CN100342060C - Preparation of superfine metal oxide by electrolytic method - Google Patents
Preparation of superfine metal oxide by electrolytic method Download PDFInfo
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- CN100342060C CN100342060C CNB2004100792401A CN200410079240A CN100342060C CN 100342060 C CN100342060 C CN 100342060C CN B2004100792401 A CNB2004100792401 A CN B2004100792401A CN 200410079240 A CN200410079240 A CN 200410079240A CN 100342060 C CN100342060 C CN 100342060C
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- exchange membrane
- hydroxide
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Abstract
The present invention uses an electrochemical method to prepare ultra-fine metal oxide. The method uses a cation exchange membrane (5) to divide an electrolytic tank (8) into an anode chamber (3) and a cathode chamber (9), a salt solution of metal oxide to be prepared is added to the anode chamber (3), different electrolytic voltage is controlled, and metal ions in the anode chamber (3) can reach the cathode chamber (9) through the cation exchange membrane. Since a cathode (6) consumes H<+> ions in a solution in the cathode chamber, OH<-> ions can be released and can generate metal hydroxide with the metal ions. The metal hydroxide is uniformly precipitated, and the ultra-fine hydroxide can be obtained by filtering, washing and drying precipitates in the cathode chamber (9). The different hydroxide can be roasted to be ultra-fine oxide of the hydroxide at different temperatures, and the particle size range of particles of the ultra-fine oxide is mainly between 60 to 100 nm. The method has the characteristics of simple technology and easily controlled operating conditions, and has wide application prospects and favorable economic benefit.
Description
Technical field
The present invention utilizes electrolytic method to prepare super-fine metal oxide.
Background technology
Super-fine metal oxide, its particle diameter scope is between 1～100nm.The difference that highly significant is arranged with the micron grain material with composition on performance.Ultramicronising along with its oxide compound; its surface electronic structure and crystalline structure change; have special light, electricity, magnetic, heat, sound, power, chemistry and biology performance, be widely used in fields such as aerospace, national defense industry, magnetic recording equipment, computer engineering, environment protection, chemical industry, medicine, biotechnology and nuclear industry.Super-fine metal oxide preparation and application are more and more paid attention to by people, and wherein the preparation of its material has become one of focus of investigation of materials today.Along with continually developing and the expansion of range of application of nano material preparation technology, will produce great effect to traditional chemical industry and other industries.Present method adopts and utilizes cationic exchange membrane (5) is that barrier film is electrolyzer second, anode two Room, in electrolytic process, the metal ion of anolyte compartment (3) obtains the precipitation of hydroxide of its corresponding salt in cathode compartment (9) by cationic exchange membrane (5), high temperature sintering prepares super-fine metal oxide, technology is simple, easy to implement the method, have broad application prospects and favorable economic benefit.
Summary of the invention
The object of the invention is: utilize electrolytic method to prepare super-fine metal oxide.This method utilizes cationic exchange membrane (5) for barrier film electrolyzer (8) to be divided into anolyte compartment (3) and cathode compartment Room (9) two, and the current density of negative electrode (6) is controlled at 0.01～0.80A/cm
2Scope, in electrolytic process, the metal ion of anolyte compartment (3) arrives cathode compartment by cationic exchange membrane (5).The OH that ionization produces in cathode compartment (9)
-Evenly generating precipitation of hydroxide with its metal ion comes out.Because better its formation speed of control just can avoid density unevenness to spare phenomenon, and degree of supersaturation is controlled in the suitable scope, thus the speed of growth of control particle, the superfine metal oxyhydroxide that the acquisition cohesion is less, purity is high.
(3) adding concentration is controlled at 0.01～6.00mol/dm in the anolyte compartment in present method employing
3The chloride salt solution that will prepare its metal oxide in the scope, in electrolytic process, its metal ion arrives cathode compartment (9) by cationic exchange membrane (5) under electric field action.Cationic exchange membrane had both played the effect of transmitting cation carrier, and the centrifugation of separating electrolyzer is arranged again.In anolyte compartment (3) electrolytic process, anode has chlorine to emit on (4).Can discharge hydrogen or consume hydrogen ion at cathode compartment (9) electrolytic solution.
In the metal chloride electrolyzed saline solution process of anolyte compartment (3), reaction equation is as follows:
2Cl
-＝Cl
2↑+2e
-
In the metal chloride electrolyzed saline solution process of cathode compartment (9), different reaction systems obtains different reaction product.
In the metal chloride salts solution, reaction equation is as follows:
2H
2O+2e
-＝H
2↑+2OH
-
In metal-nitrate solutions, reaction equation is as follows:
In sulfate liquor, reaction equation is as follows:
2H
2O+2e
-＝H
2↑+2OH
-
Because the OH of negative electrode (6)
-Constantly discharge with constant speed, evenly form precipitation of hydroxide with the metal ion that passes cationic exchange membrane (5) arrival cathode compartment (9) and separate out, reaction equation is as follows:
M
x++xOH
-＝M(OH)
x↓
The metallic cation of anolyte compartment (3) enters cathode compartment by cationic membrane (5), and owing to cathode compartment (9) obtains hydrogen or effectively consumes hydrogen ion in electrolysis, and slowly-releasing goes out OH
-With the metallic cation precipitation from homogeneous solution.Again because negative electrode (6) uniform slow release OH
-, under the violent stirring effect of agitator (7), can reach effective outside atmosphere that microcrystal forms, also can avoid its precipitation of hydroxide to deposit on the negative electrode simultaneously, thereby in cathode compartment (9) metallic cation and OH
-Form the superfine metal precipitation of hydroxide.To its sedimentation and filtration, washing, drying can obtain its ultra-fine oxyhydroxide or oxide compound.Calcination under different temperature can obtain its superfine oxide to different oxyhydroxide, and its particle diameter scope mainly is distributed between 60～100nm.
The metal scope of application with preparation of superfine metal oxide by electrolytic method: magnesium, titanium, aluminium, zirconium, zinc, calcium.
Description of drawings
Referring to accompanying drawing
Fig. 1 is an electrolyzer synoptic diagram of the present invention
1 direct supply, 2 anolyte compartment's vapor pipe 3 anolyte compartments, 4 anodes (positive pole) 5 cationic exchange membranes, 6 negative electrodes (negative pole) 7 are equipped with agitator 8 electrolyzers 9 cathode compartment 10 cathode compartment vapor pipes, 11 agitator motor and the negative pole wiring transfer equipments of negative electrode
Fig. 2 is an electrolysis process principle schematic of the present invention
Preparation example with the range of application of preparation of superfine metal oxide by electrolytic method
On behalf of this method, example only can prepare following super-fine metal oxide herein, the concrete scope of application: with the metal scope of application of preparation of superfine metal oxide by electrolytic method.
Preparation example 1
1 installs cationic exchange membrane (5) between electrolyzer (8), thereby electrolyzer is divided into cathode and anode two Room, adds 1.00mol/dm respectively in anolyte compartment (3) with in cathode compartment (9)
3Magnesium chloride and 2.00mol/dm
3Sodium-chlor, the current density of negative electrode (6) is controlled at 0.08A/cm
2About, under electric field action, the Mg in anolyte compartment (3)
2+Constantly arrive cathode compartment (9) by cationic exchange membrane (5).(3) electrolysis obtains chlorine in the anolyte compartment, has hydrogen to discharge in cathode compartment (9) electrolysis, under the violent stirring effect of the agitator in cathode compartment (7), can obtain Mg (OH)
2Precipitation is filtered, and washing at 550 ℃ of pyrolytic decompositions, can obtain the MgO that granularity mainly is distributed in 60～100nm.
Preparation example 2
Cationic exchange membrane (5) is installed between electrolyzer (8), thereby electrolyzer is divided into cathode and anode two Room, in two Room, add 1.00mol/dm respectively
3Sodium-chlor and 1.00mol/dm
3Liquor alumini chloridi, the current density of negative electrode (6) is controlled at 0.10A/cm
2About, in electrolytic process, the Al of anolyte compartment (3)
3+Constantly arrive at cathode compartment by cationic exchange membrane (5).Anolyte compartment (3) has chlorine to discharge, and in cathode compartment (9), electrolysis obtains hydrogen or effectively consume hydrogen ion accomplishing that simultaneously slowly-releasing goes out OH
-, under the violent stirring effect of agitator (7), can prepare Al (OH)
3Precipitation is filtered, and washing at 600 ℃ of pyrolytic decompositions, can obtain the Al of granularity at 60～100nm
2O
3Powder.
Claims (2)
1. prepare the method for super-fine metal oxide with electrolysis process, it is characterized in that:
A. use cationic exchange membrane (5) that electrolyzer (8) is divided into and have only the positively charged ion can free anolyte compartment (3) and cathode compartment (9), and the negatively charged ion in two Room can not pass through by cationic exchange membrane;
B. in anolyte compartment (3), add concentration and be controlled at 0.01～6.00mol/dm
3Between need prepare the salts solution of its metal oxide, because the existence of cationic exchange membrane (5), in electrolytic process, metal ion in the anolyte compartment (3) can pass through cationic exchange membrane (5) and enter cathode compartment, under the violent stirring effect of agitator (7), OH-with negative electrode (6) slowly-releasing in cathode compartment (9) evenly generates precipitation of hydroxide, precipitation of hydroxide filtration, washing, the drying of anticathode chamber (9), can obtain its ultra-fine oxyhydroxide, calcination under different temperature can obtain its superfine oxide to different oxyhydroxide;
C. current density is controlled at 0.01～0.80A/cm
2Scope.
2. according to claim 1ly prepare the method for super-fine metal oxide with electrolysis process, the metal scope of application is magnesium, titanium, aluminium, zirconium, zinc, calcium.
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| CNB2004100792401A CN100342060C (en) | 2004-09-16 | 2004-09-16 | Preparation of superfine metal oxide by electrolytic method |
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|---|---|---|---|
| CNB2004100792401A CN100342060C (en) | 2004-09-16 | 2004-09-16 | Preparation of superfine metal oxide by electrolytic method |
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| CN100342060C true CN100342060C (en) | 2007-10-10 |
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| CN102732902A (en) * | 2011-04-15 | 2012-10-17 | 洪若瑜 | Preparation method of conductive metal oxide nanorod |
| CN102417186A (en) * | 2011-09-07 | 2012-04-18 | 黑龙江科技学院 | Novel method for preparing nano silica powder |
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| CN106967993A (en) * | 2017-05-10 | 2017-07-21 | 东北大学 | A kind of electrolytic chlorination aluminum for aluminum oxide method |
| CN107236964A (en) * | 2017-05-10 | 2017-10-10 | 东北大学 | A kind of method that cobalt chloride electricity conversion directly prepares cobalt hydroxide |
| CN107311365A (en) * | 2017-09-07 | 2017-11-03 | 彭春来 | A kind of steel galvanization quickening liquid ionization removes iron purification environmental-protection processing system and method |
| CN112877718A (en) * | 2021-01-12 | 2021-06-01 | 北京科技大学 | Method for preparing high-purity magnesia-alumina spinel precursor |
| CN112877746A (en) * | 2021-01-12 | 2021-06-01 | 北京科技大学 | Method for preparing high-purity lutetium aluminum garnet precursor |
| CN113149152A (en) * | 2021-05-12 | 2021-07-23 | 洪忠伟 | Water quality activation device and method special for washing machine and dish-washing machine without chemical washing powder |
Citations (6)
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|---|---|---|---|---|
| US4597957A (en) * | 1984-03-06 | 1986-07-01 | Japan Metals And Chemicals Co., Ltd. | Process for electrolytically producing metallic oxide for ferrite |
| JPS63247385A (en) * | 1987-04-03 | 1988-10-14 | Tosoh Corp | Production of metallic hydroxide |
| US4882014A (en) * | 1988-02-24 | 1989-11-21 | Union Oil Company Of California | Electrochemical synthesis of ceramic films and powders |
| CN1072740A (en) * | 1991-11-30 | 1993-06-02 | 默克专利股份有限公司 | Use preparation of metal oxide sols by electrolysis |
| US5660709A (en) * | 1994-05-26 | 1997-08-26 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Electrochemical process and device for the production of metallic hydroxides and/or metallic-oxide hydroxides |
| US20040108220A1 (en) * | 2001-01-30 | 2004-06-10 | Hans-Oskar Stephan | Electrochemical production of nanoscale metal (mixed) oxides |
-
2004
- 2004-09-16 CN CNB2004100792401A patent/CN100342060C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4597957A (en) * | 1984-03-06 | 1986-07-01 | Japan Metals And Chemicals Co., Ltd. | Process for electrolytically producing metallic oxide for ferrite |
| JPS63247385A (en) * | 1987-04-03 | 1988-10-14 | Tosoh Corp | Production of metallic hydroxide |
| US4882014A (en) * | 1988-02-24 | 1989-11-21 | Union Oil Company Of California | Electrochemical synthesis of ceramic films and powders |
| CN1072740A (en) * | 1991-11-30 | 1993-06-02 | 默克专利股份有限公司 | Use preparation of metal oxide sols by electrolysis |
| US5660709A (en) * | 1994-05-26 | 1997-08-26 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Electrochemical process and device for the production of metallic hydroxides and/or metallic-oxide hydroxides |
| US20040108220A1 (en) * | 2001-01-30 | 2004-06-10 | Hans-Oskar Stephan | Electrochemical production of nanoscale metal (mixed) oxides |
Non-Patent Citations (1)
| Title |
|---|
| 电合成纳米金属氧化物 杨文霞，潘湛昌，张小琴，化工装备技术，第24卷第6期 2003 * |
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