water, add the 14.6g aluminum oxide behind the thorough mixing again.
At room temperature stir adding TEAOH and hydrofluoric acid after 2 hours, the mol ratio that add each component this moment is Al 2O 3: P 2O 5: 1.25SiO 2: 75H 2O: TEAOH: 0.06HF.
At room temperature continue to stir after 24 hours gradually elevated temperature to 80 ℃, continue to stir 3-5 hour, along with the evaporation of moisture in the reaction process, the viscosity of system becomes greatly gradually, is colloidal.Colloid is dropped into baking oven, and 120 ℃ of heating are more than 12 hours, and moisture evaporates fully, becomes dried glue.
With dried glue grind into powder, to get the dried glue of 6.5g and place reaction kettle top, the reaction kettle bottom is the mixing solutions of 7.5g triethylamine and 15g water.Reaction kettle sealing back is 180 ℃ of following crystallization 48 hours, cooling back products therefrom thorough washing, filters the back 120 ℃ of dryings 5 hours, and 550 ℃ of roastings promptly got the SAPO-34 molecular sieve in 6 hours, and its percent crystallinity is 123.3%.
[embodiment 2]
According to each Step By Condition of embodiment 1, but temperature of reaction is promoted to 200 ℃, the percent crystallinity that obtains SAPO-34 at last is 105%.
[embodiment 3]
According to each Step By Condition of embodiment 1, but temperature of reaction is reduced to 160 ℃, the percent crystallinity that obtains SAPO-34 at last is 127.5%.
[embodiment 4]
According to each Step By Condition of embodiment 1, but the mol ratio of each component is adjusted into Al 2O 3: P 2O 5: 1.25SiO 2: 75H 2O: TEAOH: 0.04HF, the percent crystallinity that obtains SAPO-34 at last is 120.5%.
[embodiment 5]
According to each Step By Condition of embodiment 1, but the mol ratio of each component is adjusted into Al 2O 3: P 2O 5: 1.25SiO 2: 75H 2O: TEAOH: 0.08HF, the percent crystallinity that obtains SAPO-34 at last is 126.3%.
[embodiment 6]
According to each Step By Condition of embodiment 1, but will the reaction times extend to 72h, the percent crystallinity that obtains SAPO-34 at last is 116.4%.
[embodiment 7]
According to each Step By Condition of embodiment 1, be 146.7% but the template triethylamine of reaction kettle bottom is changed to the percent crystallinity that the morphine woods obtains SAPO-34 at last.
[embodiment 8]
According to each Step By Condition of embodiment 7, but temperature of reaction is promoted to 200 ℃, the percent crystallinity that obtains SAPO-34 at last is 129.4%.
[embodiment 9]
According to each Step By Condition of embodiment 7, but temperature of reaction is promoted to 160 ℃, the percent crystallinity that obtains SAPO-34 at last is 151.2%.
[embodiment 10]
According to each Step By Condition of embodiment 7, but the mol ratio of each component is adjusted into Al 2O 3: P 2O 5: 1.25SiO 2: 75H 2O: TEAOH: 0.04HF, the percent crystallinity that obtains SAPO-34 at last is 141.3%.
[embodiment 11]
According to each Step By Condition of embodiment 7, but the mol ratio of each component is adjusted into Al 2O 3: P 2O 5: 1.25SiO 2: 75H 2O: TEAOH: 0.08HF, the percent crystallinity that obtains SAPO-34 at last is 150.5%.
[embodiment 12]
According to each Step By Condition of embodiment 7, but will the reaction times extend to 72h, the percent crystallinity that obtains SAPO-34 at last is 129.5%.
[embodiment 13]
The sieve catalyst examination
Adopting fixed-bed catalytic reactor, is liquid phase template and the comparative example 1 that does not add fluorochemical, comparative example 2 and to adopt triethylamine, morphine woods respectively be that liquid phase template and embodiment 1, the embodiment 7 gained SAPO-34 molecular sieves that add fluorochemical carry out catalysis examination experiment respectively with adopting triethylamine, morphine woods respectively.Experiment condition does, the catalyzer tonburden is 2.0 grams, and 460 ℃ of temperature of reaction, reaction pressure are normal pressure, and raw material adopts pure methyl alcohol, and air speed is 6 gram methanol/gram catalyst hour.The result sees table 1, table 2.
The methanol conversion of four groups of catalyzer all near 100% situation under; By table 1, table 2 can find out fluorochemical is incorporated into the synthetic SAPO-34 reaction system of gas phase after; The catalytic performance that the SAPO-34 molecular sieve is applied to the reaction for preparing light olefins from methanol system is enhanced; When using triethylamine as template, the selectivity of ethene and propylene rises to 81.0 from 79.2, when using the morphine woods as template; The selectivity of ethene and propylene from 79.6 rise to 81.9, two groups of catalyzer the anti-coking performance all be enhanced.
Table 1
Figure BSA00000242383500051
Table 2
Figure BSA00000242383500061

Claims (7)

1. the preparation method of a SAPO-34 molecular sieve in turn includes the following steps:
(a) with the precursor compound of phosphorus, aluminium, the silicon solution I that gets soluble in water, adding organic amine and fluorochemical get solution II in solution I, the mol ratio of each material in the solution II are consisted of: Al 2O 3: a SiO 2: bP 2O 5: cH 2O: d organic amine: the e fluorochemical, wherein the span of a is 0.05～2, and the span of b is 0.05～2, and the span of c is 10～200, and the span of d is 0～10, the span of e is 0.03～0.6;
(b) with solution II elevated temperature to 70～90 ℃ colloid, then colloid is warming up to 100～160 ℃ and obtains dried glue;
(c) dried glue is placed reaction kettle upper gaseous phase position; With mass ratio 0.1～4: 1 the water and the mixture of organic amine place liquid phase position, reaction kettle bottom, crystallization temperature be under 140～220 ℃ of conditions organic amine steam and the reaction of dried glue 12～72 hours the SAPO-34 molecular sieve.
2. the preparation method of SAPO-34 molecular sieve according to claim 1 is characterized in that fluorochemical is a hydrofluoric acid.
3. the preparation method of SAPO-34 molecular sieve according to claim 1, the presoma that it is characterized in that phosphorus is an ortho-phosphoric acid; The presoma of aluminium is selected from activated alumina, pseudo-boehmite or aluminum isopropylate; The presoma of silicon is a silicon sol; Organic amine is selected from least a in triethylamine, tetraethyl-oxyammonia or the morphine quinoline.
4. the preparation method of SAPO-34 molecular sieve according to claim 1, it is characterized in that the precursor compound of phosphorus, aluminium, silicon soluble in water solution I, at room temperature stir after 1～3 hour add organic amine, fluorochemical gets solution II.
5. the preparation method of SAPO-34 molecular sieve according to claim 1, after 12～24 hours elevated temperature to 80～90 ℃ in stirring at room to it is characterized in that in the step (b) solution II, continue then to stir 3～5 hours colloid.
6. the preparation method of SAPO-34 molecular sieve according to claim 1 is characterized in that in the step (b) temperature of solution II is risen to 120～140 ℃, obtains dried glue after 12～24 hours.
7. the preparation method of SAPO-34 molecular sieve according to claim 1 is characterized in that crystallization temperature is 160～200 ℃.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103420388A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method
CN103539145A (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)-34 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
CN106044791A (en) * 2016-05-30 2016-10-26 太原理工大学 Solid-phase synthesizing method of flaky lamellar SAPO-34
CN107601527A (en) * 2017-11-17 2018-01-19 陕西延长石油（集团）有限责任公司 A kind of preparation method of nanometer of molecular sieve of SAPO 34
CN107827121A (en) * 2017-11-17 2018-03-23 陕西延长石油（集团）有限责任公司 A kind of synthetic method of the molecular sieves of high-specific surface area SAPO 34
CN109928407A (en) * 2017-12-15 2019-06-25 中国石油化工股份有限公司 A kind of synthetic method of SAPO-34 molecular sieve
CN113277531A (en) * 2021-07-14 2021-08-20 中国矿业大学 Method for preparing small-crystal-grain SAPO-34 molecular sieve

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CN1467155A (en) * 2002-07-10 2004-01-14 中国石油化工股份有限公司 Method for preparing aluminium silicophosphate molecular sieve
CN1683078A (en) * 2004-04-16 2005-10-19 中国石油化工股份有限公司 Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve
CN101125665A (en) * 2007-08-08 2008-02-20 华陆工程科技有限责任公司 Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method

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CN1467155A (en) * 2002-07-10 2004-01-14 中国石油化工股份有限公司 Method for preparing aluminium silicophosphate molecular sieve
CN1683078A (en) * 2004-04-16 2005-10-19 中国石油化工股份有限公司 Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve
CN101125665A (en) * 2007-08-08 2008-02-20 华陆工程科技有限责任公司 Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103420388A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method
CN103539145A (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)-34 molecular sieve
CN103539145B (en) * 2012-07-12 2017-04-19 中国石油化工股份有限公司 Preparation method of SAPO (Si, Al, P, O)-34 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
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
CN106044791A (en) * 2016-05-30 2016-10-26 太原理工大学 Solid-phase synthesizing method of flaky lamellar SAPO-34
CN107601527A (en) * 2017-11-17 2018-01-19 陕西延长石油（集团）有限责任公司 A kind of preparation method of nanometer of molecular sieve of SAPO 34
CN107827121A (en) * 2017-11-17 2018-03-23 陕西延长石油（集团）有限责任公司 A kind of synthetic method of the molecular sieves of high-specific surface area SAPO 34
CN107601527B (en) * 2017-11-17 2020-06-30 陕西延长石油（集团）有限责任公司 Preparation method of nano SAPO-34 molecular sieve
CN109928407A (en) * 2017-12-15 2019-06-25 中国石油化工股份有限公司 A kind of synthetic method of SAPO-34 molecular sieve
CN109928407B (en) * 2017-12-15 2021-01-05 中国石油化工股份有限公司 Synthesis method of SAPO-34 molecular sieve
CN113277531A (en) * 2021-07-14 2021-08-20 中国矿业大学 Method for preparing small-crystal-grain SAPO-34 molecular sieve

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