CN103880050A - Method for synthesizing mesoporous gamma-Al2O3 by using double hydrolysis of cations and anions - Google Patents
Method for synthesizing mesoporous gamma-Al2O3 by using double hydrolysis of cations and anions Download PDFInfo
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- CN103880050A CN103880050A CN201410131082.3A CN201410131082A CN103880050A CN 103880050 A CN103880050 A CN 103880050A CN 201410131082 A CN201410131082 A CN 201410131082A CN 103880050 A CN103880050 A CN 103880050A
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Abstract
The invention relates to a method for preparing mesoporous gamma-Al2O3, and particularly relates to a method for synthesizing mesoporous gamma-Al2O3 by using double hydrolysis of cations and anions. The method for synthesizing mesoporous gamma-Al2O3 by using double hydrolysis of cations and anions comprises the following steps: by taking cheap and nontoxic inorganic salt Al(NO3)3 and NaAlO2 as aluminum sources and taking PluronicP123 as a structure-directing agent, carrying out complete hydrolysis reaction quickly by adding stoichiometric proportion of Al<3+> and AlO<2-> under the absence of a long hydrolysis process and a complicated pH adjusting process. The synthesized mesoporous gamma-Al2O3 material is solid and firm, large in mechanical strength, and especially suitable for being used as a catalyst carrier, and has high specific surface area which is greater than 340m<2>/g, narrow pore size distribution which is just 3-5nm, and thermal stability of greater than 700 DEG C.
Description
Technical field
The present invention relates to mesoporous γ-Al
2o
3preparation method, is specially the two mesoporous γ-Al of hydrolysis of zwitterion
2o
3method.
Background technology
1996, people's reported first such as Pinnavaia successfully synthesized heat-staple meso-porous alumina.From then on, the each study group in the whole world has extensively carried out the study on the synthesis of meso-porous alumina.On the whole, synthetic template used may be summarized to be several as follows:
Anion surfactant, the people such as Vaudry utilize long-chain carboxylic acid's negatively charged ion for structure directing agent is at ethanol, have successfully synthesized high-specific surface area in the organic solvents such as chloroform, the meso-porous alumina that pore size distribution is narrow.The people such as Yada utilize sodium lauryl sulphate for template, have synthesized layered mesoporous aluminum oxide, and along with further hydrolysis, lamellar phase can also change mutually to six sides.Favorable to the peoplely wait people taking the sodium alkyl sulfate of different carbon chain lengths or its mixture as template together, also synthesized the meso-porous alumina of laminate structure.But the people such as Sicard study and show, owing to having strong reactive force between tensio-active agent and the inorganic species of aluminium, template is bad to be removed, and high-temperature roasting meeting causes caving in of meso-hole structure.
Cats product; The people such as Cabrera utilize cetyl trimethylammonium bromide for template, and under aqueous systems, have synthesized meso-porous alumina in conjunction with trolamine.By reconciliation statement surface-active agent, water, and the ratio of trolamine can also carry out to the aperture of meso-porous alumina modulation from 3.3nm to 6.0nm.But this method repeatability is poor.
Nonionogenic tenside; Nonionogenic tenside, in the time preparing mesoporous aluminum oxide material, is proved to be comparatively successfully a kind of.Pinnavaia study group utilizes electroneutral PEO tensio-active agent as template, and aluminum alkyls, as aluminium source, has successfully synthesized meso-porous alumina.The material of synthesized is shown as the pore passage structure of small holes caused by worms shape.The people such as Yang also find, not only aluminum oxide, and some other oxide compound, as TiO
2, ZrO
2, Nb
2o
5, Ta
2o
5, SnO
2, WO
3deng utilizing PluronicP123 block polymer to synthesize for template.And various nonionic surface active agent all can be used to synthesising mesoporous aluminum oxide, as Tergitols, Tritons, Pluronics etc.Can also regulate and control the aperture of material by the length that changes PEO unit in nonionogenic tenside.
Nonsurfactant; People's first passage sol-gel methodes such as Wei, with dibenzoyl-L-TARTARIC ACID, the nonsurfactant biological micromolecules such as glucose and maltose are that template has been synthesized mesopore silicon oxide.At present, nonsurfactant method has also been used the synthetic of meso-porous alumina.The people such as Wei are template with nonsurfactant dibenzoyl-L-TARTARIC ACID, and aluminum isopropylate is aluminium source, under alcohol system (a small amount of water), have synthesized the concentrated meso-porous alumina of pore size distribution.Mainly still in non-aqueous system, carry out but these nonsurfactants are synthetic, one is aluminum isopropylate for aluminium source, and this makes it infeasible economically.And in this way synthetic aluminum oxide hole wall one be unformed.
Although recent two decades comes, meso-porous alumina synthetic obtained larger progress.But these methods one need to be used expensively, and poisonous aluminum alkyls is as aluminium source, and productive expense is high, large to operator's actual bodily harm.Or need to be very very long, complicated hydrolysis, pH value regulate process, make the production cycle long, severe reaction conditions.This makes the preparation of meso-porous alumina be difficult to realize industrialization.
Summary of the invention
It is low that object of the present invention will be found a kind of cost exactly, pollute little, the synthetic method of the simple meso-porous alumina of preparation condition.
The two mesoporous γ-Al of hydrolysis of zwitterion
2o
3method, comprise the following steps:
(1) P123 (polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer) is dissolved in distilled water, forms P123 solution;
(2) by Al (NO
3)
39H
2o joins in P123 solution, and stirring and dissolving forms mixture;
(3) by NaAlO
2solution is added dropwise in mixture, stirs;
(4) NaAlO
2after solution adds, continue to stir 4 hours, obtain gel;
(5) gel is transferred in stainless steel cauldron, 60～120 DEG C of crystallization 1～4 day; Crystallization temperature is preferably 80～100 DEG C;
(6) take out the material after product, pass through successively suction filtration, washing, obtain the organic and inorganic complex body of tensio-active agent and aluminum oxide;
Washing process will ensure residual Na
+concentration enough low because remain in the Na in sample
+the pore passage structure that will destroy sample in the process of roasting, causes the decline of sample specific surface;
(7) the organic and inorganic complex body after washing is 80 DEG C of vacuum-dryings 24 hours, drier in 150 DEG C of baking ovens, and then roasting 2-4 hour in the retort furnace of 450～700 DEG C, can obtain mesoporous γ-Al
2o
3;
Wherein, the mol ratio of reaction mass is: Al (NO
3)
39H
2o: NaAlO
2: P123: H
2o=1: 3: x: 278,0.01<x<0.08, is preferably 0.02<x<0.05.
The P123 solution that step (1) is described, the weight percent of P123 is 4.7～13.1%, is preferably 5～7%.
The gel that step (4) obtains, at room temperature ageing 1～2 day, then carry out (5) step.
The two mesoporous γ-Al of hydrolysis of zwitterion provided by the invention
2o
3method, with cheap, nontoxic inorganic salt Al (NO
3)
3and NaAlO
2for aluminium source, taking PluronicP123 as structure directing agent, by adding the Al of stoichiometric ratio
3+and AlO
2 -, hydrolysis reaction carries out completely very soon, without very long hydrolytic process and complicated pH regulator process.Mesoporous γ-the Al synthesizing
2o
3material solid-rigid, physical strength is large, is particularly suitable as support of the catalyst, has >340m
2the tool high-specific surface area of/g, pore size distribution is narrow, only has 3～5nm, and has the thermostability of >700 DEG C.
Brief description of the drawings
Fig. 1 is the mesoporous γ-Al of embodiment 1 gained
2o
3n
2adsorption and desorption isotherms;
Fig. 2 is the mesoporous γ-Al of embodiment 1 gained
2o
3xRD low angle diagram;
Fig. 3 is the mesoporous γ-Al of gained after embodiment 1 gained organic and inorganic complex body and roasting
2o
3xRD wide-angle diffraction figure;
Fig. 4 is the N2 Adsorption and desorption isotherms of the mesoporous γ-Al2O3 of embodiment 2 gained;
Fig. 5 is the XRD wide-angle diffraction figure of the mesoporous γ-Al2O3 of gained after embodiment 2 gained organic and inorganic complex bodys and roasting.
Embodiment
The specific embodiment of the present invention is described in conjunction with the embodiments, and the P123 in the present embodiment is the technical grade product of being produced by Weir chemical inc, Nanjing, and molecular weight is 5650.
Embodiment 1:
Under violent stirring, by NaAlO
2solution dropwise joins Al (NO
3)
3in the mixed water solution of P123, under room temperature, stir 4 hours.Solution mole consist of Al (NO
3)
39H
2o: NaAlO
2: P123: H
2o=1: 3: 0.01: 278, this reaction mixture is at room temperature left standstill after 24 hours, be transferred in stainless steel cauldron, crystallization 24 hours, takes out at 100 DEG C, suction filtration, washing, removes surperficial floating matter.At 80 DEG C, dry, obtain organic and inorganic complex body, this organic and inorganic complex body is dried to 6 hours at 150 DEG C, then within 4 hours, obtain mesoporous γ-Al 500 DEG C of roastings
2o
3.
Fig. 1 is mesoporous γ-Al
2o
3n
2adsorption and desorption isotherms; Fig. 2 is mesoporous γ-Al
2o
3xRD low angle diagram; (a) organic-inorganic meets thing; (b) 600 DEG C; (c) 700 DEG C.Mesoporous γ-the Al of gained after Fig. 3 organic and inorganic complex body and roasting
2o
3xRD wide-angle diffraction figure.
Embodiment 2:
Under violent stirring, by NaAlO
2solution dropwise joins Al (NO
3)
3in the mixed water solution of P123, under room temperature, to stir 4 hours, mole consisting of of solution mole consists of Al (NO
3)
39H
2o: NaAlO
2: P123: H
2o=1: the mixture of 3: 0.08: 278, this reaction mixture is at room temperature left standstill after 24 hours, be transferred in stainless steel cauldron, crystallization 24 hours, takes out at 100 DEG C, suction filtration, washing, removes surperficial floating matter.At 80 DEG C, dry, obtain organic and inorganic complex body, this organic and inorganic complex body is dried to 6 hours at 150 DEG C, then within 4 hours, obtain mesoporous γ-Al 500 DEG C of roastings
2o
3.
Fig. 4 is mesoporous γ-Al
2o
3n
2adsorption and desorption isotherms; Mesoporous γ-the Al of gained after Fig. 5 organic and inorganic complex body and roasting
2o
3xRD wide-angle diffraction figure.
Claims (3)
1. the method for the two mesoporous γ-Al2O3 of hydrolysis of zwitterion, is characterized in that: comprises the following steps,
(1) P123 is dissolved in distilled water, forms P123 solution;
(2) by Al (NO
3)
39H
2o joins in P123 solution, and stirring and dissolving forms mixture;
(3) by NaAlO
2solution is added dropwise in mixture, stirs;
(4) NaAlO
2after solution adds, continue to stir 4 hours, obtain gel;
(5) gel is transferred in stainless steel cauldron, 60～120 DEG C of crystallization 1～4 day;
(6) take out the material after product, pass through successively suction filtration, washing, obtain the organic and inorganic complex body of tensio-active agent and aluminum oxide;
(7) after the organic and inorganic complex body after washing is dried, in the retort furnace of 450～700 DEG C, roasting 2～4 hours, can obtain mesoporous γ-Al
2o
3;
Wherein, the mol ratio of reaction mass is: Al (NO
3)
39H
2o: NaAlO
2: P123: H
2o=1: 3: x: 278,0.01<x<0.08.
2. the two mesoporous γ-Al of hydrolysis of zwitterion according to claim 1
2o
3method, it is characterized in that: the P123 solution that step (1) is described, the weight percent of P123 is 4.7～13.1%.
3. the two mesoporous γ-Al of hydrolysis of zwitterion according to claim 1
2o
3method, it is characterized in that: the gel that step (4) obtains, at room temperature ageing 1～2 day, then carry out (5) step.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226255A (en) * | 2015-10-20 | 2016-01-06 | 四川科能锂电有限公司 | The preparation technology of nickel ion doped |
| CN106186014A (en) * | 2016-07-21 | 2016-12-07 | 中国石油大学(华东) | A kind of mesoporous γ Al2O3 synthetic method of function admirable |
| CN106219582A (en) * | 2016-07-21 | 2016-12-14 | 中国石油大学(华东) | A kind of preparation method with super large mesoporous pore volume γ Al2O3 |
| CN106673032A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | High-acidity low-crystallinity alumina dry glue and preparation method thereof |
| CN109985622A (en) * | 2019-05-10 | 2019-07-09 | 中国石油大学(华东) | One kettle way prepares γ-Al2O3The Au-Pd catalyst of load |
| CN117427665A (en) * | 2023-12-22 | 2024-01-23 | 橙雨化学(大连)有限公司 | Te modified mesoporous Al 2 O 3 Material, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515215A (en) * | 2011-10-09 | 2012-06-27 | 上海大学 | Preparation method for wormhole-like mesoporous gamma-Al2O3 with narrow pore size distribution |
-
2014
- 2014-04-02 CN CN201410131082.3A patent/CN103880050A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515215A (en) * | 2011-10-09 | 2012-06-27 | 上海大学 | Preparation method for wormhole-like mesoporous gamma-Al2O3 with narrow pore size distribution |
Non-Patent Citations (2)
| Title |
|---|
| PENG BAI ET AL.: "Cation–anion double hydrolysis derived mesoporous c-Al2O3 as an environmentally friendly and efficient aldol reaction catalyst", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| 白鹏: "介孔氧化铝合成新方法及其在功能材料合成中的扩展应用", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226255A (en) * | 2015-10-20 | 2016-01-06 | 四川科能锂电有限公司 | The preparation technology of nickel ion doped |
| CN106673032A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | High-acidity low-crystallinity alumina dry glue and preparation method thereof |
| CN106186014A (en) * | 2016-07-21 | 2016-12-07 | 中国石油大学(华东) | A kind of mesoporous γ Al2O3 synthetic method of function admirable |
| CN106219582A (en) * | 2016-07-21 | 2016-12-14 | 中国石油大学(华东) | A kind of preparation method with super large mesoporous pore volume γ Al2O3 |
| CN106219582B (en) * | 2016-07-21 | 2019-07-09 | 中国石油大学(华东) | A kind of preparation method for holding γ-Al2O3 with super large mesoporous hole |
| CN106186014B (en) * | 2016-07-21 | 2019-07-09 | 中国石油大学(华东) | A kind of mesoporous γ-Al2O3 synthetic method of function admirable |
| CN109985622A (en) * | 2019-05-10 | 2019-07-09 | 中国石油大学(华东) | One kettle way prepares γ-Al2O3The Au-Pd catalyst of load |
| CN117427665A (en) * | 2023-12-22 | 2024-01-23 | 橙雨化学(大连)有限公司 | Te modified mesoporous Al 2 O 3 Material, preparation method and application thereof |
| CN117427665B (en) * | 2023-12-22 | 2024-03-15 | 橙雨化学(大连)有限公司 | Te modified mesoporous Al 2 O 3 Material, preparation method and application thereof |
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Application publication date: 20140625 |