CN104928710B - Electrolytic cell for producing manganese dioxide - Google Patents
Electrolytic cell for producing manganese dioxide Download PDFInfo
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- CN104928710B CN104928710B CN201510354093.2A CN201510354093A CN104928710B CN 104928710 B CN104928710 B CN 104928710B CN 201510354093 A CN201510354093 A CN 201510354093A CN 104928710 B CN104928710 B CN 104928710B
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Abstract
The invention discloses an electrolytic cell for producing manganese dioxide, which comprises a cell body, wherein a liquid inlet and a waste liquid overflow port are arranged on the cell body, positive and negative electrodes are arranged in the cell body, the cell body sequentially comprises granite, an anticorrosive layer, a lacing wire layer and a steel plate from inside to outside, a steam heating pipe is arranged at the bottom of the cell body, the waste liquid overflow port is positioned at the upper part of the cell body, and an area for accommodating a heat preservation bubble layer is arranged above the waste liquid overflow port. The electrolytic cell for producing manganese dioxide provided by the invention adopts a multilayer composite structure, has good acid resistance and high strength, is heated at the bottom of the cell body, is provided with a region for accommodating a heat-preservation bubble layer above the cell body, and forms bubble coverage of the whole cell by using hydrogen as a foaming gas source, so that the temperature in the reaction cell is raised, the effects of dissolving bottom sediment of the cell, reducing pressure drop of the bottom of the cell and the like are achieved, meanwhile, the corrosion of hydrogen escape on gas equipment in a factory building is reduced, and finally, a space is found for reducing the voltage of the cell.
Description
Technical Field
The invention relates to an electrolytic cell, in particular to an electrolytic cell for producing manganese dioxide.
Background
With the continuous development of the battery industry, particularly the popularization of electric bicycles and power automobiles, manganese dioxide special for novel battery anode materials such as zinc-manganese batteries, alkaline batteries, lithium manganate batteries and the like is rapidly developed. It is expected that with the gradual promotion of the market, lead-acid batteries will gradually withdraw, electrolytic manganese dioxide for novel batteries will be rapidly developed, the development of the whole electrolytic manganese dioxide product market is driven, and the demand of electrolytic manganese dioxide products will increase year by year.
The electrolytic manganese dioxide product is prepared by electrolyzing a manganese sulfate solution, pyrolusite or sclerousite is used as a raw material, is converted into relatively pure divalent manganese salt through chemical conversion, and is electrolyzed in a sulfuric acid medium to obtain the electrolytic manganese dioxide. The industrialization of the "high temperature electrolysis of a sulphuric acid-containing manganese sulphate liquor" for the production of electrolytic manganese dioxide was successfully achieved in the united states over the end of the 20 th century, and since then the process has almost not changed for more than half a century.
The method comprises the following steps of electrolyzing a sulfuric acid-containing manganese sulfate solution at a high temperature, wherein the reaction generated in the electrolytic process is as follows:
anode: mn (Mn) 2+ -2e - +4OH - ＝MnO 2 +2H 2 O
Cathode: 2H + +2e - ＝H 2 ↑
And (3) total reaction: mnSO 4 +2H 2 O＝＝MnO 2 +H 2 SO 4 +H 2 (heating is advantageous for increasing the reaction rate).
The existing manganese dioxide electrolytic bath heat preservation method generally adopts a heat preservation ball or a covering heat preservation device and other methods. But the adoption of the heat-insulating ball or the covering heat-insulating device not only occupies the space of the tank body, but also influences the distribution of the positive and negative electrodes. In addition, the covering and insulating device has short circuit between positive and negative electrodes (anode: mn) 2+ -2e - +4OH - ＝MnO 2 +2H 2 O, water vapor is released and easily condensed into water droplets on the cover heat-insulating device to the positive and negative electrode linking devices, causing short circuits) and the risk of hydrogen explosion (cathode: 2H + +2e - ＝H 2 The gas hydrogen emitted by the oil wells is covered in the heat preservation device to form a relatively closed environment, and if the volume concentration of the hydrogen in the air is between 4.1% and 74.2%, the hydrogen is extremely easy to explode).
Disclosure of Invention
The invention aims to solve the technical problem of providing the electrolytic cell for producing manganese dioxide, which has good acid resistance and high strength, can realize high-efficiency heat preservation, and greatly reduces the loss of heat; meanwhile, the heat which is taken away by the gas in the electrolytic cell and the corrosion of hydrogen to surrounding equipment are reduced.
The invention provides an electrolytic cell for producing manganese dioxide, which comprises a cell body, wherein the cell body is provided with a liquid inlet and a waste liquid overflow port, and a positive electrode and a negative electrode are arranged in the cell body, wherein the cell body sequentially comprises granite, an anticorrosive layer, a lacing wire layer and a steel plate from inside to outside, a steam heating pipe is arranged at the bottom of the cell body, the waste liquid overflow port is positioned at the upper part of the cell body, and an area for accommodating a heat-preservation bubble layer is arranged above the waste liquid overflow port.
In the electrolytic cell for producing manganese dioxide, the lacing wire layer comprises a plurality of rows of lacing wires, and the upper and lower rows of lacing wires are vertically staggered.
The electrolytic cell for producing manganese dioxide is characterized in that the anticorrosive layer is made of non-woven glass fiber reinforced plastics.
In the electrolytic cell for producing manganese dioxide, the foam adsorption layer is formed by polishing the inner wall of the granite in the heat-preservation bubble layer area.
The electrolytic cell for producing manganese dioxide is characterized in that the positive electrode and the negative electrode are a plurality of anodes and cathodes which are arranged side by side in a staggered manner, the anodes and the cathodes extend out of the area where the heat preservation bubble layer is located and are connected with the busbar splitter plate, electrode contacts of the anodes and the cathodes are inverted V-shaped, triangular electrodes matched with the inverted V-shaped electrode contacts are arranged on the busbar splitter plate, and conductive glue is coated on the inverted V-shaped electrode contacts and the contact positions of the triangular electrodes on the busbar splitter plate.
In the electrolytic cell for producing manganese dioxide, the anode is a Ti glass-grain plate or a Ti-Mn alloy coating, and the cathode is a copper tube.
The electrolytic cell for producing manganese dioxide is characterized in that the waste liquid overflow port is connected with the low-level tank through a waste liquid overflow pipe, a flow regulating valve is arranged on the waste liquid overflow pipe, the liquid inlet is connected with the high-level tank, the high-level tank is located above the low-level tank, and a seabed plug and an insulating sleeper stone are arranged at the bottom of the electrolytic cell.
In the electrolytic cell for producing manganese dioxide, the steam heating pipe is a titanium heating pipe, the titanium heating pipe is distributed at the bottom of the cell body according to a zigzag shape, the positive and negative electrodes are alternately distributed along the cell body at equal intervals, and the positive and negative electrodes are positioned at the positive peak or the negative peak of the zigzag titanium heating pipe.
Compared with the prior art, the invention has the following beneficial effects: the electrolytic tank for producing manganese dioxide provided by the invention adopts a multilayer composite structure, has good acid resistance and high strength, is heated at the bottom of the tank body, is provided with a region for accommodating a heat-preservation bubble layer above the tank body, and forms bubble coverage of the whole tank by using hydrogen as a foaming gas source, so that the temperature in the reaction tank is raised, the effects of dissolving bottom sediment of the tank, reducing pressure drop of the tank bottom and the like are achieved, and meanwhile, the corrosion of hydrogen escape to gas equipment in a factory building is reduced; compared with the traditional heat preservation device, the device greatly saves the space of the cell body and effectively avoids the short circuit of the electrodes, thereby conveniently increasing the number of groups of the cathode plate and the anode plate, optimizing the inter-polar distance of the electrolytic cell and finally searching the space for reducing the cell voltage.
Drawings
FIG. 1 is a schematic diagram of an electrolytic cell for producing manganese dioxide in accordance with the present invention;
FIG. 2 is a schematic sectional view of the electrolytic cell for producing manganese dioxide according to the present invention;
fig. 3 is a schematic view of a connection structure of an electrode contact and a busbar splitter plate in the tank body.
In the figure:
1. tank 2 anode 3 cathode
4. Waste liquid overflow port 5 and waste liquid overflow pipe 6 steam heating pipe
7. Low-position groove 8 seabed plug 9 insulation sleeper stone
10. Electrolyte level of electrolyte 12 in heat-preservation bubble layer area 11
13. Busbar flow distribution plate 14 electrode contact 15 triangular electrode
101. Granite 102 anticorrosive layer 103 tie layer
104. Steel plate
Detailed Description
The invention is further described below with reference to the figures and examples.
FIG. 1 is a schematic diagram of an electrolytic cell for producing manganese dioxide according to the present invention; FIG. 2 is a schematic sectional view of the electrolytic cell for producing manganese dioxide according to the present invention.
Referring to fig. 1 and fig. 2, the electrolytic tank for producing manganese dioxide provided by the present invention comprises a tank body 1, wherein a liquid inlet (not shown) and a waste liquid overflow port 4 are arranged on the tank body 1, positive and negative electrodes are arranged in the tank body 1, wherein the tank body sequentially comprises a granite 101, an anticorrosive layer 102, a tie bar layer 103 and a steel plate 104 from inside to outside, a steam heating pipe 6 is arranged at the bottom of the tank body 1, the waste liquid overflow port 4 is located at the upper part of the tank body, and a heat preservation bubble layer area 10 is arranged above the waste liquid overflow port 4; the heat preservation bubble layer region 10 is located above the electrolyte 11.
According to the electrolytic tank for producing manganese dioxide, the waste liquid overflow port 4 is connected with the low-level tank 7 through the waste liquid overflow pipe 5, the waste liquid overflow port 4 is located at the position of an electrolytic solution level 12, the waste liquid overflow pipe 5 is provided with a flow regulating valve (not shown), the liquid inlet is connected with the high-level tank, the high-level tank is located above the low-level tank, and the bottom of the electrolytic tank is provided with the seabed plug 8 and the insulating sleeper stone 9.
The electrolytic cell for producing manganese dioxide provided by the invention adopts a multilayer composite structure, and has the advantages of good acid resistance, easy processing and low cost. The steel plate 104 and the lacing wire layer 103 mainly function to protect the inner two layers, the lacing wire layer 103 comprises a plurality of rows of lacing wires, and the upper row of lacing wires and the lower row of lacing wires are vertically staggered so as to better bear the weight in the groove; the anti-corrosion layer 102 is mainly used for effectively preventing the invasion of high-acid and high-temperature electrolyte in the tank, and has the effects of insulating, preventing the waste and potential safety hazard caused by electric leakage of the tank body; the anticorrosive layer 102 is preferably made of non-woven glass fiber reinforced plastics, and can better meet the process requirement of electrolytic manganese dioxide. The granite 101 is mainly used for effectively defending the corrosion-resistant layer which is easily damaged when the large-scale electrode is installed in the groove, and plays a role in protecting the corrosion-resistant layer 102. The granite inner wall located in the heat preservation air bubble layer area 10 is polished to form a foam adsorption layer, so that foam can be better adsorbed, and the heat preservation effect is improved.
According to the electrolytic tank for producing manganese dioxide, the bottom of the tank body 1 is heated, the area for accommodating the heat preservation bubble layer is arranged above the tank body, and hydrogen is used as a foaming gas source to form bubble coverage of the whole tank, so that the temperature in the reaction tank is raised, the effects of dissolving tank bottom sediment, reducing tank bottom pressure drop and the like are achieved, and meanwhile, the corrosion of hydrogen escaping to gas equipment in a factory building is reduced. Compared with the traditional heat preservation device, the device greatly saves the space of the cell body and effectively avoids the short circuit of the electrodes, thereby conveniently increasing the number of groups of the cathode plate and the anode plate, optimizing the inter-polar distance of the electrolytic cell and finally searching the space for reducing the cell voltage. The steam heating pipe 6 is preferably a titanium heating pipe, the titanium heating pipe is distributed at the bottom of the tank body 1 according to a zigzag shape, the positive and negative electrodes are alternately distributed at equal intervals along the tank body 1, and the positive and negative electrodes are positioned at the positive peak or the negative peak of the zigzag titanium heating pipe so as to improve the heating efficiency and better control the heating temperature.
According to the electrolytic cell for producing manganese dioxide, the positive electrode and the negative electrode are a plurality of anodes 2 and cathodes 3 which are arranged in a staggered mode side by side, the anodes 2 and the cathodes 3 extend out of the heat preservation bubble layer area 10 and are connected with the busbar splitter plate 13, the electrode contacts 14 of the anodes 2 and the cathodes 3 are inverted V-shaped, triangular electrodes 15 matched with the inverted V-shaped electrode contacts are arranged on the busbar splitter plate 13, the contact area between the electrodes and the power transmission busbar is increased, and the generation of resistance can be effectively reduced, as shown in fig. 3; the contact positions of the inverted V-shaped electrode contacts and the triangular electrodes 15 on the busbar flow distribution plate are coated with conductive adhesive, so that the contact resistance is reduced, personnel are protected from electric shock, electrolyte is protected from being polluted, and the purpose of saving electricity is further achieved.
The electrolytic cell for producing manganese dioxide provided by the invention selects titanium as an anode. Titanium as an anode has excellent mechanical properties and corrosion resistance, has small density and high strength, and has good processability and is easy to form. However, when titanium is used as an anode in an electrolysis process, a passivation phenomenon is easily generated, and conductivity is seriously reduced after passivation. Titanium is a thermodynamically very active metal between iron and zinc in an electrochemical sequence, and has a standard equilibrium electrode potential of-1.63V, but a protective oxide film (passivation film) is very easily formed on the surface of titanium, so that the actual electrode potential is far biased to a positive value, and this passivation film having high resistance makes titanium have excellent corrosion properties. When titanium is used as an anode, a passive film on the surface of the titanium is continuously thickened due to the passivation effect of anode current, so that the cell voltage in the electrolysis process is sharply increased, and the power consumption is increased until the electrolysis process cannot be continued. The invention relates to a titanium anode passivation prevention method, which aims to avoid titanium anode passivation and improve current density during application so as to reduce power consumption and improve productivity.
Although the present invention has been described with respect to one or more embodiments thereof, it will be understood by those skilled in the art that the foregoing and various other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.
Claims (4)
1. An electrolytic tank for producing manganese dioxide comprises a tank body, wherein a liquid inlet and a waste liquid overflow port are formed in the tank body, and positive and negative electrodes are arranged in the tank body;
the lacing wire layer comprises a plurality of rows of lacing wires, and the upper row of lacing wires and the lower row of lacing wires are vertically staggered;
the positive electrode and the negative electrode are a plurality of anodes and cathodes which are arranged in a side-by-side staggered manner, the anodes and the cathodes extend out of the area where the heat preservation bubble layer is located and are connected with the busbar splitter plate, electrode contacts of the anodes and the cathodes are inverted V-shaped, triangular electrodes matched with the inverted V-shaped electrode contacts are arranged on the busbar splitter plate, and conductive adhesive is coated at the contact positions of the inverted V-shaped electrode contacts and the triangular electrodes on the busbar splitter plate;
the anode is a Ti glass line plate or a Ti-Mn alloy coating, and the cathode is a copper tube;
the steam heating pipe is a titanium heating pipe, the titanium heating pipe is distributed at the bottom of the tank body according to a zigzag shape, the positive electrode and the negative electrode are alternately distributed along the tank body at equal intervals, and the positive electrode and the negative electrode are positioned at the positive peak or the negative peak of the zigzag titanium heating pipe.
2. The electrolytic cell for producing manganese dioxide according to claim 1, wherein said corrosion resistant layer is non-woven glass reinforced plastic.
3. The electrolytic cell for producing manganese dioxide according to claim 1, wherein the inner wall of the granite in the area of the insulating bubble layer is ground to form a foam adsorption layer.
4. The electrolytic cell for producing manganese dioxide according to claim 1, wherein said waste liquid overflow port is connected to said lower tank through a waste liquid overflow pipe, said waste liquid overflow pipe is provided with a flow control valve, said liquid inlet is connected to said upper tank, said upper tank is located above said lower tank, and the bottom of said electrolytic cell is provided with a seabed plug and an insulating sleeper.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510354093.2A CN104928710B (en) | 2015-06-24 | 2015-06-24 | Electrolytic cell for producing manganese dioxide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510354093.2A CN104928710B (en) | 2015-06-24 | 2015-06-24 | Electrolytic cell for producing manganese dioxide |
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| CN104928710A CN104928710A (en) | 2015-09-23 |
| CN104928710B true CN104928710B (en) | 2017-06-20 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2630261Y (en) * | 2003-07-11 | 2004-08-04 | 黄石市汇波防腐技术有限公司 | Integral prestress glass-steel resin concrete electrolytic tank |
| CN201704422U (en) * | 2010-05-13 | 2011-01-12 | 新疆新鑫矿业股份有限公司阜康冶炼厂 | Conductive busbar of electrolysis bath and electrolysis bath employing same |
| CN102011146A (en) * | 2010-12-31 | 2011-04-13 | 重庆天泰铝业有限公司 | Technical method for electrolytic aluminium under 3.5 V cell voltage |
| CN102392273A (en) * | 2011-11-15 | 2012-03-28 | 天华化工机械及自动化研究设计院 | Resin concrete electrolytic tank and manufacturing method thereof |
| CN103436913A (en) * | 2013-08-13 | 2013-12-11 | 四川省尼科国润新材料有限公司 | Device for electrolytically depositing nickel or cobalt |
| CN103726067A (en) * | 2013-12-24 | 2014-04-16 | 柳州豪祥特科技有限公司 | Electrolysis system for producing electrolytic manganese dioxide |
-
2015
- 2015-06-24 CN CN201510354093.2A patent/CN104928710B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2630261Y (en) * | 2003-07-11 | 2004-08-04 | 黄石市汇波防腐技术有限公司 | Integral prestress glass-steel resin concrete electrolytic tank |
| CN201704422U (en) * | 2010-05-13 | 2011-01-12 | 新疆新鑫矿业股份有限公司阜康冶炼厂 | Conductive busbar of electrolysis bath and electrolysis bath employing same |
| CN102011146A (en) * | 2010-12-31 | 2011-04-13 | 重庆天泰铝业有限公司 | Technical method for electrolytic aluminium under 3.5 V cell voltage |
| CN102392273A (en) * | 2011-11-15 | 2012-03-28 | 天华化工机械及自动化研究设计院 | Resin concrete electrolytic tank and manufacturing method thereof |
| CN103436913A (en) * | 2013-08-13 | 2013-12-11 | 四川省尼科国润新材料有限公司 | Device for electrolytically depositing nickel or cobalt |
| CN103726067A (en) * | 2013-12-24 | 2014-04-16 | 柳州豪祥特科技有限公司 | Electrolysis system for producing electrolytic manganese dioxide |
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| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Qizhi Inventor after: Wan Weihua Inventor after: Lu Bin Inventor after: Wang Shaoli Inventor after: Shi Lei Inventor after: Wei Gebin Inventor before: Fu Kaili Inventor before: Fu Zhengmao |
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Effective date of registration: 20160115 Address after: 546138 guest mayor, 888 Mei Road, the Guangxi Zhuang Autonomous Region Applicant after: Guangxi Non-Ferrous Metals Group Huiyuan Manganese Industry Co., Ltd. Address before: 201101 Shanghai Minhang District City 1597 Longming Road No. 51, Room 401 Applicant before: SHANGHAI WEIZHI INTELLECTUAL PROPERTY SERVICE CO., LTD. |
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| CP01 | Change in the name or title of a patent holder |
Address after: 546138 888 Meibin Road, Mayor of Laibin, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Huiyuan Manganese Industry Co., Ltd. Address before: 546138 888 Meibin Road, Mayor of Laibin, Guangxi Zhuang Autonomous Region Patentee before: Guangxi Non-Ferrous Metals Group Huiyuan Manganese Industry Co., Ltd. |