(1) Dressing
Cobalt is associated with iron , copper and nickel ore. There are mainly four kinds of cobalt ore in China: copper nickel cobalt ore, copper cobalt ore, iron cobalt ore and cobalt ore. Different beneficiation methods are required for different main minerals.
Copper nickel cobalt ore
The cobalt in the ore is similar to copper and nickel in the same mineral. In the process of beneficiation, nickel and cobalt cannot be separated. Therefore, it is not necessary to design a separate process for selecting cobalt-containing minerals. The selected concentrate is cobalt-containing. Copper-nickel concentrate and cobalt-containing nickel-containing sulfur concentrate, which is recovered in smelting anode electrolytic sludge and slag.
2. Copper-cobalt ore
This ore production mainly Shanxi Zhongtiaoshan non-ferrous metals company Grate ditch, Hubei Daye Nonferrous company recorded a mountain of copper and Huili Lala plants and other mineral deposits. The main cobalt-containing minerals are sulfide minerals such as chalcopyrite, pyrite and pyrrhotite. The chalcopyrite can be separated from the latter by flotation to produce copper concentrate and cobalt-sulfur concentrate. A small amount of cobalt can still be recovered from the anodic electrolytic sludge of the smelting copper concentrate.
3. Iron cobalt ore
The minerals produced in this area include Zibo North Jinzhao North, Shandong Jinling Tieshan, Shandong Laiwu Iron Mine and Hubei Huangshi Tieshan. The main cobalt-containing minerals are pyrite minerals such as pyrite, pyrrhotite and a small amount of chalcopyrite. The flotation method can be used to separate the sulfide and magnetite, and then a small amount of chalcopyrite and pyrite and pyrrhotite are separated by flotation, and magnetite is separated by magnetic separation to produce copper concentrate. , cobalt-sulfur concentrate and iron concentrate. Sulfur is a harmful component of iron making. Such ore must be selected before it enters the furnace. Therefore, mines with selected plants generally have a flotation process. Therefore, such mines can recover cobalt and sulfur concentrates.
4. Cobalt ore
Hunan Changsha Xialuping Cobalt Mine is currently mined by township enterprises and recycled by Hengyang Smelter. Hainan Andingju Dingcobalt Mine has a high grade of ore and a cobalt grade of 1.632%. Currently, a cobalt company is designing and preparing for mining. Its cobalt-containing minerals are mainly hydroxides and aqueous oxide hydroxides. The ore dressing test process is shown in Figure 3.11.4. According to the results of the relevant ore dressing experiments, it can be produced together with the Hailu Shilu copper-cobalt mine and can be exploited in the open pit.
(2) Processing technology
The technical requirements for processing and producing metallic cobalt and high-purity cobalt oxide are high, the smelting process is complicated, and the problems of high energy consumption and pollution are generally not suitable for folk smelting. According to different cobalt refining raw materials, there are mainly the following smelting and recycling processes.
1. Cobalt ore smelting process
In the early days of the founding of the People's Republic, cobalt ore was mainly used as a raw material for the preparation of cobalt oxide. The process basically reduces the smelting of cobaltite ore into a cobalt iron by a blast furnace or an electric arc furnace. After annealing or roasting, the cobalt-containing solution is obtained by acid leaching, and then purified to precipitate cobalt potassium nitrite, and then baked and then The industrial cobalt oxide powder is obtained by pulverization. Manufacturers such as Chaozhou Smelter and Zhangzhou Cobalt Smelter have used this process to recover cobalt. No manufacturer has used this raw material to produce cobalt products.
2. Smelting process of cobalt-sulfur concentrate
Domestically, cobalt-containing pyrite and pyrrhotite concentrates are known as cobalt-sulfur concentrates and are one of the main raw materials for cobalt refining in China. Nanjing Steel, Huludao Zinc, Hubei, Shandong actinic phosphorus fertilizer plant and plant Zibo Cobalt four manufacturers use this material. The product of Huludao Zinc Plant is No. 2 electro-cobalt, which adopts the method of sulphating roasting → leaching → fatty acid de-ironing copper → sinking cobalt → reducing casting anode → anolyte purification → diaphragm electrolysis, which has been discontinued due to high production cost. Nanjing Steel Plant used oxidizing roasting-sintering slag in medium temperature chlorination roasting process, and Hubei Guanghua Phosphate Fertilizer Plant used oxidizing roasting-sintering sulphate roasting process. However, since cobalt-sulfur concentrates are too low in cobalt, generally less than 0.3%, and the process of recovering cobalt is complicated and generally unprofitable, these plants have stopped production after a period of production. Shandong Zibo Cobalt Plant uses cobalt-sulfur concentrate and cobalt-containing raw materials to produce cobalt sulfide, cobalt oxide, cobalt chloride, cobalt sulfate and other products.
3. Arsenic and cobalt ore smelting process
Cangzhou Cobalt Smelter is the only manufacturer in China that uses this raw material. The raw materials are imported from Morocco. The plant uses electric furnace melting → arsenic roasting → two-stage leaching to remove iron and arsenic → Na2S2O3 de-coppering → sinking cobalt → reduction casting anode → purification → diaphragm Electrolytic production of cobalt oxide and electro-cobalt.
4. Smelting process of cobalt extraction in by-products of smelting
The cobalt slag produced by the purification of nickel electrolyte is the main raw material. The production process of Gansu Jinchuan Nonferrous Metals Co., Ltd. is cobalt slag → leaching and iron removal → secondary precipitation of cobalt → reduction of cast anode → anolyte purification → diaphragm electrolysis. With the help of many production, design and scientific research units, the company has determined a new process for cobalt extraction from converter slag based on a large number of experimental studies. The process uses cobalt desulfurization to obtain cobalt sulfur, converter to blow cobalt-rich sulfur, and pressurized oxidation and leaching technology. The leaching rate of nickel, cobalt and copper is high, the reaction speed is fast, the sedimentation performance of the leaching slag is good, and the recovery rate of cobalt smelting is about 50%. Jinchuan Nonferrous Metals Co., Ltd. uses sulfuric acid dissolution method to recover cobalt from cobalt electrolysis system to purify cobalt slag. The recovery rate of cobalt is over 85%. At the same time, sulfuric acid dissolves cobalt slag and produces pure cobalt oxide powder.
5. Process for extracting cobalt from cobalt-containing scrap
The process of secondary cobalt extraction is relatively simple, the raw materials are cheap, and it is not necessary to produce metallic cobalt. Therefore, some domestic manufacturers have begun to use cobalt-containing waste to produce cobalt products. Zhenjiang Smelter uses various cobalt-containing industrial wastes and cobalt-sulfur concentrates to produce various types of cobalt salts. The process is cobalt raw materials→purification and purification→synthesis→all kinds of cobalt salts. Jiangsu Suining Chemical Factory uses the waste materials such as magnetic steel slag and grinding wheel to produce cobalt salt. The process is cobalt raw material → acid solution liquid → iron removal → extraction → crystallization. In addition, the Cangzhou Cobalt Smelter handled the waste catalyst, the Huludao Zinc Plant processed the magnetic steel slag, and the Shanghai and Shenyang smelters treated the superalloy.
At present, domestic production of high-purity electrolytic cobalt, cobalt oxide powder and cobalt salt can be produced by various raw materials produced in the mine. The production and processing technology has also been greatly developed. Solvent extraction technology is widely used in wet-process cobalt smelting.
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