At present, the cobalt resources identified by the world continent are about 11 million tons. Global cobalt resources are unevenly distributed. Cobalt resources are mainly distributed in a few countries in the world. Among them, the Democratic Republic of Congo (Zaire) has a cobalt reserve of 42.2%, ranking first in the world, followed by Cuba, Australia, Zambia, New Caly. Tonia, Russia and Canada, these countries account for about 98% of the world's total cobalt reserves. China is a cobalt-poor country, and about half of domestic industrial cobalt is imported every year. World continent cobalt limited resources, huge ocean seabed iron manganese nodules (shell) storage, with high cobalt, cobalt resource potential is great development prospects.
Most of the world's cobalt resources are distributed in cobalt-bearing laterite-type nickel deposits, which are mostly produced in sedimentary copper sulfide and cobalt deposits and magma-type cobalt-copper sulfide nickel deposits. However, the current world cobalt production mainly comes from copper sulfide cobalt deposits and copper sulfide nickel deposits. China's cobalt resources are mainly produced in magmatic copper sulfide nickel deposits. Cobalt deposits in the world of industrial interest are: copper sulfide deposits of cobalt, copper-nickel sulfide deposits containing cobalt, cobalt lateritic nickel deposit, multi-metal vein deposits containing cobalt, cobalt-containing iron skarn deposits, including cobalt pyrite lead zinc deposits and cobalt deposits. Cobalt is a multi-affinity element and can be broadly similar to the elemental chemistry similar to the crystal chemistry of iron, nickel, manganese and magnesium . Therefore, cobalt can form not only an independent cobalt mineral with sulfur or sulfur-like plasma, but also can be similar to iron, nickel, manganese, magnesium and other minerals, and enter the mineral lattice of iron, nickel, manganese and magnesium to form cobalt-containing. Sulfide, sulfide-like or silicate. To date, more than 100 kinds of cobalt and cobalt-containing minerals have been found in the earth's crust, and dozens of them have industrial value. The cobalt that can be used as a resource is mainly cobalt and an independent cobalt mineral which are sulfide and sulfide-like. Cobalt is complex in the earth's crust and can form a variety of cobalt-containing minerals and rock-forming minerals. Therefore, the determination of the occurrence of cobalt is of great significance for cobalt beneficiation and geochemical prospecting and resource evaluation.
In 1993, the Fifth Geological Survey of the Jilin Provincial Geological Survey found a large area of ​​cobalt mineralization in the Daheng Road area of ​​Baishan City, Jilin Province, with a mineralized area of ​​about 28 km. The average grade of oxidized ore cobalt in the mineralized zone is 0.043%, the primary ore is 0.053%, and the cobalt metal reserves are about 30,000 tons, belonging to the low-grade large cobalt deposit. It has been determined that cobalt in the ore is heterogeneous and polymorphic and belongs to complex cobalt ore. The main cobalt-containing mineral phases are iron-containing sulfides, oxides, carbonates, sulfates, clay minerals and silicates. Among them, the cobalt mineral adsorption state (silicate inlay state) cobalt accounts for about one-third of the total cobalt content of the ore. This is a special state of cobalt that cannot be ignored. The cobalt in this state is usually beneficiated. The method is difficult to select, which is the main reason for the low cobalt recovery rate of the cobalt deposit.
Since 1993, some research institutes have conducted many ore dressing experiments, but the problem of low cobalt recovery rate has not been solved. How to improve the recovery rate of cobalt has become the primary problem of whether the cobalt deposit can be exploited. At present, the world's ore dressing problems for sulfides and sulfide-like cobalt in primary ore have been solved (both in flotation), while cobalt is extracted from other chemical forms of cobalt, especially in low-grade complex oxidized ores. Many unresolved issues. In this study, on the basis of ascertaining the state of cobalt in the cobalt deposit, the oxidized ore is used as the beneficiation object, and the new process of cobalt extraction process is established with the aim of increasing the recovery rate of cobalt. The technical route of the beneficiation is determined as wet extraction. Tests were carried out on three leaching systems of sulfuric acid, hydrochloric acid-sodium chloride and citric acid-ammonium hydrogen fluoride. Under the fast, economic and effective guiding principle, the citric acid-ammonium hydrogen fluoride leaching system was finally determined as the best leaching scheme. The optimum leaching conditions were: citric acid concentration of 12.5 g/L, ammonium hydrogen fluoride of 37.5 g/L, solid-liquid ratio of 1:10, leaching temperature of normal temperature, leaching time of stirring for 4 h, and standing for 14 h. The cobalt recovery rate is 90%.
In order to make maximum use of mineral resources and reduce the cost of mineral processing, the extraction and separation process of cobalt and associated metals (Ni, Cu and Fe) in the leachate was studied. The methods and processes are: (1) oil with 33% P〓- coal (70% of the amide) iron extraction, the organic phase was washed with 6mol / LHCl stripping; (2) the aqueous raffinate phase with 20% Lix〓- The kerosene extracted copper, the organic phase was stripped with 1.80mol/L H〓SO〓; (3) the raffinate aqueous phase was extracted with 20% N〓+50% octanol-kerosene, and the organic phase was back extracted with 0.5mol/L HCl. (4) The raffinate aqueous phase was extracted with 50% n-octanoic acid-kerosene (saponification degree: 15%), and the organic phase was back extracted with 1.8 mol/L H〓SO〓. The obtained products were FeCl〓6H〓O, CuSO〓·5H〓O, CoCl〓·6H〓O and NiSO〓·6H〓O, respectively, and their purity reached the reagent grade standard.
The research has achieved the following research results:
1. The cobalt in the ore of the Dahenglu cobalt deposit is heterogeneous polymorphism. The main cobalt-containing mineral phase contains iron-containing sulfides, oxides, carbonates, sulfates, clay minerals and silicates, among which clay minerals The cobalt in the adsorption state (silicate inlaid state) accounts for about one-third of the total cobalt content of the ore. The cobalt in this state is difficult to select by the usual beneficiation method, which is caused by the low cobalt recovery rate of the cobalt deposit. One of the main reasons.
A new process for the extraction of cobalt by wet method was established. It was determined that the citric acid-ammonium hydrogen fluoride leaching system was the best solution for the extraction of cobalt from oxidized ore. The cobalt recovery rate was 90%.
3. Established a comprehensive recycling process for cobalt and associated metals (Ni, Cu and Fe). It provides a new method and approach for the extraction, development and utilization of low-grade complex cobalt oxide ore cobalt.
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