CN106637281A - Method for producing electrolytic manganese dioxide - Google Patents
Method for producing electrolytic manganese dioxide Download PDFInfo
- Publication number
- CN106637281A CN106637281A CN201710030895.7A CN201710030895A CN106637281A CN 106637281 A CN106637281 A CN 106637281A CN 201710030895 A CN201710030895 A CN 201710030895A CN 106637281 A CN106637281 A CN 106637281A
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- Prior art keywords
- cathode
- air
- tin
- electrolyte
- manganese dioxide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides an energy-saving type manganese dioxide electrolysis process and a method of an electrolytic cell device, aiming at solving the problems that the energy consumption is great in a production process of electrolytic manganese dioxide and environment pollution is generated. The electrolysis process is characterized in that a Pt/TiN-CNx nano gas dispersion electrode with a high electrochemical performance is used as a cathode of an electrolytic cell; the electrolytic cell device with an opening air chamber which is isolated at a cathode contact air side by utilizing a corrosion-resisting material is utilized; one side of the cathode is in contact with electrolyte and the other side of the cathode is in contact with the air; oxygen gas in the air is subjected to reduction reaction on the cathode and the reduction reaction can be operated at normal pressure or under a pressurized condition; cell voltage is more effectively reduced and energy sources are saved; a condition that the electrolyte at a solution side excessively permeates into the cathode to corrode a current collector can be avoided by pressurizing; a condition that the electrolyte permeates into the air chamber and is leaked is avoided and the service life of the electrode is prolonged. The service life of the Pt/TiN-CNx nano gas dispersion electrode is three times or more as much as that of a traditional Pt/C gas dispersion electrode under the condition that the air in the air chamber is normal-pressure 1 atmospheric pressure; the voltage of the electrolytic cell is very low and is only 0.7V; the voltage of the cell of a Cu hydrogen evolution electrode reaches 1.8V.
Description
Technical field
Electrolytic manganese field of the present invention, is related to a kind of method with energy-saving electrolytic preparation electrolytic manganese dioxide, and being characterized in that makes
With the high Pt/TiN-CNx nano gas diffusion electrode of chemical property as electrolytic cell negative electrode, cathode contacts air side is with resistance to
Corrosion material isolates the electrolytic cell assembly of discharge chamber, can more effectively reduce tank voltage with normal pressure or pressurization operation, energy saving, more
Long electrode life.
Background technology
Electrolytic manganese dioxide industry is always the industry of highly energy-consuming, and current production technology is cloudy using liberations of hydrogen such as copper, graphite
Pole carries out electrolysis production, and tank voltage is 2.5～4.0V1, huge energy consumption, up to 2000～4000kWht-1, and current efficiency
Though up to 95%～98%, negative electrode also by-product hydrogen is produced, the acidic electrolysis solution acid mist corrosion plant and equipment taken out of
Production environment pollution is also resulted in, and has deflagrability, affect workers ' health and safety.In order to solve this problem, 2010 we
A kind of preparation method of energy-saving electrolytic manganese dioxide (ZL201010578846.5) is invented, has not changed electrolytic manganese dioxide
Under conditions of technological principle and anode reaction, using gas-diffusion electrode traditional cathode for hydrogen evolution is replaced, because improve negative electrode electricity
Position makes tank voltage reduce 1.229V in theory, and negative electrode does not separate out hydrogen while reducing energy consumption, it is to avoid the generation of acid mist, protection
Environment.But though the energy-saving effect of this method depends mainly on the principle of new method, also with the performance of cathode material itself,
Predominantly electrocatalysis and stability (i.e. life-span), and air is to the transfer ways and pressure thight phase of cathode contacts air side
Close.
For this purpose, it is an object of the invention to propose a kind of energy-saving electrolytic manganese dioxide method, can more effectively reduce life
Tank voltage, the reducing energy consumption of electrolytic manganese dioxide are produced, electrode life is greatly improved.
The content of the invention
Energy consumption is big and generation environment pollutes in order to solve the problems, such as electrolytic manganese dioxide production process, the invention provides
A kind of method of energy-saving electrolysis process and electrolytic cell assembly.
A kind of method for producing electrolytic manganese dioxide, it is characterised in that made using Pt/TiN-CNx nano gas diffusion electrode
For negative electrode, electrolyte is 20～40gdm-3H2SO4+ 100～140gdm-3MnSO4+ solution, temperature is 80 DEG C, and anode is titanium
Base coated anode.Pt/TiN-CNx is adopted for catalyst, wherein CNx is nano wire, Pt, TiN are nano-particle.
The present invention uses the electrolytic cell assembly (figure that open plenum is isolated in cathode contacts air side corrosion resistant material
1) there is reduction reaction in, negative electrode one side and electrolyte contacts, another side and air contact, the oxygen in air, can be with negative electrode
Normal pressure or pressurization operation, not only more effectively reduce tank voltage, energy saving, and pressurization can also avoid solution side electrolyte from excessively penetrating into
Negative electrode and corrode collector, it is to avoid electrolyte seepage flow air inlet chamber and reveal.
Pt/TiN-CNx nano gas diffusion electrodes adopt Pt/TiN-CNx for catalyst (wherein CNx be nano wire, Pt,
TiN is nano-particle), it is traditional Pt/C gas-diffusion electrodes of catalyst that contrast has used Pt/C (wherein Pt is nano-particle)
And Cu hydrogen-precipitating electrodes.Pt/TiN-CNx nano gas diffusion electrode is than traditional Pt/C gas-diffusion electrodes and Cu hydrogen-precipitating electrodes
With more preferable electro catalytic activity：In 30gdm-3H2SO4+120g·dm-3MnSO4100Am used in solution-2Current electrifying
Electrolysis, Pt/TiN-CNx nano gas diffusion electrodes, Pt/C gas-diffusion electrode oxygen reduction cathode current potentials be respectively 0.01V ,-
0.02V is (relative to Hg/Hg2SO4Reference electrode), the cathode hydrogen evolution current potential of Cu electrodes is -1.1V (relative to Hg/Hg2SO4Reference
Electrode) (Fig. 2).
Using the method for the energy-saving electrolysis process and electrolytic cell assembly of the present invention, under the atmospheric pressure normal pressure of air chamber air 1,
Pt/TiN-CNx nano gas diffusion electrode has lower bath voltage than traditional Pt/C gas-diffusion electrodes, especially more
Long life-span, respectively 0.7V, 1578h and 0.9V, 469h, the life-span of Pt/TiN-CNx nano gas diffusion electrodes is tradition
More than 3 times of Pt/C gas-diffusion electrodes, and use the tank voltage of Cu hydrogen-precipitating electrodes to reach 1.8V.
Description of the drawings
The following drawings is only intended in schematic illustration and explanation is done to the present invention, is not delimit the scope of the invention.
Wherein：
Fig. 1：Using Pt/TiN-CNx nano gas diffusion electrode as negative electrode the cell construction for having an open plenum
Fig. 2：Pt/TiN-CNx nano gas diffusion electrode is with Pt/C gas-diffusion electrodes in 100Am-2Under current density
Cathode potential
Drawing reference numeral explanation：
1-anode, 2-Pt/TiN-CNx nano gas diffusion electrodes, 3-there is the air chamber of opening
Specific embodiment：
Embodiment one
Under the atmospheric pressure normal pressure of air chamber air 1, Pt/TiN-CNx nano gas diffusion electrodes are mounted in electrolytic cell, are put into
30g·dm-3H2SO4+120g·dm-3In MnSO4 solution, temperature is 80 DEG C, and electric current is 100Am-2It is electrolysed
Manganese dioxide.As a comparison, traditional Pt/C gas-diffusion electrodes and Cu hydrogen-precipitating electrodes are mounted in electrolytic cell under same normal pressure
Carry out energization electrolysis.
Pt/TiN-CNx nano gas diffusion electrode has lower bath voltage than traditional Pt/C gas-diffusion electrodes,
Especially longer life-span, respectively 0.7V, 1578h and 0.9V, 469h, and use the tank voltage of Cu hydrogen-precipitating electrodes to reach 1.8V.
Embodiment two
The atmospheric pressure of air chamber air 1.2 is slightly depressed, and Pt/TiN-CNx nano gas diffusion electrodes are mounted in electrolytic cell, is put
Enter 30gdm-3H2SO4+120g·dm-3MnSO4In solution, temperature is 80 DEG C, and electric current is 100Am-2The electrolysis that is powered obtains electricity
Solution manganese dioxide.As a comparison, traditional Pt/C gas-diffusion electrodes and Cu hydrogen-precipitating electrodes are mounted in electrolytic cell by same plus pressure
Inside carry out energization electrolysis.
Pt/TiN-CNx nano gas diffusion electrode has lower electrolytic cell pressure than traditional Pt/C gas-diffusion electrodes, and
Life-span, respectively 0.6V, 1632h and 0.8V, 493h are extended than normal pressure, and uses the tank voltage of Cu hydrogen-precipitating electrodes to reach 1.8V.
Claims (2)
1. a kind of method for producing electrolytic manganese dioxide, it is characterised in that using Pt/TiN-CNx nano gas diffusion electrode as
Negative electrode, electrolyte is 20～40gdm-3H2SO4+ 100～140gdm-3MnSO4+ solution, anode is coated titanium anode；Adopt
It is catalyst with Pt/TiN-CNx, wherein CNx is nano wire, Pt, TiN are nano-particle.
2. a kind of method for producing electrolytic manganese dioxide as claimed in claim 1, it is characterised in that using empty in cathode contacts
Gas side corrosion resistant material isolates the electrolytic cell assembly of open plenum, negative electrode one side and electrolyte contacts, another side and air
There is reduction reaction, energy normal pressure or pressurization operation in contact, the oxygen in air, not only more effectively reduce tank voltage, section in negative electrode
The about energy, pressurization can also avoid solution side electrolyte from excessively penetrating into negative electrode and corrode collector, it is to avoid electrolyte seepage flow air inlet chamber
And reveal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710030895.7A CN106637281A (en) | 2017-01-17 | 2017-01-17 | Method for producing electrolytic manganese dioxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710030895.7A CN106637281A (en) | 2017-01-17 | 2017-01-17 | Method for producing electrolytic manganese dioxide |
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| Publication Number | Publication Date |
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| CN106637281A true CN106637281A (en) | 2017-05-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710030895.7A Pending CN106637281A (en) | 2017-01-17 | 2017-01-17 | Method for producing electrolytic manganese dioxide |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031532A (en) * | 2010-12-03 | 2011-04-27 | 北京科技大学 | Energy-saving electrolytic manganese dioxide preparation method |
| CN104593806A (en) * | 2015-01-04 | 2015-05-06 | 北京科技大学 | Method for preparing gas diffusion electrode for strongly acidic electrolyte |
-
2017
- 2017-01-17 CN CN201710030895.7A patent/CN106637281A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031532A (en) * | 2010-12-03 | 2011-04-27 | 北京科技大学 | Energy-saving electrolytic manganese dioxide preparation method |
| CN104593806A (en) * | 2015-01-04 | 2015-05-06 | 北京科技大学 | Method for preparing gas diffusion electrode for strongly acidic electrolyte |
Non-Patent Citations (3)
| Title |
|---|
| JING TANG 等: "Gas diffusion electrode with platinum/titanium nitride-carbon nitride nanocatalysts for the energy-saving and environment-friendly electrodeposition of manganese dioxide", 《JOURNAL OF CLEANER PRODUCTION》 * |
| 张慧 等: "氧阴极节能环保制备电解二氧化锰新方法", 《中国锰业》 * |
| 张慧 等: "电解制备二氧化锰强酸性电解液中气体扩散电极的稳定性与失效行为", 《物理化学学报》 * |
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Application publication date: 20170510 |