CN103818926A - Preparation method of hierarchical-pore CoAlPO-5 molecular sieve - Google Patents

Preparation method of hierarchical-pore CoAlPO-5 molecular sieve Download PDF

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CN103818926A
CN103818926A CN201410014857.9A CN201410014857A CN103818926A CN 103818926 A CN103818926 A CN 103818926A CN 201410014857 A CN201410014857 A CN 201410014857A CN 103818926 A CN103818926 A CN 103818926A
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molecular sieve
coalpo
preparation
stage porous
aluminum isopropylate
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赵新红
李晓斌
陈静
问娟娟
祁永东
赵江波
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Lanzhou University of Technology
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Lanzhou University of Technology
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Abstract

The invention relates to a preparation method of a hierarchical-pore CoAlPO-5 molecular sieve. The preparation method comprises the following steps: (1) uniformly mixing a succinic acid-choline chloride-tetraethylammonium bromide ternary eutectic mixture EM, aluminium isopropoxide and cobalt acetate tetrahydrate, then adding a proper amount of phosphoric acid and hydrofluoric acid so as to obtain a mixed system of a:Co2O3.Al2O3.b:P2O5.c:HF.d:EM, wherein coefficients are accounted in molar ratio that a is equal to 0.2-0.6, b is equal to 1.1-2.2, c is equal to 0.45-1.35 and d is equal to 62.0-124.0, and heating to 120 DEG C, so as to be mixed uniformly to obtain the mixture; (2) heating the mixture to 175 DEG C, carrying out crystallization for 15 minutes at an ordinary pressure or a self-generated pressure; (3) cooling the crystallization product to a room temperature, carrying out centrifugal washing repeatedly with water and acetone, and drying for 2 h at 90 DEG C so as to obtain a powder product of the hierarchical-pore CoAlPO-5 molecular sieve.

Description

The preparation method of multi-stage porous CoAlPO-5 molecular sieve
Technical field
The present invention relates to the technology of preparing of molecular sieve.
Background technology
AlPO 4-5 type molecular sieve [Al 12p 12o 48] be a kind of aluminophosphate molecular sieve of the AFI of having topological framework, the molecular sieve of the type has the circular pore passage structure of twelve-ring, and its diameter is 7.3 × 7.3 nm, belongs to hexagonal system, unit cell dimension a=1.38 nm, c=0.86 nm.Due to AlPO 4-5 is neutral backbone structure, and surface acidity is very weak, almost there is no ion-exchange performance, so researchist, by isomorphous substitution, introduces AlPO by transition metal (as Fe, Mn and Co etc.) 4in-5 molecular sieves, obtain active centre separated from one another, high dispersing.And the special pore passage structure of molecular sieve is for active centre provides suitable space, makes it possess oxidation activity center and the selectivity to product simultaneously, thereby generates efficiently target product.
The crystalline size of tradition micropore Me/AlPO-5 molecular sieve is generally at micron order, the diffusion of reactant and product molecule has been limited in its relatively long and narrow duct, although mesoporous Me/AlPO-5 molecular sieve has regular mesopore orbit and good molecular transport performance, the hydrothermal stability that it is lower and slightly acidic have limited its application in industry equally.The multi-stage porous Me/AlPO-5 molecular sieve of immediate development demonstrates than traditional micropore and the better catalytic activity of mesopore molecular sieve owing to combining the advantage of micropore and mesopore molecular sieve simultaneously in multiple catalyzed reaction, and Ryoo etc. have synthesized a series of multi-stage porous AlPO take organosilane tensio-active agent as soft template 4-5 molecular sieves, the cheap sucrose of the employings such as Yang is that mesoporous template has been synthesized the heteroatomic multi-stage porous MeAlPO-5 of a series of containing metals molecular sieve, and in the catalytic oxidation of multiple hydrocarbon polymer, has obtained higher performance.The Me/AlPO-5 molecular sieve reported before this makes some progress on multi-stage porous is synthetic, but these synthetic methods produce higher autogenous pressure in crystallization process makes it in operation, have larger potential safety hazard, and the step of partial synthesis method is also comparatively loaded down with trivial details.
Summary of the invention
The object of the present invention is to provide a kind of normal pressure fast synthesis method of multi-stage porous CoAlPO-5 molecular sieve, to overcome the shortcoming that is unfavorable for the synthesis mechanism of probing into molecular sieve under the long and High Temperature High Pressure of the crystallization time of tradition in synthetic.
The present invention is the preparation method of multi-stage porous CoAlPO-5 molecular sieve, the steps include:
(1) succinic acid-choline chloride 60-tetraethylammonium bromide ternary eutectic EM, aluminum isopropylate and Cobalt diacetate tetrahydrate are mixed, then add appropriate phosphoric acid and hydrofluoric acid, the mixed system obtaining is a: Co 2o 3al 2o 3b:P 2o 5c: HFd:EM, wherein coefficient is counted in molar ratio: a=0.2 ~ 0.6, b=1.1 ~ 2.2, c=0.45 ~ 1.35, d=62.0 ~ 124.0, are heated to 120 ℃, and it is mixed, and obtain mixture;
(2) mixture is heated to 175 ℃, crystallization 15 minutes under normal pressure or autogenous pressure;
(3) crystallization product is cooled to room temperature, water and acetone centrifuge washing is repeatedly dried 2 hours at 90 ℃, obtains the powdery product of multi-stage porous CoAlPO-5 molecular sieve.
The present invention has following characteristics: adopt succinic acid-choline chloride 60-tetraethylammonium bromide ternary eutectic as solvent and template, can synthesize the CoAlPO-5 molecular sieve with hierarchical porous structure without the mesoporous template of extra interpolation.The vapour pressure producing due to eutectic mixture is lower, the crystallization process of molecular sieve can be carried out in normal pressure or open container, be conducive to adopt the synthesis mechanism of in-situ characterization means research molecular sieve, and the potentially dangerous brought of the High Temperature High Pressure of having avoided traditional hydro-thermal or solvent thermal to produce in building-up process.By microwave radiation rapid heating, not only change the space structure of molecule, promoted polytype chemical reaction to carry out, can also accelerate chemical reaction, improve the crystallization velocity of molecular sieve, there is multi-stage porous CoAlPO-5 molecular sieve mesoporous between crystal thereby be easy to form.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) spectrogram of the multi-stage porous CoAlPO-5 molecular sieve of synthesized of the present invention, Fig. 2 is scanning electron microscope (SEM) photo of the multi-stage porous CoAlPO-5 molecular sieve of synthesized of the present invention, Fig. 3 is transmission electron microscope (TEM) photo of the multi-stage porous CoAlPO-5 molecular sieve of synthesized of the present invention, the N of the multi-stage porous CoAlPO-5 molecular sieve that Fig. 4 is synthesized of the present invention 2physics adsorption desorption and pore size distribution (PSD) spectrogram.
Embodiment
The present invention is the preparation method of multi-stage porous CoAlPO-5 molecular sieve, the steps include:
(1) succinic acid-choline chloride 60-tetraethylammonium bromide ternary eutectic EM, aluminum isopropylate and Cobalt diacetate tetrahydrate are mixed, then add appropriate phosphoric acid and hydrofluoric acid, the mixed system obtaining is a: Co 2o 3al 2o 3b:P 2o 5c: HFd:EM, wherein coefficient is counted in molar ratio: a=0.2 ~ 0.6, b=1.1 ~ 2.2, c=0.45 ~ 1.35, d=62.0 ~ 124.0, are heated to 120 ℃, and it is mixed, and obtain mixture;
(2) mixture is heated to 175 ℃, crystallization 15 minutes under normal pressure or autogenous pressure;
(3) crystallization product is cooled to room temperature, water and acetone centrifuge washing is repeatedly dried 2 hours at 90 ℃, obtains the powdery product of multi-stage porous CoAlPO-5 molecular sieve.
According to above-described preparation method, with Al 2o 3meter, the mol ratio of aluminum isopropylate and eutectic mixture is 1.0: 62.0 ~ 124.0.
According to above-described preparation method, the mol ratio of aluminum isopropylate and phosphoric acid is 1.0: 1.1 ~ 2.2.
According to above-described preparation method, the mol ratio of aluminum isopropylate and hydrofluoric acid is 1.0: 0.45 ~ 1.35.
According to above-described preparation method, the mol ratio of aluminum isopropylate and Cobalt diacetate tetrahydrate is 1.0: 0.2 ~ 0.6.
According to above-described preparation method, the cobalt source of reaction system adopts Cobalt diacetate tetrahydrate, and mineralizer adopts HF acid.
According to above-described preparation method, step (2) adopts at carry out microwave radiation heating to 175 ℃, normal pressure crystallization 15 minutes.
Further launch the present invention with embodiment more specifically below.
Embodiment 1:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.4, b=1.1, c=0.45, d=62.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2) said mixture is transferred in microwave synthesizer, under microwave radiation condition, is heated to 175 ℃, crystallization 15 minutes under normal pressure or autogenous pressure;
(3), by obtained crystallization product cool to room temperature, water and acetone centrifuge washing is repeatedly dried 2 hours at 90 ℃ in air dry oven, obtains the powdery product of heteroatoms phosphoric acid aluminum molecular screen CoAlPO-5;
(4) through XRD, SEM, TEM and N 2physics adsorption desorption detects, and this powdery product is multi-stage porous CoAlPO-5 molecular sieve.
Embodiment 2:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.4, b=1.1, c=0.90, d=62.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2), (3), (4) step are with embodiment 1.
Embodiment 3:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.4, b=1.1, c=1.35, d=62.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2), (3), (4) step are with embodiment 1.
Embodiment 4:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.2, b=1.1, c=1.35, d=62.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2), the step of (3), (4) is with embodiment 1.
Embodiment 5:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.6, b=1.1, c=1.35, d=62.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2), the step of (3), (4) is with embodiment 1.
Embodiment 6:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.4, b=2.2, c=0.45, d=62.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2), the step of (3), (4) is with embodiment 1.
Embodiment 7:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.4, b=2.2, c=0.90, d=62.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2), the step of (3), (4) is with embodiment 1.
Embodiment 8:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.4, b=2.2, c=1.35, d=62.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2), the step of (3), (4) is with embodiment 1.
Embodiment 9:
(1) by succinic acid, choline chloride 60, tetraethylammonium bromide, aluminum isopropylate and Cobalt diacetate tetrahydrate mixed grinding evenly after, proceed to there-necked flask, add appropriate phosphoric acid and hydrofluoric acid with liquid-transfering gun, the mixture obtaining is a Co 2o 3al 2o 3b P 2o 5c HFd EM, wherein coefficient is counted in molar ratio: a=0.4, b=1.1, c=1.35, d=124.0, are heated to molten state (120 ℃) with electric mantle it are mixed;
(2), the step of (3), (4) is with embodiment 1.
The N of microwave synthetic sample 2physics adsorption desorption characterization data
Figure 417721DEST_PATH_IMAGE001

Claims (7)

1. the preparation method of multi-stage porous CoAlPO-5 molecular sieve, the steps include:
(1) succinic acid-choline chloride 60-tetraethylammonium bromide ternary eutectic EM, aluminum isopropylate and Cobalt diacetate tetrahydrate are mixed, then add appropriate phosphoric acid and hydrofluoric acid, the mixed system obtaining is a: Co 2o 3al 2o 3b:P 2o 5c: HFd:EM, wherein coefficient is counted in molar ratio: a=0.2 ~ 0.6, b=1.1 ~ 2.2, c=0.45 ~ 1.35, d=62.0 ~ 124.0, are heated to 120 ℃, and it is mixed, and obtain mixture;
(2) mixture is heated to 175 ℃, crystallization 15 minutes under normal pressure or autogenous pressure;
(3) crystallization product is cooled to room temperature, water and acetone centrifuge washing is repeatedly dried 2 hours at 90 ℃, obtains the powdery product of multi-stage porous CoAlPO-5 molecular sieve.
2. the preparation method of multi-stage porous CoAlPO-5 molecular sieve according to claim 1, is characterized in that: with Al 2o 3meter, the mol ratio of aluminum isopropylate and eutectic mixture is 1.0: 62.0 ~ 124.0.
3. the preparation method of multi-stage porous CoAlPO-5 molecular sieve according to claim 1, is characterized in that: the mol ratio of aluminum isopropylate and phosphoric acid is 1.0: 1.1 ~ 2.2.
4. the preparation method of multi-stage porous CoAlPO-5 molecular sieve according to claim 1, is characterized in that: the mol ratio of aluminum isopropylate and hydrofluoric acid is 1.0: 0.45 ~ 1.35.
5. the preparation method of multi-stage porous CoAlPO-5 molecular sieve according to claim 1, is characterized in that: the mol ratio of aluminum isopropylate and Cobalt diacetate tetrahydrate is 1.0: 0.2 ~ 0.6.
6. the preparation method of multi-stage porous CoAlPO-5 molecular sieve according to claim 1, is characterized in that: the cobalt source of reaction system adopts Cobalt diacetate tetrahydrate, and mineralizer adopts HF acid.
7. the preparation method of multi-stage porous CoAlPO-5 molecular sieve according to claim 1, is characterized in that: step (2) adopts at carry out microwave radiation heating to 175 ℃, normal pressure crystallization 15 minutes.
CN201410014857.9A 2014-01-14 2014-01-14 Preparation method of hierarchical-pore CoAlPO-5 molecular sieve Pending CN103818926A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107638888A (en) * 2017-10-31 2018-01-30 李俊霞 New catalyst and preparation method thereof used in one kind production MEK
CN107777702A (en) * 2017-11-09 2018-03-09 常州大学 A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4801364A (en) * 1983-07-15 1989-01-31 Uop Separation and conversion processes using metal aluminophosphates
CN101602513A (en) * 2009-07-18 2009-12-16 太原理工大学 The method that in eutectic mixture, prepares aluminium phosphate molecular sieve
CN102583436A (en) * 2011-01-06 2012-07-18 兰州理工大学 Quick synthesis method of heteroatomic aluminophosphate molecular sieve SAPO-5 in eutectic body

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4801364A (en) * 1983-07-15 1989-01-31 Uop Separation and conversion processes using metal aluminophosphates
CN101602513A (en) * 2009-07-18 2009-12-16 太原理工大学 The method that in eutectic mixture, prepares aluminium phosphate molecular sieve
CN102583436A (en) * 2011-01-06 2012-07-18 兰州理工大学 Quick synthesis method of heteroatomic aluminophosphate molecular sieve SAPO-5 in eutectic body

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵新红等: "多级孔含铁磷铝分子筛的制备及在苯酚羟基化反应中的应用", 《当代化工》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107638888A (en) * 2017-10-31 2018-01-30 李俊霞 New catalyst and preparation method thereof used in one kind production MEK
CN107638888B (en) * 2017-10-31 2020-08-25 台州路豹鞋业有限公司 Catalyst for producing methyl ethyl ketone and preparation method thereof
CN107777702A (en) * 2017-11-09 2018-03-09 常州大学 A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening
CN107777702B (en) * 2017-11-09 2020-05-26 常州大学 Preparation method of hierarchical-pore heteroatom aluminum phosphate molecular sieve for oxidative desulfurization

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Application publication date: 20140528