Method for recovering highly pure manganese dioxide from waste manganese dry batteries, and use of highly pure manganese dioxide

A manganese dioxide and manganese dry battery technology, applied in chemical instruments and methods, manganese oxide/manganese hydroxide, oxidized water/sewage treatment, etc. The problem of high temperature can achieve the effect of low roasting temperature, fast degradation speed, and improved product purity and yield.

Active Publication Date: 2016-12-21
CHINA UNIV OF PETROLEUM (EAST CHINA)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] The purpose of the present invention is to provide a strong redox process, direct low-temperature treatment to remove impurities in waste dry batteries and recover high-purity manganese dioxide technology, to overcome the large power consumption of hydrometallurgy, difficult process control and high temperature of pyrometallurgy. Product quality is difficult to stabilize and other problems, and this high-purity manganese dioxide is used as a catalyst to degrade phenol wastewater discharged from petrochemical industry

Method used

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  • Method for recovering highly pure manganese dioxide from waste manganese dry batteries, and use of highly pure manganese dioxide
  • Method for recovering highly pure manganese dioxide from waste manganese dry batteries, and use of highly pure manganese dioxide
  • Method for recovering highly pure manganese dioxide from waste manganese dry batteries, and use of highly pure manganese dioxide

Examples

Experimental program
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Effect test

Embodiment 1

[0030] Take "Huatai brand" zinc-manganese waste dry batteries, crush them with a bite mill, and sieve them through 5-mesh and 50-mesh vibrating sieves to remove the plastic skin, zinc skin, carbon rods, plastic caps, sealing rings, copper caps, etc. Wash the remaining black powder twice with water, twice with absolute ethanol, and filter; then add 50 mL of 0.5mol / L sodium hydroxide, stir at room temperature for 30 minutes, raise the temperature to 70°C, stir and rinse for 10 minutes, remove grease and wax, and Filter out the filter residue; add 50 mL of 0.5 mol / L sulfuric acid, rinse with water for 30 min at room temperature, and wash with water until the washing liquid is neutral, then filter out the sample. Take a certain amount of black powder and mix it with the oxidizing additive KMnO 4 , at 500°C, after constant temperature airtight roasting for 1.0h, take out the black manganese dioxide powder, wash it with water until the conductivity remains unchanged, and measure the...

Embodiment 2

[0032] Get the "Nanfu brand" alkaline manganese waste dry battery, pulverize it with a bite mill, carry out the sieving and water washing steps of Example 1 respectively, wash the black powder obtained twice with 30vol% ethanol aqueous solution, and filter; then go through step 1 Alkali washing, acid washing steps, filter out black samples. Take a certain amount of black powder and mix it with oxidizing additive KClO 4 , at 320°C, after constant temperature airtight roasting for 1.0h, take out the black manganese dioxide powder, wash it with water until the conductivity remains unchanged, and measure the purity of manganese dioxide by sodium oxalate-potassium permanganate back titration method to reach 94.21wt%, which is The recovery rate reached 78.61%. Use an appropriate amount of this manganese dioxide to degrade 200 mg L at room temperature -1 After 150mL of phenol wastewater was degraded for 2.0h, the chemical oxygen demand (COD) of the wastewater was determined to be 4...

Embodiment 3

[0034] Take "Philip brand" alkaline waste dry batteries, crush them with a bite mill, and filter out the black samples through the steps of screening, water washing, alcohol washing, alkali washing, and pickling in Example 2 respectively. Take a certain amount of black powder and mix it with the oxidizing additive KMnO 4 , at 500°C, after constant temperature airtight roasting for 1.0h, take out the black manganese dioxide powder, wash with water until the conductivity remains unchanged, and measure the purity of manganese dioxide by sodium oxalate-potassium permanganate back titration to reach 92.35wt%. The recovery rate reached 55.23%. Appropriate amount of this manganese dioxide is used to degrade 100m g L at room temperature -1 After 200mL of phenol wastewater was degraded for 1.0h, the chemical oxygen demand (COD) of the wastewater was determined to be 236.8mg·L -1 down to 33.5mg·L -1 , reaching the national discharge standard for industrial wastewater.

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Abstract

The invention discloses a method for recovering highly pure manganese dioxide from waste manganese dry batteries, and a catalysis application of the highly pure manganese dioxide. The method concretely comprises the following steps: carrying out fragmenting sorting, vibration screening, water washing desalination, alcohol washing degreasing, alkali washing, pickling and neutral water washing on waste dry batteries, filtering out manganese dioxide-containing black powder, mixing the manganese dioxide powder with a strong oxidation additive or strong oxidant solution under closed conditions through using the catalysis activity of manganese dioxide, and carrying out low temperature oxygen-rich roasting to remove carbon and acetylene black in order to prepare the highly pure manganese dioxide which can be applied to catalytic degradation of petroleum chemical engineering phenol wastewater. The idea of treating wastes by using wastes is used to reasonably utilize solid wastes and separate and purify the active catalyst used for treating industrial wastewater. The method has the advantages of low energy consumption, greenness and environmental protection, simple process flow, realization of avoiding of pyrolysis of manganese dioxide through low temperature oxygen-rich roasting and conversion of low-valence alkali manganese salt, high purity and large output of the above product, high recovery rate, rapid catalytic degradation of the petroleum chemical engineering phenol wastewater, and high catalytic degradation efficiency, and allows the chemical oxygen demand (COD) of treated industrial wastewater to reach national industrial wastewater discharge standards.

Description

technical field [0001] The invention belongs to the field of high-purity manganese dioxide preparation, specifically a technology for directly recovering high-purity manganese dioxide from waste dry batteries (zinc-manganese batteries and alkaline manganese batteries). The high-purity manganese dioxide recovered by the technology can be As a catalyst to degrade phenol wastewater in petrochemical industry. technical background [0002] my country is a big country in the production and consumption of dry batteries. The annual output of disposable dry batteries has exceeded 40 billion, and the per capita annual consumption of dry batteries is as high as dozens of knots. It is bound to produce a large number of waste dry batteries. Chemical substances harmful to the human body will pollute groundwater and soil, causing difficulties in environmental governance; at the same time, waste disposal is also an important waste of resources. After dry batteries are used, except that the n...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01G45/02C02F1/72B01J23/34C02F101/34
CPCC01G45/02C02F1/725B01J23/34C01P2006/80C02F2101/345
Inventor 陈金庆吕宏凌牛晓辉韩墨
Owner CHINA UNIV OF PETROLEUM (EAST CHINA)
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