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Production method for simultaneously preparing metal manganese and manganese dioxide in ion exchange membrane electrolytic method

An ion exchange membrane and manganese dioxide technology, applied in the fields of electroplating and metal hydrometallurgy, can solve the problems of high energy consumption, acid mist environmental pollution, low current efficiency, etc., achieve high current efficiency, less environmental pollution, and realize resource The effect of recycling

Pending Publication Date: 2019-01-01
LANZHOU JIAOTONG UNIV
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Problems solved by technology

[0004] The purpose of the present invention is to solve the problems of low current efficiency, high energy consumption, and serious environmental pollution of acid mist in conventional electrolytic production of manganese and manganese dioxide, and to provide a method for simultaneously electrodepositing metal manganese and manganese dioxide in a double-membrane three-chamber electrolytic cell. The production method can not only overcome the existing defects, but also produce sulfuric acid by-products, bringing additional economic benefits to the enterprise

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  • Production method for simultaneously preparing metal manganese and manganese dioxide in ion exchange membrane electrolytic method

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Embodiment 1

[0036] The composition of catholyte is 1.5mol / L manganese sulfate, 100g / L ammonium acetate, pH=6.8, 0.008g / L gelatin; the composition of anolyte is 1mol / L manganese sulfate, 2.2mol / L sulfuric acid, 0.6mg / L fatty acid Methyl ester ethoxylate sulfonate; initial concentration of dilute sulfuric acid in the middle compartment is 1%. The anode is made of titanium-based titanium manganese oxide electrode, the cathode is made of stainless steel plate; the cation exchange membrane is made of ASTOM-CIMS, the anion exchange membrane is made of ASTOM-ACM ion exchange membrane; chamber, middle compartment; through direct current electrolysis, the current density at the anode is 900A / m 2 , the cathode current density is 300A / m 2 , under the condition of electrolyte temperature of 50℃, the obtained manganese deposition layer is bright and dense, and the crystal form of manganese dioxide particles is better; the cathode current efficiency is 78.8%, the acid recovery rate is 51.8%, and the e...

Embodiment 2

[0038]The composition of catholyte is 1.2mol / L manganese sulfate, 90g / L ammonium acetate, pH=6.8, 0.006g / L thiourea; the composition of anolyte is 1mol / L manganese sulfate, 2.1mol / L sulfuric acid, 0.5mg / L Sodium dodecylbenzenesulfonate; the initial concentration of dilute sulfuric acid in the middle compartment is 1%. The anode is made of titanium-based titanium manganese oxide electrode, the cathode is made of stainless steel plate; the cation exchange membrane is made of ASTOM-CIMS, the anion exchange membrane is made of ASTOM-ACM ion exchange membrane; Chamber, middle compartment; through direct current electrolysis, the current density at the anode is 800A / m 2 , the cathode current density is 320A / m 2 , under the condition of electrolyte temperature of 50℃, the obtained manganese deposition layer is bright and dense, and the crystal form of manganese dioxide particles is better; the cathode current efficiency is 75.8%, the acid recovery rate is 50.1%, and the energy consu...

Embodiment 3

[0040] The composition of catholyte is 1mol / L manganese sulfate, 80g / L ammonium acetate, pH=6.8, 0.001g / L selenium dioxide; the composition of anolyte is 1.2mol / L manganese sulfate, 2.1mol / L sulfuric acid, 0.5mg / L L sodium dodecylbenzenesulfonate; the initial concentration of dilute sulfuric acid in the middle compartment is 0.8%. Graphite is used for the anode, and titanium plate is used for the cathode; ASTOM-CIMS is used for the cation exchange membrane, and ASTOM-ACM ion exchange membrane is used for the anion exchange membrane; catholyte, anolyte, and dilute sulfuric acid solution are injected into the cathode chamber, anode chamber, and middle compartment respectively; Through direct current electrolysis, the current density at the anode is 850A / m 2 , the cathode current density is 300A / m 2 , under the condition of electrolyte temperature of 60℃, the obtained manganese deposition layer is bright and dense, and the crystal form of manganese dioxide particles is better; t...

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Abstract

The invention discloses a production method for simultaneously preparing metal manganese and manganese dioxide in an ion exchange membrane electrolytic method. An electrolytic bath is successively divided into a cathode chamber, a septation chamber and an anode chamber by utilizing an anion exchange membrane and a cation exchange membrane, a cathode and an anode as well as a cathode solution and an anode solution are respectively correspondingly arranged in the cathode chamber and the anode chamber, the cathode solution is a manganese sulfate solution comprising additives and a buffering agent, the anode solution is an acidic manganese sulfate solution comprising a surfactant, and the septation chamber is filled with a thin sulfuric acid solution; and when the constant-current electrolysisis performed, the manganese ions reduce metal manganese element on the cathode, the manganese dioxide electric deposition reaction occurs on the cathode, and 1mol / L to 2mol / L of sulfuric acid solution can be obtained in the septation chamber by virtue of electrochemical regeneration manner. By adopting the production method, the electric deposition of manganese on the cathode and the electrolyticgeneration of manganese dioxide on the anode can be simultaneously performed, the current efficiency is high, the environmental pollution is light, and a sulfuric acid byproduct can be produced and can be recycled to the anode solution, so that the reutilization of the resource can be realized; and a metal manganese product and manganese dioxide product are good in quality and high in purity.

Description

technical field [0001] The invention provides a production method for simultaneously preparing metal manganese and manganese dioxide by an ion-exchange membrane electrolysis method, which is a new process technology that organically combines electrochemistry and membrane separation, and belongs to the fields of metal hydrometallurgy and electroplating. Background technique [0002] Electrolytic production of manganese dioxide is carried out at high temperature and high concentration of sulfuric acid. The voltage applied to the cathode is consumed for hydrogen evolution, resulting in severe acid mist, and the operating conditions are relatively harsh. In the electrolytic manganese industry, the voltage applied to the anode is consumed for oxygen evolution and the generation of manganese dioxide anode sludge, which has problems such as low current efficiency, high energy consumption, and serious pollution. The manganese dioxide sludge produced by the anode will consume the man...

Claims

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Application Information

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IPC IPC(8): C25B1/21C25C1/10C25B1/22C25B13/08C25C7/04
CPCC25B1/21C25B1/22C25B13/08C25C1/10C25C7/04
Inventor 周键王三反孙三祥
Owner LANZHOU JIAOTONG UNIV
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