Industrial production example of electrolytic manganese metal

2021-05-02

First, the production examples of the metal manganese industry in Guizhou Guizhou Yuping Tai Lung Manganese Industry Co., Ltd. is a specialty metal materials factory in Hunan, Guangdong, Hunan pregnant electrolytic manganese plants, Xiushan Chongqing researchers and other joint investments, "People's Republic of China Company Law" set up For joint-stock enterprises, private capital accounts for 80% of the shares.
The company is located in the Dalong Economic Development Zone of Guizhou Province at the junction of Guizhou Province and Hunan Province, and is located in Yuping County. It is only 1km away from Dalong Railway Station. The 320 National Highway from Shanghai to Ruili passes by the factory and the traffic is very convenient.
The company was established in June 2001 and completed the first phase of the project at the end of the year. The annual production capacity reached 12,000 tons. The second phase of the project was completed in May 2003. The annual production capacity reached 17,500 tons. The plant passed ISO-9001 certification in 2003.
The company's products mainly include high-purity selenium- free, high-purity low-silicon, high-purity selenium, low-carbon, low-hydrogen electrolytic manganese and other products. In 2002, it produced 11,000t of products, and it was produced in Japan, the United States and Europe and domestic trimanganese tetraoxide production plants. And the use of stainless steel plants is well reflected.
The process flow of electrolytic manganese production is shown in Figure 1.

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The raw material manganese ore Powder is produced in Xiushan County of Chongqing and Songtao County of Guizhou Province. The ore powder contains Mn19.0%~20.5%.
The main technical and economic indicators vary by product type and are listed below.
1 Technical and economic indicators of selenium-containing manganese metal products:
Manganese ore powder (containing Mn20%) 5.9~6.1t/t
Sulfuric acid (98%) 1.8~1.9t/t
Liquid ammonia 0.08~0.10t/t
DC power consumption 6100~6300kW•h/t
2Technology and economic technology of selenium-free metal manganese products:
Manganese ore powder (including Mn20%) 6.0~6.2t/t
Sulfuric acid (98%) 2.0~2.2t/t
Liquid ammonia (99.5%) 0.1~0.15t/t
DC power consumption 8300~8600kW•h/t
The analysis data of several electrolytic manganese metal products are as follows:
1 Low hydrogen electrolytic manganese metal sheet Ingredient Content /% Ingredient Content /%
Mn≥ 99.90 Si≤ 0.002
C≤ 0.01 Se≤ 0.0001
S ≤ 0.04 H ≤ 0.001
P≤ 0.001 N≤ 0.01
Fe ≤ 0.002 O ≤ 0.15
2 Selenium-free electrolytic manganese metal sheet Ingredients Content /% Ingredient Content /%
Mn≥ 99.96 Co≤ 0.0001
C≤ 0.007 Ni≤ 0.0001
S ≤ 0.03 Zn ≤ 0.005
P≤ 0.0002 Pb≤ 0.003
Fe≤ 0.0008 As≤ 0.0003
Si≤ 0.0015 Cr≤ 0.002
Se≤ 0.0005 H≤ 0.0013
Ca≤ 0.005 O≤ 0.07
Mg≤ 0.002 N≤ 0.005
Na≤ 0.0003 piece thickness 1.2mm
3 Selenium-containing electrolytic manganese metal sheet Ingredients content /%
Mn ≥ 99.80
C≤ 0.015
S ≤ 0.03
P ≤ 0.001
Fe≤ 0.005
Si≤ 0.002
Se ≤ 0.08
Slice thickness 1~0.8mm[next]
2. Guangxi Dameng Manganese Industry Co., Ltd.
Guangxi Dameng Manganese Industry Co., Ltd. (with Daxin Manganese Mine as the core enterprise) spent more than RMB 15 million. Since the completion of the 15000t/a manganese Sulfate plant and the 4000t/a electrolytic manganese plant in December 1999 and August 2000 respectively, Relying on its own economic strength and resource advantages, in October 2003, manganese sulfate was expanded to 45,000 t/a, electrolytic manganese was expanded to 15,000 t/a, and electrolytic manganese was completed in June 2004. The third phase of the project, by then, the company's electrolytic manganese production capacity will reach 35,000 t / a, 2005 production capacity will exceed 50,000 t / a, Guangxi, and even the country's manganese salt deep processing development rate is the fastest, the largest variety of products, the largest output Business.
The process of electrolytic manganese production is shown in Figure 2.

Guangxi Manganese Manganese Industry Co., Ltd. electrolytic manganese metal production process, using manganese carbonate plus acid (no warming) leaching, solution by oxidation neutralization and iron removal, sulfurization and removal of heavy metals into the electrolytic cell for electrolysis, electrolytic products passivated, baked After drying and peeling, the package becomes stable and becomes the product. The technical conditions of each process are as follows.
1 leaching, mineral acid ratio 1:0.48~0.52 (including anolyte acid); solid-liquid ratio 1:6.5~7.5; reaction temperature is 55~70 °C; reaction time 3.5~4h.
2 Electrolysis, bath concentration: Mn36~38g/L; (NH ₄ ) ₂ SO ₄ 100~120g/L; SeO ₂ 0.03~0.05g/L; bath temperature 38~42°C; tank voltage 4.5~5V; current Density 365~385A/m ² ; Catholyte composition: Mn ²⁺ 15~20g/L; the same name pole distance 75~80mm.
The plant has the following process characteristics:
1 The equipment is large, such as the leaching tank volume is 169m ³ and the filter press has a filtration area of ​​240m ² . The large-scale equipment can not only reduce the floor space, improve the work efficiency, but also help to improve the index, such as with the leaching tank. The volume is increased and the insulation performance is better. According to the production results, the two metal manganese plants of Damao Company adopt CN; mso-bidi-language: AR-SA">Ø 6m×6m and Ø 5m×5m leaching tanks. According to the production results, the former leaching temperature to the reaction end point is always maintained at a high temperature of 85~90°C, while the latter It only reaches 65~70°C, and it can be reduced to 55~57°C in winter. The Mn leaching rate is reduced from 85%~90% to 80%~85%.
② The Daxin manganese carbonate as the starting material, only grade manganese stable, liquid system in the process is also easier to control the indicators (via beneficiation plant respectively selected from the concentrate w (Mn) ≥20%), and do not add MnO ₂ has a certain advantage in reducing production cost because Fe is present in the form of high-priced iron. [next]
3. Hunan Xiangtan Xianghe Electrolytic Material Co., Ltd. (formerly Xiangtan Manganese Mine Electrochemical Production Line)
The company's electrolytic manganese metal was put into production in 1976, with an annual production capacity of 1000t. The main product specification is DJMn99.7. By 1992, it expanded to 6000t/a. At the end of 1999, DJMn99.9 high-purity and low-selenium products have been developed.
Since the production of electrolytic manganese metal by Xiangtan Xianghe Electrolytic Material Co., Ltd., the production process has been continuously improved, and the product quality and process parameters have been continuously improved and improved. The process flow chart of Xiangtan Xianghe Electrolytic Material Co., Ltd. is shown in Figure 3. See Table 1 for technical requirements for production materials. Production technical conditions and technical indicators are shown in Table 2.

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The product chemistry anxiety points (%) quality indicators are listed as follows:
Mn C S Se Si Fe P
High purity and low selenium type ≥99.9 0.012 0.026 0.0004 0.0026 0.0023 0.0009
Ordinary DJMn ≥99.8 0.013 0.021 0.053 0.0035 0.0028 0.0011
Ordinary DJMn ≥99.7 0.012 0.017 0.069 0.0032 0.0023 0.0010
Fourth, China Nuclear Industry Jianfeng Chemical Plant Electrolytic Manganese Plant
1 Factory Profile Jianfeng Chemical General Plant (August 16th Factory) is a large-scale industrial enterprise directly transferred by Chongqing Municipality in December 2002. It was built in 1966 in the beautiful Wujiang River in Fuling District, Chongqing. It now has nearly 2 billion yuan in fixed assets and 6,000 employees. The annual production and sales volume is more than 800 million yuan, forming a production, supply and marketing, science and industry. It is a large-scale comprehensive enterprise with import and export management rights. Its products span more than 20 kinds of eight categories including chemical, power supply, electrolysis, machinery, packaging and building materials.
Jianfeng Electrolytic Manganese Plant began to set up in 1984, designed and built by itself. Production began in 1988. Now it is expanding the electrolytic manganese metal plant with an annual output of 10,000 tons. After completion, it will form an electrolytic manganese metal production capacity of 15,000 tons per year. .
2 Production process and technical parameters A. Preparation of qualified liquid The sulfuric acid of manganese carbonate ore powder is added to the leaching tank, the leaching temperature is 80 ° C, after 1 h of reaction, heat preservation for 2 h, then manganese dioxide ore powder is added to oxidize the ferrous iron to three The valence iron is further neutralized by adding liquid ammonia to adjust the pH to 6.5, and the ferric iron is hydrolyzed to form iron hydroxide precipitate, and the iron is removed.
After one filtration, the solid-liquid separated liquid is removed by adding sodium fumarate (SDD) to remove the heavy metal in the liquid, and then the electrolytic additive is added. After the secondary filtration, the liquid-solid separation liquid is allowed to stand for three times by standing and adding the purifying agent. After filtration, the electrolysis process is sent as a replenishing solution. [next]
B. The qualified liquid in the electrolysis process is sent to the high level tank through the transfer pump, and flows through the high level tank to the electrolysis cell for electrolysis. Under the action of the current, the electrolyte electrolyzes the manganese on the cathode plate. After 24 hours of electrolysis, the metal manganese on the cathode plate is thick. Up to 1.9~2.5mm, the cathode plate is taken out and then passivated. After being rinsed with hot water, it is dried in an oven and then peeled off.
3 main consumption indicators manganese carbonate ore powder (grade 22%) 5.8t / t
Sulfuric acid (98%) 2.0t/t
Liquid ammonia (99.5%) 0.15t/t
Manganese dioxide (MnO ₂ 51%) 0.3t/t
Power consumption 6600kWh/t
Water consumption 210t/t
4 main process parameters control crude liquid:
Mn ²⁺ concentration 40g/L
(NH ₄ ) ₂ SO ₄ 95~110g/L
pH 6.5
Electrolyzer bath:
Mn ²⁺ 15~16g/L
(NH ₄ ) ₂ SO ₄ 91~110g/L
pH 6.8
Electrolytic bath temperature 42~48°C
Cathode current density 370A/m ²
Anode current density 700A/m ²
5 product chemical composition (%)
Mn C S P Fe Se Si
99.88 0.016 0.02 0.003 0.005 0.06 0.07
6 production process (see Figure 4)