CN108330514A - A kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode - Google Patents
A kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode Download PDFInfo
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- CN108330514A CN108330514A CN201810385368.2A CN201810385368A CN108330514A CN 108330514 A CN108330514 A CN 108330514A CN 201810385368 A CN201810385368 A CN 201810385368A CN 108330514 A CN108330514 A CN 108330514A
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Abstract
The invention discloses a kind of hydrometallurgy preparation methods of iridium tin rubidium zirconium quaternary composite oxides anode, belong to field of hydrometallurgy.Obtained anode is made of Titanium base and oxide coating, and stannic oxide and iridium dioxide are Rutile Type in coating, and rubidium oxide and zirconium dioxide are amorphous phase, part stannic oxide and iridium dioxide can form rutile-type solid solution in being sintered preparation process.With conventional Ti/IrO2Anode is compared, and the incorporation of tin enhances corrosion resistance of the iridium in sulfuric acid system, extends anode service life, and the addition of zirconium promotes oxygen evolution activity substance IrO2The precipitation of crystal, effectively raises the oxygen evolution activity surface area of anode, and the addition of rubidium enhances the electric conductivity of anode, reduces anode potential.Preparation flow of the present invention is simple, obtained anode has preferable analysis oxygen catalytic activity and service life, further, since the precious metal element in coating is replaced by tin and zirconium, the production cost for effectively reducing anode is a kind of very hydrometallurgy anode with prospect of the application.
Description
Technical field
The present invention relates to a kind of technical field of wet metallurgy more particularly to a kind of iridium tin rubidium zirconium quaternary composite oxides inertia
The preparation method of anode.
Background technology
With being constantly progressive for society, have to the consuming of the pollution of environment and the energy in industrial production more stringent
It is required that energy-saving and emission-reduction have become the theme of 21 century social development.In recent ten years, the coloured industry development in China is rapid, copper,
The increase of production of the metals such as zinc is rapid.Compared with pyrometallurgical smelting, hydrometallurgy big, efficient, operating condition with production capacity
It is good, pollute compared with light and high valuable metal comprehensive recovery advantage, currently, 80% or so zinc and 20% or so in the world
Copper is extracted by hydrometallurgy.Anode has hydrometallurgical as core main body and important equipment in hydrometallurgy process
The title of " heart ".The quality of anode performance will have a direct impact on energy consumption and cathode product quality in wet smelting process.
Currently, the anode that hydrometallurgy industry uses is mostly pure Pb anodes and Pb alloy anodes, such as：Pb-Ag、Pb-Ag-
Sn and Pb-Sb-Sn-Ag etc..Though it is with corrosion-resistant in easy processing molding, low manufacture cost, sulfuric acid electrolyte, service life is long
The advantages that, but there is also big in oxygen overpotential on anode height, electrolytic process anode Pb dissolving pollutions cathode product, electrolytic process
The shortcomings of generation of the amount earth of positive pole can increase labour cost.According to statistics, overpotential for oxygen evolution of the pure Pb anodes in electrolytic process can
Up to 860mV, and the overpotential for oxygen evolution of Pb-Ag alloy anodes, also in 600mV or so, thus increased useless power consumption accounts for about Zinc electrolysis
30% or so of total energy consumption, therefore, exploitation and the application of high oxygen separated active anode have received widespread attention.
Titanium is referred to as valve metal, has stable oxide layer protection, there is good durability and dimensional stability under electrolysis conditions.
Compared with pure Pb anodes and Pb alloy anodes, coated titanium anode is with appearance and size is stable, overpotential for oxygen evolution is low, electrolytic process
The advantages that Anodic will not pollute cathode product has obtained making extensively in the electrolysis production process of high purity product in recent years
With.Ruthenic oxide (RuO2) and iridium dioxide (IrO2) due to its good analysis oxygen catalytic performance, it is chiefly used in coated titanium anode
It prepares.And it finds in use, Ti/RuO2Though anode shows excellent analysis oxygen catalytic performance, preferably reduce
The overpotential for oxygen evolution of electrolytic process Anodic, but in sulfuric acid system, Ti/RuO2The service life of anode is shorter, about 100 days,
Constrain its application in hydrometallurgy process.Ti/IrO2Though the analysis oxygen catalytic performance slightly worse than Ti/RuO of anode2Anode, but
It shows preferable corrosion resistance in sulfuric acid system, and service life was up to 1 year or more, but iridium is expensive, Ti/
IrO2The cost of manufacture of anode is higher, limits its large-scale application.To meet industrial needs, researcher will
IrO2And RuO2It is used in mixed way with some inertia constituent elements Deng the high constituent element of analysis oxygen catalytic activity, is prepared into multicomponent composite oxide painting
Layer improves the service life of anode, reduces being produced into for anode on the basis of ensureing excellent analysis oxygen catalytic activity
This.Currently, multicomponent composite oxide coating composition is mainly IrO2-Ta2O5、IrO2-RuO2、IrO2-SnO2、RuO2-SnO2With
IrO2-RuO2-TiO2Deng, but there are still the skies further improved for its analysis oxygen catalytic activity, anode service life and production cost
Between.
Invention content
The object of the present invention is to provide a kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode, the preparations
Method flow is simple, and obtained anode has preferable analysis oxygen catalytic activity, long service life and cheap is prepared into
This.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode, the method includes：
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, is cleaned by ultrasonic and dries；
Step 2, by RbCl, SnCl4、H2IrCl6It is miscible with tetrabutyl zirconate progress, it obtains needed for configuration coating solution
Solute；
Step 3, by volume ratio be 1:1 n-butanol and the mixed solvent of isopropanol are added in matched solute, are obtained
Coating solution；
The coating solution prepared is coated in pretreated Titanium base surface by step 4, through drying
Iridium tin rubidium zirconium quaternary composite oxides inert anode is obtained after dry, sintering processes.
In obtained coating solution, the molar concentration of tin and iridium is 0.01-0.10mol/L, and the molar concentration of rubidium is
The molar concentration of 0.02-0.10mol/L, zirconium are 0.05-0.15mol/L.
In the step 4：
Coating is applied to 10-40 layers, and drying temperature is 100-200 DEG C, and drying time is 10-15 minutes；
Sintering temperature is 400-600oC, and sintering time is 10-15 minutes, and it is 1 hour to burn the time eventually.
In the step 4：
Stannic oxide and iridium dioxide are Rutile Type in the coating, and rubidium oxide and zirconium dioxide are amorphous phase, are being burnt
Stannic oxide can form rutile-type solid solution with iridium dioxide during knot.
As seen from the above technical solution provided by the invention, simple, the obtained anode of above-mentioned preparation method flow
It is that one kind extremely having promising hydrometallurgy anode with preferable catalytic activity and service life.
Description of the drawings
Fig. 1 is Ti/IrO of the present invention2-SnO2-Rb2O-ZrO2The preparation flow figure of quaternary composite oxides inert anode.
Specific implementation mode
Embodiment one：
First by the titanium plate of 10mm × 10mm × 1mm through 60oC alkali cleanings 30 minutes, the etching 2.5 of 10% oxalic acid is small under 90oC
When, deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh RbCl, SnCl of certain mass4、H2IrCl6It is miscible with tetrabutyl zirconate.
RbCl, SnCl after will be miscible4、H2IrCl6It is dissolved in by 1 with the mixed solution of tetrabutyl zirconate:1 proportioning mixing
N-butanol and isopropanol in the mixed solvent, obtain coating solution.RbCl, SnCl in coating solution4、H2IrCl6With zirconic acid four
The molar concentration of butyl ester is respectively 0.020,0.084,0.036 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120oC
10 minutes, then be sintered 10 minutes at 450oC, postcooling is taken out to room temperature.After above-mentioned steps repeat 25 times, anode plate is existed
It is sintered 1 hour under 450oC, obtains the quaternary composite oxides anode of the rubidium zirconium of tin containing iridium.
Further, the quaternary composite oxides anode prepared can be placed in the sulfuric acid solution of 0.5mol/L, is adopted
The oxygen evolution potential of anode is determined with three-electrode system, is platinum electrode to electrode, saturated calomel electrode is reference electrode,
When current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.36V vs.SCE.It is to assess anode in sulfuric acid system
Service life in current density is 2A/cm to the anode for preparing2Under conditions of carried out accelerated life test, work as tank voltage
Judgement anode failure when rising 5V compared with testing initial voltage.It is calculated according to experiment measurement result and empirical equation, it is obtained
Its true service life of the rubidium zirconium quaternary composite oxides of tin containing iridium anode is expected to be higher than 2 years.
Embodiment two：
First by the titanium plate of 10mm × 10mm × 1mm through 60oC alkali cleanings 30 minutes, 90oC10% oxalic acid etches 2.5 hours,
Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh RbCl, SnCl of certain mass4、H2IrCl6It is miscible with tetrabutyl zirconate.
By RbCl, SnCl after standing4、H2IrCl6It is dissolved in by 1 with the mixed solution of tetrabutyl zirconate:1 proportioning mixing
N-butanol and isopropanol in the mixed solvent, obtain coating solution.RbCl, SnCl in coating solution4、H2IrCl6With zirconic acid four
The molar concentration of butyl ester is respectively 0.040,0.030,0.030 and 0.100mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120oC
15 minutes, then be sintered 15 minutes at 500oC, postcooling is taken out to room temperature.After above-mentioned steps repeat 25 times, anode plate is existed
It is sintered 1 hour under 500oC, obtains the quaternary composite oxides anode of the rubidium zirconium of tin containing iridium.
Further, the quaternary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three
Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity
Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.34V vs.SCE.For use of the assessment anode in sulfuric acid system
Service life in current density is 2A/cm to the anode for preparing2Under conditions of carried out accelerated life test, when tank voltage and reality
Initial voltage is tested compared to judgement anode failure when rising 5V.It is calculated according to experiment measurement result and empirical equation, it is obtained to contain iridium
Its true service life of tin rubidium zirconium quaternary composite oxides anode is expected to be higher than 2 years.
Embodiment three：
First by the titanium plate of 10mm × 10mm × 1mm through 60oC alkali cleanings 30 minutes, 90oC10% oxalic acid etches 2.5 hours,
Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh RbCl, SnCl of certain mass4、H2IrCl6It is miscible with tetrabutyl zirconate.
By RbCl, SnCl after standing4、H2IrCl6It is dissolved in by 1 with the mixed solution of tetrabutyl zirconate:1 proportioning mixing
N-butanol and isopropanol in the mixed solvent, obtain coating solution.RbCl, SnCl in coating solution4、H2IrCl6With zirconic acid four
The molar concentration of butyl ester is respectively 0.060,0.024,0.056 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120oC
15 minutes, then be sintered 15 minutes at 400oC, postcooling is taken out to room temperature.After above-mentioned steps repeat 25 times, anode plate is existed
It is sintered 1 hour under 400oC, obtains the quaternary composite oxides anode of the rubidium zirconium of tin containing iridium.
Further, the quaternary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three
Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity
Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.30V vs.SCE.For use of the assessment anode in sulfuric acid system
Service life in current density is 2A/cm to the anode for preparing2Under conditions of carried out accelerated life test, when tank voltage and reality
Initial voltage is tested compared to judgement anode failure when rising 5V.It is calculated according to experiment measurement result and empirical equation, it is obtained to contain iridium
Its true service life of tin rubidium zirconium quaternary composite oxides anode is expected to be higher than 2 years.
Embodiment four：
First by the titanium plate of 10mm × 10mm × 1mm through 60oC alkali cleanings 30 minutes, 90oC10% oxalic acid etches 2.5 hours,
Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the SnCl of certain mass4、RbCl、H2IrCl6It is miscible with tetrabutyl zirconate.
By RbCl, SnCl after standing4、H2IrCl6It is dissolved in by 1 with the mixed solution of tetrabutyl zirconate:1 proportioning mixing
N-butanol and isopropanol in the mixed solvent, obtain coating solution.RbCl, SnCl in coating solution4、H2IrCl6With zirconic acid four
The molar concentration of butyl ester is respectively 0.020,0.020,0.020 and 0.140mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120oC
10 minutes, then be sintered 10 minutes at 600oC, postcooling is taken out to room temperature.After above-mentioned steps repeat 30 times, anode plate is existed
It is sintered 1 hour under 600oC, obtains the rubidium zirconium quaternary composite oxides anode of tin containing iridium.
Further, the quaternary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three
Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity
Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.38V vs.SCE.For use of the assessment anode in sulfuric acid system
Service life in current density is 2A/cm to the anode for preparing2Under conditions of carried out accelerated life test, when tank voltage and reality
Initial voltage is tested compared to judgement anode failure when rising 5V.It is calculated according to experiment measurement result and empirical equation, it is obtained to contain iridium
Its true service life of tin rubidium zirconium quaternary composite oxides anode is expected to be higher than 1 year.
It is worth noting that, the content not being described in detail in the embodiment of the present invention belongs to professional and technical personnel in the field's public affairs
The prior art known.
The anode prepared according to the method for the invention has following features compared with existing anode：
1) preparation flow is succinct, and required equipment is few and simple, and equipment investment is low, and easy to operate, technology is easily promoted；
2)ZrO2Incorporation promote active material IrO2The precipitation of crystal, makes gained quaternary composite oxides anode and passes
Unite IrO2Oxide anode compares the specific surface area active with bigger, improves the analysis oxygen catalytic performance of anode；
3) incorporation of Rb improves the electric conductivity of anode, reduces anode potential；
4) inertia constituent element SnO2And ZrO2Incorporation, reduce the usage amount of precious metal iridium, significantly reduce the production of anode
Cost；
5) active component IrO2With inertia constituent element SnO2Solid solution effect, improve active component IrO2It is resistance in sulfuric acid system
Corrosive nature.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (4)
1. a kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode, which is characterized in that the method includes：
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, is cleaned by ultrasonic and dries；
Step 2, by RbCl, SnCl4、H2IrCl6It is miscible with tetrabutyl zirconate progress, obtain the solute needed for configuration coating solution；
Step 3, by volume ratio be 1:1 n-butanol and the mixed solvent of isopropanol are added in matched solute, are coated
Solution；
The coating solution prepared is coated in pretreated Titanium base surface, drying, burning by step 4
Iridium tin rubidium zirconium quaternary composite oxides inert anode is obtained after knot processing.
2. the preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode according to claim 1, which is characterized in that
In obtained coating solution, the molar concentration of tin and iridium is 0.01-0.10mol/L, and the molar concentration of rubidium is 0.02-
The molar concentration of 0.10mol/L, zirconium are 0.05-0.15mol/L.
3. the preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode according to claim 1, which is characterized in that
Coating described in step 4 is applied to 10-40 layers, and drying temperature is 100~200 DEG C, and drying time is 10-15 minutes；
Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and it is 1 hour to burn the time eventually.
4. the preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode according to claim 1, which is characterized in that
Stannic oxide and iridium dioxide are Rutile Type in coating described in step 4, and rubidium oxide and zirconium dioxide are amorphous phase, part dioxy
Rutile-type solid solution can be formed in being sintered preparation process by changing tin and iridium dioxide.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810385368.2A CN108330514A (en) | 2018-04-26 | 2018-04-26 | A kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode |
| CN201910302460.2A CN109972177B (en) | 2018-04-26 | 2019-04-16 | Preparation method of long-life iridium-zirconium composite oxide inert anode |
Applications Claiming Priority (1)
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|---|---|---|---|
| CN201810385368.2A CN108330514A (en) | 2018-04-26 | 2018-04-26 | A kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode |
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| Publication Number | Publication Date |
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| CN108330514A true CN108330514A (en) | 2018-07-27 |
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| CN201810385368.2A Withdrawn CN108330514A (en) | 2018-04-26 | 2018-04-26 | A kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode |
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Application publication date: 20180727 |