CN1745897A - Production of gel by membrane reaction and nanometer catalyst - Google Patents
Production of gel by membrane reaction and nanometer catalyst Download PDFInfo
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- CN1745897A CN1745897A CNA2005100193058A CN200510019305A CN1745897A CN 1745897 A CN1745897 A CN 1745897A CN A2005100193058 A CNA2005100193058 A CN A2005100193058A CN 200510019305 A CN200510019305 A CN 200510019305A CN 1745897 A CN1745897 A CN 1745897A
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Abstract
A process for preparing gel and nano-catalyst by membrane reaction method includes such steps as respectively putting the raw materials at inside and outside of membranes, hydrolyzing reacting to obtain gel, drying and calcining to obtain catalyst nanoparticles. Its advantages are high uniformity of transparency for gel and high performance and granular uniformity for catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of gel, specifically a kind of method by production of gel by membrane reaction.
The invention still further relates to the method that is equipped with nanocatalyst by the film reaction legal system.
Background technology
Sol-gel process is a kind of important method of preparation inorganic material, and the research report that particularly this method is applied to prepare various nano-powder materials in recent years is more.This method comprises a plurality of physical and chemical processes that carry out the transition to solid material from solution usually, as hydrolysis, polymerization, experiences into steps such as glue, drying and dehydrating, calcining is densified.The advantage of this method is: be reflected under the relatively mild solution condition and carry out; Can obtain homogeneous phase multicomponent system; Utilize the rheological characteristic of colloidal sol or gel on other solid materials, to film, preparation thin-film material etc.Its shortcoming is: need careful control reaction condition, otherwise be difficult to prepare the colloidal sol of homogeneous transparent.The metal organic salts that adopt as reacting precursor more when particularly preparing metallic oxide nano powder, the small organic molecule that reaction generates is wrapped in and is difficult in the gel remove, usually adopt high-temperature calcination that organic carbon is removed, but organic carbonization may bring the powder body material surface micro-structural in the high-temperature calcination process, as the distribution in hole, the variation of coherent condition, thereby influence the performance of material, particularly as the powder body material of catalyst, it influences more so.These defectives have greatly limited the extensive use of nanochemistry material.
Summary of the invention
Technical problem to be solved by this invention is: at having the deficiency that sol-gel process prepares gel now, provide a kind of method of production of gel by membrane reaction, it has solved, and the gel homogeneous transparent of method for preparing is poor, the unmanageable problem of reaction condition.
The present invention also provides a kind of film reaction legal system to be equipped with the method for nanocatalyst, and it has solved, and the nanocatalyst granularity of existing method preparation is inhomogeneous, the problem of poor performance.
Technical scheme of the present invention is achieved in that its adopts film medium as the chemical reaction interface, places reaction raw materials in the film respectively and the film prepared in reaction that is hydrolyzed forms outward.Wherein: be metal salt solution in the film, film is mobile water outward, and film medium is a kind of in dialysis membrane, amberplex, permeable membrane, milipore filter or the micro-filtration membrane.Raw material proportioning of the present invention is a prior art, and those skilled in the art is according to different raw materials and reaction, and is easy to just can draw in conjunction with sol-gel process.Hydrolysis also is to carry out under normal temperature, normal pressure, belongs to the known technology of this area.
The preparation method of nanocatalyst of the present invention adopts film medium as the chemical reaction interface, metal salt solution is placed in the film, film outward becomes colloidal sol for the water that the flows prepared in reaction that is hydrolyzed, colloidal sol is ageing a few hours one-tenth gel in film, makes nano powder catalyst after gel drying, the calcining.
As the chemical reaction interface, the control hydrolysis prepares high performance colloidal sol with film mediums such as dialysis membrane, amberplex, permeable membrane, milipore filter or micro-filtration membrane in the present invention.Colloidal sol by byproduct of reaction or impurity such as film separation removal organic matters, thereby obtains the gel even, transparent, that composition is pure in gelation, and by Drying of gels, calcining are prepared nano-powder material.Experiment showed, that the gel with this method preparation all has greatly improved the powder body material epigranular of preparation, function admirable than the gel with common sol-gel process preparation at aspects such as uniformity, transparency, the degree of polymerization and degrees of purity.Used the successful preparation of this method titanium dioxide, tin ash, aluminium oxide isogel and nanocatalyst.Wherein titanium deoxide catalyst is more than 5 times of nano titanium oxide of common sol-gel process preparation to organic catalytic efficiency in the photooxidative degradation water; TiO with this method preparation
2/ SnO
2Composite catalyst has the catalytic activity height, the characteristics that technology is simple, cost is low, and catalyst uses its catalytic activity not descend through 20 times repeatedly, shows that its contamination resistance is strong, is the good catalyst of photooxidation reaction; Nano aluminium oxide with this method preparation can be used as the catalyst carrier supported ionic, the preparation organic catalyst compound.Prepared alumina load Fe
3+, SO
4 2-The acetic acid synthesized positive butyl ester yield of catalyst reaches 93%, 95% respectively.
The present invention is applicable to the fields such as preparation of doping, nano-powder material and metal oxide catalyst of preparation, the gel of various inorganic gels.Characteristics such as the present invention has the technology advanced person, and method is simple, reliable, and cost is low, and prepared material property is good.
The inventive method has been utilized the separation function and the separation function of film, and at first to a kind of reactant of reaction system control input, because the selective permeation ability of film, the colloidal sol that makes generation is not to the film external diffusion, and other small molecule by-products can and be removed through film.Because film control input reactant is fully uniform feed way, avoided the inhomogeneous of the reinforced local reaction thing that causes of common sol-gel process, precipitation that causes or colloidal sol muddiness are when generating colloidal sol, by film separating by-products and impurity, thereby make good gel.The film reaction legal system is equipped with the inorganic gel schematic diagram and sees Fig. 1, can select the motive force (poor, the pressure differential of film both sides concentration of reactants) of material permeance film and material flow is controlled reaction as the control parameter process.
The technological process that the film reaction legal system is equipped with inorganic gel and nano powder catalyst is:
Description of drawings
Fig. 1 prepares the schematic diagram of gel for the present invention
The specific embodiment
The invention will be further described by the following examples:
Embodiment 1
Is the precursor of preparation with the tetrabutyl titanate, is formulated as the solution of 20%-50% with absolute ethyl alcohol, place the macromolecule dialysis membrane reactor, film is the water for flowing outward, hydrolysis promptly takes place after reinforced, generates colloidal sol.Colloidal sol ageing in film formed gel in 10 hours, continued dialysis 24 hours, obtained even, transparent gel.Gel makes nano-TiO after 120 ℃ of dryings, 400 ℃ of temperature programmed controls are calcined
2Powder body material.This nano-TiO
2Powder is as the catalyst of degradation of organic substances photooxidation reaction, than the nano-TiO of common sol-gel process preparation
2The catalytic efficiency of catalyst exceeds more than 4 times.
Embodiment 2
It is water-soluble to get a certain amount of butter of tin, is made into the solution of 0.1-0.25mol/L, and the salt acid for adjusting pH value is about 3, places the ion-exchange membrane reactor, and film is the water for flowing outward, reaction 4-8 hour that is hydrolyzed, preparation colloidal sol.Colloidal sol ageing in film formed gel in 5 hours, and continued to be the phase that flows, to exchange 48 hours to remove chlorion, obtain even, transparent SnO with water
2Gel.SnO
2Gel makes nano SnO after 150 ℃ of dryings, 600 ℃ of temperature programmed controls are calcined
2Powder body material, this SnO
2Powder body material can be used as nanocatalyst.
Embodiment 3
Aluminum nitrate is water-soluble, and preparation 0.1mol/L solution places the ion-exchange membrane reactor, and film is outward an alkaline solution, control pH value of solution value about 9, the reaction that is hydrolyzed, preparation colloidal sol.After hydrolysis was finished, film changed the mobile phase of water outward into, exchanges to neutrality, obtains gel.Gel obtains nano alumina particles through 120 ℃ of dryings, temperature programmed control to 400 ℃-600 ℃ of calcinings.Alumina powder jointed material can be used as nanocatalyst.
Embodiment 4
Copper sulphate is water-soluble, and preparation 0.3mol/L solution places the ion-exchange membrane reactor, and film is outward an alkaline solution, control pH value of solution value about 9, the reaction that is hydrolyzed, preparation colloidal sol.After hydrolysis was finished, film changed the mobile phase of water outward into, exchanges to neutrality, obtains gel.Gel obtains the nano cupric oxide particle through 120 ℃ of dryings, temperature programmed control to 500 a ℃ calcining.The cupric oxide powder material can be used as nanocatalyst.
Embodiment 5
Zinc sulfate is water-soluble, and preparation 0.2mol/L solution places ultrafiltration membrane reactor, and film is outward an alkaline solution, control pH value of solution value about 9, the reaction that is hydrolyzed, preparation colloidal sol.After hydrolysis was finished, film changed the mobile phase of water outward into, exchanges to neutrality, obtains gel.Gel obtains nano granular of zinc oxide through 120 ℃ of dryings, temperature programmed control to 500 a ℃ calcining.The Zinc oxide powder material can be used as nanocatalyst.
Claims (6)
1, a kind of method of production of gel by membrane reaction, its adopts film medium as the chemical reaction interface, places reaction raw materials in the film respectively and the film prepared in reaction that is hydrolyzed forms outward.
2, according to the method for a kind of production of gel by membrane reaction of claim 1, wherein: in the film be metal salt solution, and film is mobile water outward.
3, according to the method for a kind of production of gel by membrane reaction of claim 1, wherein: film medium is dialysis membrane, amberplex, permeable membrane, milipore filter or micro-filtration membrane.
4, a kind of preparation method of nanocatalyst, it adopts film medium as the chemical reaction interface, metal salt solution is placed in the film, film outward becomes colloidal sol for the water that the flows prepared in reaction that is hydrolyzed, colloidal sol is ageing a few hours one-tenth gel in film, makes nano powder catalyst after gel drying, the calcining.
5, according to the preparation method of a kind of nanocatalyst of claim 4, wherein: the heating and temperature control during gel drying is at 100-150 ℃.
6, according to the preparation method of a kind of nanocatalyst of claim 4, wherein: the heating and temperature control during the gel calcining is at 400-600 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100193058A CN100381205C (en) | 2005-08-17 | 2005-08-17 | Production of gel by membrane reaction and nanometer catalyst |
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|---|---|---|---|
| CNB2005100193058A CN100381205C (en) | 2005-08-17 | 2005-08-17 | Production of gel by membrane reaction and nanometer catalyst |
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| CN1745897A true CN1745897A (en) | 2006-03-15 |
| CN100381205C CN100381205C (en) | 2008-04-16 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104658761A (en) * | 2015-02-26 | 2015-05-27 | 江汉大学 | Method for preparing dye-sensitized solar cell nano-TiO2 membrane photo-anode with membrane reaction method |
| CN104689770A (en) * | 2015-02-26 | 2015-06-10 | 江汉大学 | Gas phase/liquid phase membrane reaction method for preparing nano material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6158815A (en) * | 1984-08-31 | 1986-03-26 | Kao Corp | Manufacture of high-purity alumina sol |
| CN1103802C (en) * | 1996-05-24 | 2003-03-26 | 日本帕卡濑精株式会社 | Titanium dioxide ceramic paint and method of producing same |
| JP2001096140A (en) * | 1999-09-30 | 2001-04-10 | Tosoh Corp | Regeneration method of ultrafiltration membrane module for zirconia powder production |
| CN1112236C (en) * | 1999-12-29 | 2003-06-25 | 中国科学院生态环境研究中心 | Method and equipoment for synthesizing nanometer particle by film reactor |
| CN1170775C (en) * | 2002-09-29 | 2004-10-13 | 南京工业大学 | Production method of superfine nano titanium dioxide by membrane integrated hydrothermal reaction |
| FR2857355B1 (en) * | 2003-07-11 | 2007-04-20 | Air Liquide | PEROVSKITE MATERIAL, METHOD OF PREPARATION AND USE IN MEMBRANE CATALYTIC REACTOR |
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2005
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104658761A (en) * | 2015-02-26 | 2015-05-27 | 江汉大学 | Method for preparing dye-sensitized solar cell nano-TiO2 membrane photo-anode with membrane reaction method |
| CN104689770A (en) * | 2015-02-26 | 2015-06-10 | 江汉大学 | Gas phase/liquid phase membrane reaction method for preparing nano material |
| CN104658761B (en) * | 2015-02-26 | 2017-07-25 | 江汉大学 | A kind of method that film reaction method prepares dye sensibilization solar cell nanometer titanium dioxide thin film photo-anode |
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| CN100381205C (en) | 2008-04-16 |
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