CN1414138A - Method of electrolytic oxidizing cerium (III) oxide to cerium (IV) using rare earth sulphate solution ionic membrane - Google Patents
Method of electrolytic oxidizing cerium (III) oxide to cerium (IV) using rare earth sulphate solution ionic membrane Download PDFInfo
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- CN1414138A CN1414138A CN 02114300 CN02114300A CN1414138A CN 1414138 A CN1414138 A CN 1414138A CN 02114300 CN02114300 CN 02114300 CN 02114300 A CN02114300 A CN 02114300A CN 1414138 A CN1414138 A CN 1414138A
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Abstract
A process for electrolyzing cerium oxide to obtain Ce contained solution in anode chamber and the metal or alloy powder in cathode chamber features that the anode material is Pb alloy or its oxide, the cathode material is Cu, Ni or stainless steel, the isolating membrane in electrolyzer is cationic or anionic exchange membrane, the anode liquid is the acidic solution of RE sulfate, and the cathode liquid is the solution of sulfuric acid or the acidic solution of other cations. Its advantages are high uilization rate of equipment and low cost.
Description
Technical field: the present invention relates to the Non-ferrous Metallurgy field.Particularly a kind of rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV).
Technical background: the preparation of metal-powder has several different methods, and electrolytic reduction is easy to operate with it, and cost is low, is easy to control quality product and is subjected to people's attention.
Realize that at present cerium oxide [III] is cerium [IV], i.e. oxidation Ce
3+Be Ce
4+Method mainly contain two classes: a class is a chemical oxidization method, and a class is an electrochemical oxidation process.Chemical oxidization method with oxygenant with Ce
3+Be oxidized to Ce
4+Main oxygenant has oxygen, chlorine, potassium permanganate etc.Dioxygen oxidation carries out under slightly acidic or alkaline condition.The shortcoming of this method is that oxidization time is long, the service temperature height, and cerium oxide is difficult to washing and filtering, and the cerium yield is low.If make oxygenant, then there is mn ion to pollute cerium product problem, simultaneous oxidation agent price height, production cost height with potassium permanganate.The electrochemical oxidation cerium generally carries out in nitric acid system, and anode is platinum plate or platinum plating material.These material resources are in short supply, the price height.
Summary of the invention: the objective of the invention is to overcome above-mentioned existing cerium oxide (III) and be the drawback of cerium (IV) method, propose a kind of in rare earth sulfate solution both available platinum, metals such as rhodium are made anode, it is cerium (IV) that available again lead and lead alloy and oxide compound are made anodic electrolytic oxidation cerium (III), perhaps when the anolyte compartment obtains containing cerium (IV) solution, obtain the method for metal or metal-powder simultaneously at cathode compartment, by in different sections or in same section, implementing continuous varying current electrolysis, oxidation ratio and the moon of cerium have been improved, anodic current efficiency has reduced energy consumption, improved plant factor.
Technical solution of the present invention is that a kind of rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV), use ion-exchange membrane that electrolyzer is divided into anolyte compartment and cathode compartment, anode and negative electrode, anolyte and corresponding respectively anolyte compartment and the cathode compartment of placing of catholyte, when leading to the direct current electrolysis, obtain containing cerium (IV) solution in the anolyte compartment; Perhaps when the anolyte compartment obtains containing cerium (IV) solution, obtain the metal or alloy powder at cathode compartment, the special character of present method is:
(1) anolyte is the acidic solution of sulfuric acid rare earth
(2) catholyte is a sulfuric acid, or the sulfate liquor of sodium, magnesium, copper, nickel, manganese, zinc etc., or the mixed solution of above-mentioned two or more salt, or above-mentioned salt and vitriolic mixed solution
(3) the anode principal reaction is the oxidizing reaction that cerium (III) is oxidized to cerium (IV), the negative electrode principal reaction is evolving hydrogen reaction or separates out the reduction reaction of various metal or alloy powder that cathode product can be metal-powder or the binary of above-mentioned metal or the powdered alloys of multi-element metal such as hydrogen, copper, nickel, zinc, manganese.
Embodiment:
A kind of rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV), use ion-exchange membrane that electrolyzer is divided into anolyte compartment and cathode compartment, anode and negative electrode, anolyte and corresponding respectively anolyte compartment and the cathode compartment of placing of catholyte, when leading to the direct current electrolysis, obtain containing cerium (IV) solution in the anolyte compartment; Perhaps when the anolyte compartment obtains containing cerium (IV) solution, obtain the metal or alloy powder at cathode compartment, the special feature of present method is:
(1) anolyte is the acidic solution of sulfuric acid rare earth
(2) catholyte is a sulfuric acid, or the sulfate liquor of sodium, magnesium, copper, nickel, manganese, zinc etc., or the mixed solution of above-mentioned two or more salt, or above-mentioned salt and vitriolic mixed solution
(3) the anode principal reaction is the oxidizing reaction that cerium (III) is oxidized to cerium (IV), the negative electrode principal reaction is evolving hydrogen reaction or separates out the reduction reaction of various metal or alloy powder that cathode product can be metal-powder or the binary of above-mentioned metal or the powdered alloys of multi-element metal such as hydrogen, copper, nickel, zinc, manganese.
Anolyte and catholyte are formed:
Anolyte is a rare earth sulfate solution, and it consists of REO=0～0.6mol/L, [CeO
2]=0～0.6mol/L, [H
+]=0.1～6mol/L; Other positively charged ion such as Na
+, Mg
2+, Mn
2+Isoconcentration is 0～1mol/L, and negatively charged ion is [SO4
2-], its concentration is 0～5mol/L:
Catholyte consists of: [H
+]=0～10mol/L; Each metal ion such as Na
+, Mg
2+, Cu
2+, Mn
2+, Ni
2+, Zn
2+Isoconcentration is 0～2mol/L, and negatively charged ion is [SO4
2-].
Current density is controlled at 100～2000A/m
2In the scope;
Electrolyte temperature is 0 °～80 ℃ during electrolysis.
Ion-exchange membrane is cationic exchange membrane or anion-exchange membrane.
Anode is lead, lead alloy or coating or the lead oxides of galvanic deposit on other body material; Lead alloy is binary or multicomponent alloys plumbous and metals such as silver, calcium halophosphate activated by antimony andmanganese, tin; Negative electrode is copper, nickel, manganese, zinc, titanium, lead and their binary or multicomponent alloy, or stainless steel.
The distance of negative electrode, anode and ion-exchange membrane is respectively 0～100mm.
By multistage or single hop electrolysis configuration that many electrolyzers form, every section by number or several on the same stage mutually electrolyzers are not formed on the same stage.
Electrolysis mode can be the continuous varying current electrolysis of segmentation, also can be one section continuous varying current electrolysis, and varying current electrolysis promptly is: in electrolytic process as required, different sections is passed to different electric currents, or on same section,, pass to different electric currents in the different time.
The specific embodiment of the invention:
1 one kinds of rare earth sulphate solution ionic membrane electrolytic oxidations of embodiment cerium (III) is the method for cerium (IV), and negative electrode is the porous copper coin, and anode is titanium base β-P
bo
2Chamber, electrolyzer yin, yang the two poles of the earth is the plate and frame structure, and utmost point liquid circulates with magnetic drive pump, linear velocity 0.3m/s; Electrode distance 3mm, cationic membrane are HF-101; Electrolysis time 15min, current density 500A/m
2
Get 450ml and contain the cerium rare earth sulfate solution as anolyte, it consists of REO=0.23mol/L, [CeO
3+]=0.11mol/L, [H
+]=1.0mol/L, [SO4
2-]=1.8mol/L, [Mn
2+]=0.01mol/L; Other gets 1000ml acidity is catholyte for the 1.0mol/L sulphuric acid soln.Electrolysis temperature is 35 ℃; Anodic oxidation cerium current efficiency is 86.67%; Oxidation ratio 98%; Average cell voltage 2.5V.
Embodiment 2, and rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV), and cell construction, electrode diaphragm are with embodiment 1, and other conditions are also identical with embodiment 1.Anolyte consists of [REO]=0, [H
2SO
4]=0.5mol/L, volume 1000ml; Catholyte consists of [H
2SO
4]=1.5mol/L, [Cu
2+]=0.5mol/L, volume 750ml.Brush dust time 5min, electrolysis 30min must be 200 mesh sieve copper powder 3.48g, current efficiency 98%, average cell voltage 2.63V.
3 one kinds of rare earth sulphate solution ionic membrane electrolytic oxidations of embodiment cerium (III) is the method for cerium (IV), and film is an anionic membrane; Current density 600A/m
2, anode is the porous lead antimony alloy, and negative electrode is a copper coin, and anode and cathode geometric area ratio is 1: 1; Anolyte is formed [REO]=0.23mol/L, [Ce
3+]=0.18mol/L, [H
+]=1.5mol/L, [Mn
2+]=0.00mol/L, [SO
4 2-]=1.25mol/L, volume 450ml, catholyte [H
2SO
4]=2.5mol/L, volume 750ml, anolyte circulation 24min, the catholyte stirring velocity is 600r/min.Other condition is with embodiment 1; Anodic current efficiency is 73%, and the cerium oxidation ratio is 96%; Average cell voltage 2.6V.
Embodiment 4, and rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV), and the cathode and anode chamber of electrolyzer is box, and anode is a pb-ag alloy, and negative electrode is a copper coin, and ratio of cathodic to anodic area is 1: 5; Barrier film is a cationic exchange membrane.Anodic current density is 300A/m
2Anolyte [REO]=0.18mol/L, [Ce
3+]=0.07mol/L, [H
2SO
4]=0.625mol/L, volume 750ml; Catholyte consists of [H
2SO
4]=2mol/L, [Cu
2+]=0.35mol/L, other condition is with embodiment 1, electrolysis 30min, anodic current efficiency 79%; Cathode efficiency 96%; Bath voltage 2.3V.
Embodiment 5, and rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV), but anode is titanium base β-PbO
2, negative electrode is a copper coin.Anolyte forms to become [REO]=0.3mol/L, [Ce
3+]=0.3mol/L, [H
2SO
4]=1.5mol/L; Catholyte [H
2SO
4]=1.0mol/L, [Cu
2+]=0.25mol/L, volume are 750ml, and anodic current density is 800A/m
2, electrolysis 15min, anodic current efficiency is 81.2%, cathode efficiency is 97%.
Example 6, a kind of rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV), and cell construction is with embodiment 4, and anode is titanium base titanium β-PbO
2, negative electrode is a copper coin.Ion-exchange membrane is an anion-exchange membrane, and anolyte is formed [REO]=0.23mol/L, [CeO
2]=0.11mol/L, [H
+]=1.00mol/L, volume are 750ml; Catholyte [Cu
2+]=0.30mol/L, [H
+The copper sulfate acidic solution of]=3.00mol/L, volume 750ml changes primary current density every 5min in electrolytic process, and current density is respectively 1000A/m
2, 800A/m
2, 400A/m
2, 200A/m
2Its electrolysis time is 20min, and anodic current efficiency is 80%, and cathode efficiency is 95%.
Embodiment 7, and a kind of rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV), and cell construction is with embodiment 1, and totally 4 sections, electrolytic solution is formed with implementing 6; Electrolytic solution enters by first section continuously, from the 4th section discharge.First section current density is 800A/m
2Second section current density is 500Am/m
2, the 3rd section current density is 300A/m
2, the 4th section current density is 100A/m
2Anodic current efficiency 86%; Cathode efficiency 96%.
Advantage of the present invention is both can obtain containing in the anode chamber cerium (IV) solution, also can obtain in the anode chamber cerium (IV) In the time of solution, obtain the metal or alloy powder at cathode chamber, to take full advantage of electric energy, improve utilization rate of equipment and installations, fall Low production cost.
Claims (8)
1, a kind of rare earth sulphate solution ionic membrane electrolytic oxidation cerium (III) is the method for cerium (IV), use ion-exchange membrane that electrolyzer is divided into anolyte compartment and cathode compartment, anode and negative electrode, anolyte and corresponding respectively anolyte compartment and the cathode compartment of placing of catholyte, when leading to the direct current electrolysis, obtain containing cerium (IV) solution in the anolyte compartment; Perhaps when the anolyte compartment obtains containing cerium (IV) solution, obtain the metal or alloy powder at cathode compartment, present method is characterised in that:
(1) anolyte is the acidic solution of sulfuric acid rare earth
(2) catholyte is a sulfuric acid, or the sulfate liquor of sodium, magnesium, copper, nickel, manganese, zinc etc., or the mixed solution of above-mentioned two or more salt, or above-mentioned salt and vitriolic mixed solution
(3) the anode principal reaction is the oxidizing reaction that cerium (III) is oxidized to cerium (IV), the negative electrode principal reaction is evolving hydrogen reaction or separates out the reduction reaction of various metal or alloy powder that cathode product can be metal-powder or the binary of above-mentioned metal or the powdered alloys of multi-element metal such as hydrogen, copper, nickel, zinc, manganese.
2, rare earth sulphate solution ionic membrane electrolytic oxidation cerium according to claim 1 (III) is the method for cerium (IV), it is characterized in that anolyte and catholyte composition is:
Anolyte is a rare earth sulfate solution, and it consists of REO=0～0.6mol/L, [CeO
2]=0～0.6mol/L, [H
+]=0.1～6mol/L; Other positively charged ion such as Na
+, Mg
2+, Mn
2+Isoconcentration is 0～1mol/L, and negatively charged ion is [SO4
2-], its concentration is 0～5mol/L;
Catholyte consists of: [H
+]=0～10mol/L; Each metal ion such as Na
+, Mg
2+, Cu
2+, Mn
2+, Ni
2+, Zn
2+Isoconcentration is 0～2mol/L, and negatively charged ion is [SO
4 2-].
3, rare earth sulphate solution ionic membrane electrolytic oxidation cerium according to claim 1 and 2 [III] is the method for cerium (IV), and it is characterized in that: current density is controlled at 100～2000A/m
2In the scope;
4, rare earth sulphate solution ionic membrane electrolytic oxidation cerium according to claim 1 [III] is the method for cerium (IV), and electrolyte temperature is 0 °～80 ℃ when it is characterized in that electrolysis.
5, rare earth sulphate solution ionic membrane electrolytic oxidation cerium according to claim 1 (III) is the method for cerium (IV), it is characterized in that ion-exchange membrane is cationic exchange membrane or anion-exchange membrane.
6, rare earth sulphate solution ionic membrane electrolytic oxidation cerium according to claim 1 (III) is the method for cerium (IV), it is characterized in that anode is lead, lead alloy or coating or the lead oxides of galvanic deposit on other body material; Lead alloy is binary or multicomponent alloys plumbous and metals such as silver, calcium halophosphate activated by antimony andmanganese, tin; Negative electrode is copper, nickel, manganese, zinc, titanium, lead and their binary or multicomponent alloy, or stainless steel.
7, rare earth sulphate solution ionic membrane electrolytic oxidation cerium according to claim 1 (III) is the method for cerium (IV), it is characterized in that the distance of negative electrode, anode and ion-exchange membrane is respectively 0～100mm.
8, rare earth sulphate solution ionic membrane electrolytic oxidation cerium according to claim 1 (III) is the method for cerium (IV), it is characterized in that forming multiaspect or single hop configuration by many electrolyzers, and every section by number or several on the same stage mutually electrolyzers are not formed on the same stage.
Electrolysis mode can be the continuous varying current electrolysis of segmentation, also can be one section continuous varying current electrolysis, and varying current electrolysis promptly is: in electrolytic process as required, different sections is passed to different electric currents, or on same section,, pass to different electric currents in the different time.
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|---|---|---|---|
| CN 02114300 CN1257314C (en) | 2002-07-26 | 2002-07-26 | Method of electrolytic oxidizing cerium (III) oxide to cerium (IV) using rare earth sulphate solution ionic membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02114300 CN1257314C (en) | 2002-07-26 | 2002-07-26 | Method of electrolytic oxidizing cerium (III) oxide to cerium (IV) using rare earth sulphate solution ionic membrane |
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| CN1414138A true CN1414138A (en) | 2003-04-30 |
| CN1257314C CN1257314C (en) | 2006-05-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676670B (en) * | 2005-01-04 | 2010-06-09 | 华南理工大学 | Method for continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave |
| CN107674992A (en) * | 2017-09-21 | 2018-02-09 | 中国科学院过程工程研究所 | A kind of cleaning extracting method of argent |
| RU2673809C1 (en) * | 2018-06-05 | 2018-11-30 | Акционерное общество "Государственный научно-исследовательский и проектный институт редкометаллической промышленности "Гиредмет" | Method of electric oxidation of cerium ions (iii) |
| CN109666952A (en) * | 2017-10-16 | 2019-04-23 | 中国科学院过程工程研究所 | A kind of method of electro-deposition production metallic silver |
-
2002
- 2002-07-26 CN CN 02114300 patent/CN1257314C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676670B (en) * | 2005-01-04 | 2010-06-09 | 华南理工大学 | Method for continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave |
| CN107674992A (en) * | 2017-09-21 | 2018-02-09 | 中国科学院过程工程研究所 | A kind of cleaning extracting method of argent |
| CN107674992B (en) * | 2017-09-21 | 2019-08-09 | 中国科学院过程工程研究所 | A kind of cleaning extracting method of metallic silver |
| CN109666952A (en) * | 2017-10-16 | 2019-04-23 | 中国科学院过程工程研究所 | A kind of method of electro-deposition production metallic silver |
| CN109666952B (en) * | 2017-10-16 | 2020-12-04 | 中国科学院过程工程研究所 | Method for producing metallic silver by electrodeposition |
| EP3699324B1 (en) * | 2017-10-16 | 2024-06-05 | Institute of Process Engineering, Chinese Academy of Sciences | Electro-deposition method for producing metallic silver |
| RU2673809C1 (en) * | 2018-06-05 | 2018-11-30 | Акционерное общество "Государственный научно-исследовательский и проектный институт редкометаллической промышленности "Гиредмет" | Method of electric oxidation of cerium ions (iii) |
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|---|---|
| CN1257314C (en) | 2006-05-24 |
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