CN105174279A - Preparation method of nanosize aluminum phosphate molecular sieve - Google Patents
Preparation method of nanosize aluminum phosphate molecular sieve Download PDFInfo
- Publication number
- CN105174279A CN105174279A CN201510593307.1A CN201510593307A CN105174279A CN 105174279 A CN105174279 A CN 105174279A CN 201510593307 A CN201510593307 A CN 201510593307A CN 105174279 A CN105174279 A CN 105174279A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- hours
- phosphate molecular
- aluminum phosphate
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a nanosize aluminum phosphate molecular sieve, belonging to the fields of new catalytic material synthesis and energy chemical industry. The preparation method comprises the following steps: by using pseudoboehmite, a heteroatom source, phosphoric acid and organic amine as raw materials, carrying out freeze-drying on the mixture to obtain dry glue, and carrying out heating crystallization treatment on the dry glue to obtain the aluminum phosphate molecular sieve. According to the preparation method, the freeze-drying technique is firstly utilized to prepare the dry glue from the glue, and the dry glue is then crystallized. The aluminum phosphate molecular sieve prepared by the method has nanosize, and has high specific area.
Description
Technical field
The present invention relates to a kind of preparation method of nano-scale aluminium phosphate molecular sieve, belong to new catalytic material synthesis, derived energy chemical field.
Background technology
By isomorphous substitution to introducing hetero-atoms in skeleton, can give phosphate aluminium molecular sieve surface acidity, wherein Me/SAPO-11, Me/SAPO-34, Me/SAPO-5 molecular sieve etc. are widely used.Me/SAPO-11 molecular sieve has shown excellent reactive behavior because of its suitable one dimension ten-ring structure and gentle Acidity in direct-connected alkane isomerization field; Me/SAPO-34 molecular sieve has chabazite octatomic ring pore passage structure, shows high ethene, Propylene Selectivity in MTO technology; SAPO-5 is twelve-ring pore passage structure, in the reactions such as alkylation, have higher catalytic capability.In heterogeneous catalytic reaction, the diffusion couple catalyzed reaction of reactant and product affects significantly.Prepare nanoscale molecular sieve and can increase outside surface exposure, shorten orifice throat length, reduce diffusional resistance, increase the engagement capacity of reactant and catalytic active site, promote that product departs from catalytic body phase, suppress side reaction to occur.The synthesis of nanoscale molecular sieve is generated by acceleration molecular sieve nucleus, and suppress the control devices such as aggregation of particles to be realized, common method has dry gel method, synthesis method, space boundary method etc.Synthesize the Decomposition can strengthening gel by introducing heating, nucleus quantity is made to reach close to saturated state at short notice, ensuing crystallization rate is accelerated, the molecular sieve particle diameter synthesized also can be controlled, the degree of crystallinity of synthetic sample is high, and can save the necessary low temperature aging program of conventional heating methods, but its synthesis condition is comparatively harsh, molecular sieve is defined in limited space by space boundary method, hinders it to grow and prevents the polymerization of its crystal grain.Mainly comprise micro emulsion method, the sterically hindered method of inert media, hydrogel constraint rule three kinds, need additionally to add hard mould agent.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of preparation method of nano-scale aluminium phosphate molecular sieve, dry gel method is utilized to have higher solid-to-liquid ratio, easily bring out the generation of small crystal grain molecular sieve, and possess the advantage that water consumption is less, template can reuse, the present invention, on the basis playing xerogel advantage, prepares nanoscale, the high sieve sample than specific surface area by regulating and controlling dry glue preparation condition.
Concrete technical scheme is:
The preparation method of nano-scale aluminium phosphate molecular sieve, comprises the following steps:
1) following raw material is according to mol ratio proportioning, pseudo-boehmite, with Al
2o
3meter; Heteroatoms source, is designated as M, with oxide basis; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: heteroatoms source: phosphoric acid: organic amine=0.8 ~ 1.0:0 ~ 0.6:1.0:0.8 ~ 1.2;
Raw material and deionized water mix and blend 10-60 minute, the lyophilize at-80 ~-40 DEG C of gained colloid, 3.5 ~ 8.0, is then prepared dry glue in 1 ~ 4 day by regulation system pH value;
(2) by the dry glue of step (1) gained in autoclave at 160 ~ 200 DEG C crystallization after 8 ~ 72 hours, obtain crystallization product; With the deionized water of mass ratio 6 ~ 11 times of crystallization products, gained crystallization product is washed and filtered, then at 60 ~ 120 DEG C, carry out drying 2 ~ 12 hours, then roasting obtains the molecular sieve of aluminum phosphate after 2 ~ 10 hours at 350 ~ 650 DEG C.
Described heteroatoms source comprises Si, alkaline-earth metal, transition metal, the soluble compounds of thulium and/or hydrolyzable compound, the soluble compounds of the elements such as such as Si, Ge, Fe, Mg, Ca, Zn, Fe, Co, Cu, Ni, Ti, Zr, Mn, Y, La and Ce and/or hydrolyzable compound.
Described organic amine is a kind of in Di-n-Butyl Amine, triethylamine, Tri-n-Propylamine, tetraethyl ammonium hydroxide, di-n-propylamine and Diisopropylamine or both mixtures.
The preparation method of nano-scale aluminium phosphate molecular sieve provided by the invention, first adopt Freeze Drying Technique to be dry glue by colloid lyophilize, then carrying out crystallization to dry glue, aluminium phosphate molecular sieve prepared by the method has nanoscale, and specific surface area is high.
Embodiment
The specific embodiment of the present invention is described in conjunction with the embodiments.
The raw material that embodiment is used:
Pseudo-boehmite, Yantai Heng Hui Chemical Co., Ltd. produces, Al
2o
3content 70wt%;
Phosphoric acid, Xilong Chemical Co., Ltd produces, analytical pure;
Di-n-propylamine and Diisopropylamine, deionized water, DIPEA, magnesium chloride, cobaltous chloride, zirconium oxychloride, tetraethyl ammonium hydroxide, Chemical Reagent Co., Ltd., Sinopharm Group produces, analytical pure;
Acidic silicasol, Qingdao Marine Chemical Co., Ltd. produces, SiO
2content 25%.
Embodiment 1
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: phosphoric acid: organic amine=1.0:1.0:1.0;
Organic amine is the mixture of di-n-propylamine and Diisopropylamine mass ratio 1:1;
With deionized water mix and blend after 30 minutes regulation system pH value be 5.5, then the lyophilize at-80 DEG C of gained colloid is prepared dry glue in 1 day; By dry for gained glue in autoclave at 160 DEG C crystallization after 54 hours, obtain crystallization product; Be that the deionized water of crystallization product 6 times to wash it and filters by quality, then carry out drying 4 hours in 100 DEG C, then in 550 DEG C through roasting after 4 hours the AlPO-11 molecular sieve of aluminum phosphate, its particle size is 100nm, and specific surface area is 250m
2/ g.
Embodiment 2
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Magnesium chloride, in MgO; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: magnesium chloride: phosphoric acid: DIPEA=1.0:0.1:0.4:0.9;
With deionized water mix and blend after 20 minutes regulation system pH value be 7.0, then the lyophilize at-70 DEG C of gained colloid is prepared dry glue in 2 days; By dry for gained glue in autoclave at 160 DEG C crystallization after 72 hours, obtain crystallization product; Be that the deionized water of crystallization product 7 times to wash it and filters by quality, then carry out drying 6 hours in 80 DEG C, then in 600 DEG C through roasting after 3 hours the MgAPSO-18 molecular sieve of aluminum phosphate, its particle size is 200nm, and specific surface area is 220m
2/ g.
Embodiment 3
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Cobaltous chloride, in CoO; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: cobaltous chloride: phosphoric acid: Tri-n-Propylamine=0.9:0.1:1.0:0.8;
Will with deionized water mix and blend after 40 minutes regulation system pH value be 6.0, then the lyophilize at-60 DEG C of gained colloid is prepared dry glue in 2.5 days; By dry for gained glue in autoclave at 170 DEG C crystallization after 36 hours, obtain crystallization product; Be that the deionized water of crystallization product 8 times to wash it and filters by quality, then carry out drying 12 hours in 60 DEG C, then in 650 DEG C through roasting after 2 hours the CoAPO-5 molecular sieve of aluminum phosphate, its particle size is 300nm, and specific surface area is 235m
2/ g.
Embodiment 4
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Zirconium oxychloride, with ZrO
2meter; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: zirconium oxychloride: phosphoric acid: di-n-propylamine=1.0:0.05:1.0:1.2;
With deionized water mix and blend after 60 minutes regulation system pH value be 4.0, then the lyophilize at-40 DEG C of gained colloid is prepared dry glue in 4 days; By dry for gained glue in autoclave at 200 DEG C crystallization after 24 hours, obtain crystallization product; Be that the deionized water of crystallization product 11 times to wash it and filters by quality, then carry out drying 2 hours in 120 DEG C, then in 500 DEG C through roasting after 6 hours the ZrAPO-11 molecular sieve of aluminum phosphate, its particle size is 500nm, and specific surface area is 215m
2/ g.
Embodiment 5
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Acidic silicasol, with SiO
2meter; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: acidic silicasol: phosphoric acid: tetraethyl ammonium hydroxide=1.0:0.5:1.0:1.0;
With deionized water mix and blend after 30 minutes regulation system pH value be 5.0, then the lyophilize at-80 DEG C of gained colloid is prepared dry glue in 1 day; By dry for gained glue in autoclave at 170 DEG C crystallization after 48 hours, obtain crystallization product; Be that the deionized water of crystallization product 9 times to wash it and filters by quality, then carry out drying 4 hours in 100 DEG C, then in 450 DEG C through roasting after 6 hours the SAPO-34 molecular sieve of aluminum phosphate, its particle size is 150nm, and specific surface area is 218m
2/ g.
Embodiment 6
Following raw material is according to mol ratio proportioning, and pseudo-boehmite, with Al
2o
3meter; Magnesium chloride, in MgO; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: magnesium chloride: phosphoric acid: organic amine=1.0:0.05:1.0:1.2;
Organic amine is the mixture of di-n-propylamine and Diisopropylamine mass ratio 1:1;
With deionized water mix and blend after 10 minutes regulation system pH value be 3.5, then the lyophilize at-50 DEG C of gained colloid is prepared dry glue in 3 days; By dry for gained glue in autoclave at 200 DEG C crystallization after 8 hours, obtain crystallization product; Be that the deionized water of crystallization product 11 times to wash it and filters by quality, then carry out drying 5 hours in 90 DEG C, then in 350 DEG C through roasting after 10 hours the MgAPO-31 molecular sieve of aluminum phosphate, its particle size is 400nm, and specific surface area is 205m
2/ g.
Claims (3)
1. the preparation method of nano-scale aluminium phosphate molecular sieve, is characterized in that, comprises the following steps:
(1) following raw material is according to mol ratio proportioning, pseudo-boehmite, with Al
2o
3meter; Heteroatoms source, is designated as M, with oxide basis; Phosphoric acid, with P
2o
5meter;
Pseudo-boehmite: heteroatoms source: phosphoric acid: organic amine=0.8 ~ 1.0:0 ~ 0.6:1.0:0.8 ~ 1.2;
Raw material and deionized water mix and blend 10-60 minute, the lyophilize at-80 ~-40 DEG C of gained colloid, 3.5 ~ 8.0, is then prepared dry glue in 1 ~ 4 day by regulation system pH value;
(2) by the dry glue of step (1) gained in autoclave at 160 ~ 200 DEG C crystallization after 8 ~ 72 hours, obtain crystallization product; With the deionized water of mass ratio 6 ~ 11 times of crystallization products, gained crystallization product is washed and filtered, then at 60 ~ 120 DEG C, carry out drying 2 ~ 12 hours, then roasting obtains the molecular sieve of aluminum phosphate after 2 ~ 10 hours at 350 ~ 650 DEG C.
2. the preparation method of nano-scale aluminium phosphate molecular sieve according to claim 1, is characterized in that, described heteroatoms source comprises Si, alkaline-earth metal, transition metal, the soluble compounds of thulium and/or hydrolyzable compound.
3. the preparation method of nano-scale aluminium phosphate molecular sieve according to claim 1, it is characterized in that, described organic amine is a kind of in Di-n-Butyl Amine, triethylamine, Tri-n-Propylamine, tetraethyl ammonium hydroxide, di-n-propylamine and Diisopropylamine or both mixtures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510593307.1A CN105174279B (en) | 2015-09-17 | 2015-09-17 | The preparation method of nano-scale aluminium phosphate molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510593307.1A CN105174279B (en) | 2015-09-17 | 2015-09-17 | The preparation method of nano-scale aluminium phosphate molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105174279A true CN105174279A (en) | 2015-12-23 |
| CN105174279B CN105174279B (en) | 2017-06-20 |
Family
ID=54896820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510593307.1A Active CN105174279B (en) | 2015-09-17 | 2015-09-17 | The preparation method of nano-scale aluminium phosphate molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105174279B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582803A (en) * | 2016-10-31 | 2017-04-26 | 昆明理工大学 | Preparation method of catalyst for alpha-pinene hydrogenation |
| 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 |
| CN108147422A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of CHA types Activity of Magnesium Aluminophosphate Molecular Sieve and preforming synthetic method |
| CN108147427A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of CHA types hetero atom Metal-aluminophosphate Molecular Siever and preforming synthetic method |
| CN109354035A (en) * | 2018-11-24 | 2019-02-19 | 江西师范大学 | A method of AlPO-18 molecular sieve is prepared using double template |
| CN109422272A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AFI structure hetero atom Metal-aluminophosphate Molecular Siever |
| CN109422280A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AFI structure aluminium phosphate molecular sieve |
| CN109759129A (en) * | 2019-01-15 | 2019-05-17 | 昆明理工大学 | A kind of Modification on Al PO4The preparation method and application of multistage porous molecular sieve |
| CN112250083A (en) * | 2019-07-22 | 2021-01-22 | 青岛科技大学 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
| CN112279270A (en) * | 2019-07-22 | 2021-01-29 | 青岛科技大学 | Aluminum phosphate molecular sieve and preparation method thereof |
| CN113104860A (en) * | 2020-05-14 | 2021-07-13 | 青岛大学威海创新研究院 | Preparation method of SAPO-34 molecular sieve with bionic pore channel structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096496A (en) * | 1993-06-18 | 1994-12-21 | 中国科学院大连化学物理研究所 | With the diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve |
| CN101205076A (en) * | 2006-12-21 | 2008-06-25 | 中国石油天然气集团公司 | Method for preparing small-grain SAPO-11 molecular sieve |
| CN102530986A (en) * | 2012-01-10 | 2012-07-04 | 复旦大学 | Method for producing MFI type zeolites |
-
2015
- 2015-09-17 CN CN201510593307.1A patent/CN105174279B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096496A (en) * | 1993-06-18 | 1994-12-21 | 中国科学院大连化学物理研究所 | With the diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve |
| CN101205076A (en) * | 2006-12-21 | 2008-06-25 | 中国石油天然气集团公司 | Method for preparing small-grain SAPO-11 molecular sieve |
| CN102530986A (en) * | 2012-01-10 | 2012-07-04 | 复旦大学 | Method for producing MFI type zeolites |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582803A (en) * | 2016-10-31 | 2017-04-26 | 昆明理工大学 | Preparation method of catalyst for alpha-pinene hydrogenation |
| 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 |
| CN108147422A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of CHA types Activity of Magnesium Aluminophosphate Molecular Sieve and preforming synthetic method |
| CN108147427A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of CHA types hetero atom Metal-aluminophosphate Molecular Siever and preforming synthetic method |
| CN109422280A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AFI structure aluminium phosphate molecular sieve |
| CN109422272A (en) * | 2017-08-31 | 2019-03-05 | 中国科学院大连化学物理研究所 | A method of synthesis has AFI structure hetero atom Metal-aluminophosphate Molecular Siever |
| CN109354035A (en) * | 2018-11-24 | 2019-02-19 | 江西师范大学 | A method of AlPO-18 molecular sieve is prepared using double template |
| CN109354035B (en) * | 2018-11-24 | 2023-01-24 | 江西师范大学 | Method for preparing AlPO-18 molecular sieve by using double templates |
| CN109759129A (en) * | 2019-01-15 | 2019-05-17 | 昆明理工大学 | A kind of Modification on Al PO4The preparation method and application of multistage porous molecular sieve |
| CN112250083A (en) * | 2019-07-22 | 2021-01-22 | 青岛科技大学 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
| CN112279270A (en) * | 2019-07-22 | 2021-01-29 | 青岛科技大学 | Aluminum phosphate molecular sieve and preparation method thereof |
| CN113104860A (en) * | 2020-05-14 | 2021-07-13 | 青岛大学威海创新研究院 | Preparation method of SAPO-34 molecular sieve with bionic pore channel structure |
| CN113104860B (en) * | 2020-05-14 | 2024-01-30 | 青岛大学威海创新研究院 | Preparation method of SAPO-34 molecular sieve with bionic pore structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105174279B (en) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105174279A (en) | Preparation method of nanosize aluminum phosphate molecular sieve | |
| CN105236445A (en) | Microwave preparation method for nanometer-dimension aluminium phosphate molecular sieve | |
| CN105110349B (en) | The preparation method of nano-scale AEL structure molecular sieve | |
| JP6949842B2 (en) | CHA-type zeolite materials and methods for producing them using a combination of cycloalkyl- and ethyltrimethylammonium compounds. | |
| CN103561868B (en) | Improved catalyst for oxygenatedchemicals to be changed into alkene | |
| CN108147427A (en) | A kind of CHA types hetero atom Metal-aluminophosphate Molecular Siever and preforming synthetic method | |
| CN107434252B (en) | Preparation method of low-silicon nano SAPO-34 molecular sieve | |
| CN106348312B (en) | A kind of synthesis methods for inorganic compounds of regulation and control ZSM-5 molecular sieve pattern | |
| CN104229826A (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN104098110B (en) | Preparation method and application of B-Al-ZSM-5 zeolite with controllable particle diameter | |
| CN104192859B (en) | A kind of Fast back-projection algorithm method of the molecular sieve of fine grain ZSM-5 5 | |
| CN103803579B (en) | Core-shell structured ZSM-5 composite molecular sieve and preparation method thereof | |
| WO2018023365A1 (en) | Method for synthesizing nano sapo-34 molecular sieve, and sapo-34 molecular sieve catalyst and application thereof | |
| CN103922361A (en) | Preparation method of SAPO-17 molecular sieves | |
| CN103495436A (en) | Method for manufacturing ALPO-5/SAPO-34 composite molecular sieve for preparing catalyst of low carbon olefin made of organic oxygenated chemicals | |
| CN105271303A (en) | Preparing method of AEL structure rare earth substituted aluminum phosphate molecular sieve | |
| CN101555024A (en) | Synthesis method of SAPO-34 molecular sieve | |
| CN104556093A (en) | Preparation method of small-grain SAPO-34 molecular sieve | |
| CN105800634A (en) | Nanometer total-silicon beta molecular sieve and preparation method thereof | |
| WO2012071891A1 (en) | Method for synthesizing small crystal size sapo-34 molecular sieve | |
| CN102464330A (en) | Synthesis method for nanometer Beta zeolite | |
| CN104495868B (en) | A kind of preparation method of big particle diameter HTS | |
| CN104355318A (en) | Synthetic method of nano molecular sieve ZSM-5 | |
| CN105800624A (en) | Synthesis method of all-silicon beta molecular sieve | |
| CN103962171A (en) | Aluminum silicon molecular sieve-aluminum oxide composite material and in-situ growth 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 | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160407 Address after: 100007 Beijing, Dongzhimen, North Street, No. 9, No. Applicant after: China National Petroleum Corporation Applicant after: China Petroleum University (East China) Address before: 266580 Qingdao Changjiang Road, Shandong, No. 66 Applicant before: China Petroleum University (East China) |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |