CN102372288B - Method for preparing SAPO-34 molecular sieve - Google Patents

Method for preparing SAPO-34 molecular sieve Download PDF

Info

Publication number
CN102372288B
CN102372288B CN 201010261851 CN201010261851A CN102372288B CN 102372288 B CN102372288 B CN 102372288B CN 201010261851 CN201010261851 CN 201010261851 CN 201010261851 A CN201010261851 A CN 201010261851A CN 102372288 B CN102372288 B CN 102372288B
Authority
CN
China
Prior art keywords
sapo
molecular sieve
solution
organic amine
preparation
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.)
Active
Application number
CN 201010261851
Other languages
Chinese (zh)
Other versions
CN102372288A (en
Inventor
王伟
刘红星
陆贤
方敬东
赵昱
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN 201010261851 priority Critical patent/CN102372288B/en
Publication of CN102372288A publication Critical patent/CN102372288A/en
Application granted granted Critical
Publication of CN102372288B publication Critical patent/CN102372288B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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 by 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.Shown good catalytic activity in methane producing light olefins (MTO) reaction, 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 Hydrothermal Synthesis (USP4440871, CN 1037334C, CN 1038125C, CN 1048428C), i.e. crystallization and obtaining in the high-temperature water hot system.Hydrothermal method prepares molecular sieve process more complicated, needs to use a large amount of organic formwork agents, and need to isolate zeolite product at last from mother liquor.
Vapor phase process is as a kind of method of preparation molecular sieve, and at zeolite molecular sieve, particularly there has been deep research the ZSM-5 molecular sieve aspect, but aspect phosphate aluminium molecular sieve synthetic, reports at present less.So-called vapor phase process refers in building-up process, at first the Zeolite synthesis presoma is prepared into dried glue under certain condition, then dried glue is placed in reactor top, the mixing solutions that adds a certain amount of organic amine and water in the reactor bottom simultaneously is as template, and dried glue does not contact with liquid phase part.Compare with traditional Hydrothermal Synthesis, vapor phase process can reduce the usage quantity of organic formwork agent greatly, saved numerous and diverse step that product separates with mother liquor, organic formwork agent easily reclaims and reuses, and is a kind of method for preparing the easy economic environment close friend of 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, degree of crystallinity is relatively poor.CN1693202 drops into template in dried glue preparation process, but through experimental verification, the SAPO-34 molecular sieve crystallinity of this kind method preparation improves not obvious, and when using it for methanol to olefins reaction, activity is relatively poor, and coking rate is very fast.
Summary of the invention
Technical problem to be solved by this invention be overcome report in previous literature to utilize vapor phase process to prepare SAPO-34 molecular sieve relative crystallinity lower, the problem that when being used for methanol-to-olefins reaction, activity is low, coking rate is fast provides a kind of preparation method of new SAPO-34 molecular sieve.It is high that the method has a SAPO-34 molecular sieve relative crystallinity that makes, the characteristics that when being used for methanol-to-olefins reaction, activity is high, coking rate is slow.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: 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, add organic amine and fluorochemical to get solution II in solution I, the mol ratio of each material in solution II is 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 that the span of 0.05～2, b is that the span of 0.05～2, c is that the span of 10～200, d is that the span of 0～10, e is 0.03～0.6;
(b) solution II is raise temperature to 70～90 ℃ colloid, then colloid is warming up to 100～160 ℃ and obtains dried glue;
(c) dried glue is placed in reactor upper gaseous phase position, with mass ratio 0.1～4: 1 water and the mixture of organic amine are placed in liquid phase position, reactor 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 technique scheme, the fluorochemical preferred version is hydrofluoric acid; The presoma preferred version of phosphorus is 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 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 morpholine.The precursor compound of phosphorus, aluminium, silicon soluble in water solution I, at room temperature stir after 1～3 hour and add organic amine, fluorochemical to get solution II.After 12～24 hours rising temperature to 80～90 ℃ in stirring at room for solution II in step (b), then continue to stir 3～5 hours to get colloid.Temperature with solution II in step (b) rises to 120～140 ℃, obtains dried glue after 12～24 hours.
In technique scheme, the crystallization temperature preferable range of reactor is 160～200 ℃.
The present invention is by being incorporated into fluorochemical in the synthetic SAPO-34 molecular sieve of vapor phase process, improved the relative crystallinity of molecular sieve, when it is used for methanol-to-olefins reaction as catalyzer, activity is improved, coking rate also is reduced, and has obtained technique effect preferably.
The present invention is further elaborated below by embodiment.
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 again the 14.6g aluminum oxide after fully mixing.
At room temperature stir after 2 hours and add TEAOH, add the mol ratio of each component this moment is Al 2O 3: P 2O 5: 1.25SiO 2: 75H 2O: TEAOH.
At room temperature continue to stir the temperature to 80 ℃ of raising gradually after 24 hours, continue to stir 3-5 hour, along with the evaporation of moisture in 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 be placed in reactor top, the reactor bottom is the mixing solutions of 7.5g triethylamine and 15g water.After reactor sealing, 180 ℃ of lower crystallization 48 hours, after cooling rear products therefrom fully washs, filters, 120 ℃ of dryings 5 hours, 550 ℃ of roastings namely got the SAPO-34 molecular sieve in 6 hours, stipulated that its degree of crystallinity is 100%.
[comparative example 2]
According to each Step By Condition of comparative example 1, but the template triethylamine bottom reactor is changed to the morphine woods, the degree of crystallinity that obtains at last SAPO-34 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 again the 14.6g aluminum oxide after fully mixing.
At room temperature stir after 2 hours and add TEAOH and hydrofluoric acid, add the mol ratio of 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 the temperature to 80 ℃ of raising gradually after 24 hours, continue to stir 3-5 hour, along with the evaporation of moisture in 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 be placed in reactor top, the reactor bottom is the mixing solutions of 7.5g triethylamine and 15g water.After reactor sealing, 180 ℃ of lower crystallization 48 hours, after cooling rear products therefrom fully washs, filters, 120 ℃ of dryings 5 hours, 550 ℃ of roastings namely got the SAPO-34 molecular sieve in 6 hours, and its degree of crystallinity is 123.3%.
[embodiment 2]
According to each Step By Condition of embodiment 1, but temperature of reaction is promoted to 200 ℃, the degree of crystallinity that obtains at last SAPO-34 is 105%.
[embodiment 3]
According to each Step By Condition of embodiment 1, but temperature of reaction is reduced to 160 ℃, the degree of crystallinity that obtains at last SAPO-34 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 degree of crystallinity that obtains at last SAPO-34 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 degree of crystallinity that obtains at last SAPO-34 is 126.3%.
[embodiment 6]
According to each Step By Condition of embodiment 1, but will the reaction times extend to 72h, the degree of crystallinity that obtains at last SAPO-34 is 116.4%.
[embodiment 7]
According to each Step By Condition of embodiment 1, be 146.7% but the template triethylamine of reactor bottom is changed to the degree of 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 degree of crystallinity that obtains at last SAPO-34 is 129.4%.
[embodiment 9]
According to each Step By Condition of embodiment 7, but temperature of reaction is promoted to 160 ℃, the degree of crystallinity that obtains at last SAPO-34 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 degree of crystallinity that obtains at last SAPO-34 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 degree of crystallinity that obtains at last SAPO-34 is 150.5%.
[embodiment 12]
According to each Step By Condition of embodiment 7, but will the reaction times extend to 72h, the degree of crystallinity that obtains at last SAPO-34 is 129.5%.
[embodiment 13]
The molecular 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 respectively triethylamine, morphine woods be that liquid phase template and embodiment 1, the embodiment 7 gained SAPO-34 molecular sieves that add fluorochemical carry out respectively catalysis examination experiment with adopting respectively triethylamine, morphine woods.Experiment condition is, the catalyst loading amount 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 results are shown in 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 all is enhanced from the 79.6 anti-coking performances that rise to 81.9, two groups of catalyzer.
Table 1
Figure BSA00000242383500051
Table 2

Claims (6)

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, add organic amine and fluorochemical to get solution II in solution I, the mol ratio of each material in solution II is 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 that the span of 0.05～2, b is that the span of 0.05～2, c is that the span of 10～200, d is that the span of 0～10, e is 0.03～0.6;
(b) solution II is raise temperature to 70～90 ℃ colloid, then colloid is warming up to 100～160 ℃ and obtains dried glue;
(c) dried glue is placed in reactor upper gaseous phase position, with mass ratio 0.1～4: 1 water and the mixture of organic amine are placed in liquid phase position, reactor 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;
Described fluorochemical is hydrofluoric acid.
2. the preparation method of SAPO-34 molecular sieve according to claim 1, the presoma that it is characterized in that phosphorus is ortho-phosphoric acid; The presoma of aluminium is selected from activated alumina, pseudo-boehmite or aluminum isopropylate; The presoma of silicon is silicon sol; Organic amine is selected from least a in triethylamine, tetraethyl-oxyammonia or morpholine.
3. 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 and add organic amine, fluorochemical to get solution II.
4. the preparation method of SAPO-34 molecular sieve according to claim 1, after 12～24 hours rising temperature to 80～90 ℃ in stirring at room to it is characterized in that in step (b) solution II, then continue to stir 3～5 hours to get colloid.
5. the preparation method of SAPO-34 molecular sieve according to claim 1 is characterized in that in step (b) temperature of solution II is risen to 120～140 ℃, obtains dried glue after 12～24 hours.
6. the preparation method of SAPO-34 molecular sieve according to claim 1, is characterized in that crystallization temperature is 160～200 ℃.
CN 201010261851 2010-08-23 2010-08-23 Method for preparing SAPO-34 molecular sieve Active CN102372288B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010261851 CN102372288B (en) 2010-08-23 2010-08-23 Method for preparing SAPO-34 molecular sieve

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010261851 CN102372288B (en) 2010-08-23 2010-08-23 Method for preparing SAPO-34 molecular sieve

Publications (2)

Publication Number Publication Date
CN102372288A CN102372288A (en) 2012-03-14
CN102372288B true CN102372288B (en) 2013-05-08

Family

ID=45791602

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010261851 Active CN102372288B (en) 2010-08-23 2010-08-23 Method for preparing SAPO-34 molecular sieve

Country Status (1)

Country Link
CN (1) CN102372288B (en)

Families Citing this family (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
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
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
CN106044791B (en) * 2016-05-30 2018-12-07 深圳科冠华太新材料技术有限公司 A kind of solid phase synthesis process of thin slice stratiform SAPO-34
CN107827121B (en) * 2017-11-17 2020-08-11 陕西延长石油（集团）有限责任公司 Synthesis method of SAPO-34 molecular sieve with high specific surface area
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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
CN102372288A (en) 2012-03-14

Similar Documents

Publication Publication Date Title
CN102372288B (en) Method for preparing SAPO-34 molecular sieve
CN102464340A (en) Method for synthesizing silicoaluminophosphate (SAPO)-34 molecular sieve
KR101743760B1 (en) Method for manufacturing of SSZ-13 zeolite catalyst and the SSZ-13 zeolite catalyst thereby
US20130178680A1 (en) Catalyst for oxidative coupling of methane, method for preparing the same, and method for oxidative coupling reaction of methane using the same
CN102838131B (en) Sapo-34 molecular sieve and preparation method thereof
CN101962195A (en) Method for preparing hierarchical porous titanium silicalite TS-1
CN103055929A (en) Fluid catalyst for preparing olefin through catalytic cracking and preparation method thereof
CN105983440A (en) Composite nanometer thin layer molecular sieve and preparation method and application
JP2021531162A (en) Catalysts for producing ethylbenzene from ethanol and benzene, their production methods and applications
CN100374203C (en) Homogeneous temperature type catalyst for preparing dimethyl ether from methanol and use
CN104971768B (en) A kind of SAPO-34/ natural clay composite material and preparation method and application
CN108569707B (en) Multi-stage pore SAPO-34 molecular sieve and application thereof in methanol-to-olefin reaction
CN1182034C (en) Method for preparing aluminium silicophosphate molecular sieve
CN101417811A (en) Method for synthesizing SAPO-35 molecular sieve by using bi-template
CN104326483B (en) A kind of low silicon composite molecular sieve and synthetic method and application
CN102381922B (en) Method for compounding ethylene by ethanol
JP2010042344A (en) Catalyst for manufacturing lower olefin, method of manufacturing the same and method of manufacturing lower olefin using catalyst
CN103539145B (en) Preparation method of SAPO (Si, Al, P, O)-34 molecular sieve
CN102807465B (en) Method for producing propane and gasoline by using butane
CN105384178A (en) Gas-phase synthesis method for SAPO-34 molecular sieve
CN109422627B (en) Method for preparing tert-butyl glyceryl ether by glycerol etherification
CN103420388A (en) Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method
JPH0920513A (en) Preparation of micromesoporous gel
CN115155553A (en) Preparation method of amorphous aluminosilicate solid acid catalyst and application of amorphous aluminosilicate solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation
CN102372545B (en) Method for preparing olefin by alcohol dehydration

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant