GB/T 33071-2026Technical specification for the treatment and disposal of cobalt-bearing waste (English PDF)

1.2 MPa~

5.1.4.3 Distillation separation. Vacuum distillation of zinc, heating to 950 °C~970 °C, holding for 10 h~20 h, pressure -

0.05 MPa~-

0.15 MPa. Zinc vapor is condensed and recovered, leaving behind spongy cobalt and carbide clumps.

5.1.4.4 The agglomerates are ball-milled until the particle size is less than

0.15 mm, and then recycled after adjusting the composition.

1.8 MPa~

c) Kettle temperature. 180 °C~200 °C.

5.1.1 Calcination

5.1.1.1 When cobalt-containing waste contains organic matter or insoluble cobalt compounds, roasting treatment should be adopted.

5.1.1.2 High temperature is used to thermally remove organic matter and oxidize metals in cobalt-containing waste.

5.1.1.3 The main equipment should include a roasting furnace or a rotary kiln.

5.1.1.4 The cobalt-containing waste is fed into a roasting device and roasted in stages, including heating to 600 °C~700 °C, holding at that temperature for 1 h~3 h, and then cooling. After the waste has been processed and deemed acceptable, it is collected and ready for use.

5.1.1.5 Control conditions.

a) Firing temperature. 600 °C~700 °C;

b) Calcination time. 1 h to 3 h.

5.1.2 Crushing

5.1.2.1 Cobalt-containing waste containing large particles or lumps shall be crushed and ground, and the particle size after crushing and grinding shall be less than 1 mm.

5.1.2.2 The main equipment should include air jet crushers, ball mills, etc.

5.1.3 Magnetic Separation

5.1.3.1 Separate materials by utilizing their magnetic differences under magnetic force.

5.1.3.2 The main equipment should be a magnetic separator.

5.1.3.3 Cobalt-containing waste containing magnetic materials is fed into a magnetic separation device, and the separated cobalt-containing waste is collected for later use.

5.1.3.4 The magnetic field strength should be

0.1 T to

0.25 T.

5.1.4 Zinc molten

5.1.4.1 Zinc and cobalt form a low-melting-point alloy that disrupts the structure. After zinc is separated by distillation, a carbide-cobalt sponge is obtained, which is then regenerated and reused through ball milling.

5.2.1 Chemical dissolution

5.2.1.1 The metals in the waste are selectively or completely dissolved into the solution using a leaching solvent.

5.2.1.2 The main equipment should be reaction equipment lined with an anti-corrosion layer and equipped with a stirrer.

5.2.1.3 Industrial sulfuric acid or industrial hydrochloric acid are suitable leaching agents; industrial sodium persulfate, industrial hydrogen peroxide, or industrial sodium chlorate are suitable oxidizing agents. Oxygen, compressed air, etc.; industrial sulfur dioxide, industrial sodium metabisulfite, industrial ferrous sulfate, etc. are suitable reducing agents.

5.2.1.4 The treated cobalt-containing waste is placed in the selected reaction equipment, and a leaching agent is added under stirring to react with the waste, resulting in metal dissolution. For cobalt-containing leachates, oxidants or reducing agents can be added during the chemical dissolution process to promote dissolution, depending on the characteristics of the waste.

5.2.1.5 The control conditions are as follows:

a) Sulfuric acid mass fraction of the leaching agent. not greater than 98%;

b) Mass fraction of hydrochloric acid in the leaching agent. not greater than 37%;

c) Temperature. 60 °C~100 °C.

5.2.2 Pressurized and oxygenated leaching

5.2.2.1 The pretreated cobalt-containing waste is fed into an oxygen pressure vessel, where it is pressurized, oxygenated, and heated to achieve the leaching of the target metal elements.

5.2.2.2 The main equipment should be tanks, kettles, etc. lined with anti-corrosion coating, and equipped with a stirrer.

5.2.2.3 Industrial sulfuric acid or similar substances should be used as leaching agents; oxygen or similar substances should be used as oxidizing agents.

5.2.2.4 After the treated cobalt-containing waste is pre-treated in a pre-impregnation tank, it enters an oxygen pressure vessel. Oxygen is introduced into the oxygen pressure vessel to control the pressure. After the material reacts in the oxygen pressure vessel, it is sent to the flash tank for cooling, and then sent to the oxygen pressure thickener for solid-liquid separation.

5.2.2.5 The control conditions are as follows:

a) The mass fraction of sulfuric acid in the leaching agent is no more than 98%;

b) Pressure of the oxygen autoclave.

5.2.3 Electrochemical Dissolution

5.2.3.1 Using cobalt-containing alloy waste as the anode, the metal at the anode loses electrons and enters the solution under the action of a DC power supply.

5.2.3.2 The main equipment should be an electrolytic cell.

5.2.3.3 The treated cobalt-containing waste is placed in an electrolytic cell as the anode. Under the action of direct current, the metal in the anode waste is selectively dissolved. The solution is dissolved or completely dissolved to obtain a cobalt-containing leachate.

5.2.3.4 The control conditions are as follows:

a) Current density. 150 A/m2~400 A/m2;

b) Electrolyte temperature. 40 °C~60 °C;

c) Current efficiency. not less than 80%, calculated according to Appendix A;

0.5 mol/L~2 mol/L.

5.3.1 Removal of iron and aluminum

5.3.1.1 Fe2+ is oxidized by an oxidant, and then the pH difference between Fe3+, Al3+ and cobalt ions is used to achieve separation.

5.3.1.2 The main equipment should be tanks, vessels, and other reaction equipment lined with anti-corrosion coatings, and should be equipped with agitators, heaters, and pipeline mixers.

5.3.1.3 An oxidizing agent should be added to the leachate, and the reaction should be thoroughly stirred to obtain an oxidized solution. The pH should then be adjusted to allow iron, aluminum, and other substances to precipitate and separate. After sedimentation, the iron-removed liquid is obtained. Suitable oxidants include industrial hydrogen peroxide, industrial sodium persulfate, industrial sodium chlorate, and compressed air.

5.3.1.4 The control conditions are as follows:

a) The amount of oxidant added should be

1.2 to 2 times the theoretical amount used for iron removal;

b) Reaction time. 1 h ~ 3 h;

c) Reaction temperature. 60 °C~90 °C;

d) The pH during the oxidation process should be 0.5~1.5, and the mass concentration of ferrous ions in the solution after oxidation should be less than

0.1 g/L;

e) The final pH of the solution after iron removal should be 4.5~5.0, and the mass concentration of ferric ions in the solution after iron removal should be less than

0.05 g/L.

5.3.2 Removal of calcium and magnesium

5.3.2.1 Sodium hydroxide solution should be slowly added after the slurry is heated, while maintaining stirring to ensure the pH and temperature of the slurry. Sodium fluoride or fluorine can then be added. Ammonium chloride is used to remove calcium and magnesium through filtration.

5.3.2.2 The control conditions are as follows:

a) Reaction pH. 5~5.5;

b) Reaction time.

c) Reaction temperature. 90 °C~100 °C;

d) After removing calcium and magnesium precipitates with fluoride, the calcium and magnesium content in the solution should be less than

0.05 g/L.

5.3.3 Removal of heavy metals and samarium

5.3.3.1 When adding sodium sulfide solution to the slurry, the pH and reaction temperature should be controlled to precipitate heavy metals and samarium. After filtration and washing, the filter residue can be piled up. We recycle zinc, copper, lead, cadmium, chromium, and samarium, among other minerals.

5.3.3.2 The control conditions are as follows:

a) Reaction pH. 3~6;

b) Reaction time. 1 h ~ 2 h;

c) Reaction temperature. 40 °C~70 °C.

5.3.4 Extraction

5.3.4.1 Utilizing the selectivity of the extractant for metals to achieve metal separation, purification and enrichment.

5.3.4.2 Main equipment. It should include extraction tanks, extraction vessels and other equipment, and be equipped with a stirrer. The corresponding electrical equipment should be explosion-proof.

5.3.4.3 After impurity removal, the solution is mixed with the extractant, and after clarification, the loaded organic phase and aqueous phase are separated to achieve the separation of cobalt from copper, manganese, zinc, iron, aluminum, calcium, nickel, and other components. The separation of metals such as chromium and rare earth elements involves washing the organic phase with water, back-extraction with acid, and saponification with alkali. The organic phase is then reused, and the cobalt-containing raffinate is disposed of. The purified and back-extraction solutions should be treated separately. Industrial sulfuric acid and hydrochloric acid are recommended for preparing the wash water and back-extraction acid, while industrial sodium hydroxide and industrial sodium hydroxide are recommended. Prepare saponified alkaline solutions using ammonia water and other ingredients.

5.3.4.4 The extraction process flow is shown in Figure 1. Figure

5.4 Purification

5.4.1 Utilizing the selectivity of extractants for metals to achieve metal separation, purification and enrichment.

5.4.2 The main equipment is the same as in 5.3.4.2.

5.4.3 The cobalt-containing raffinate is mixed with the extractant, clarified, and the loaded organic phase and aqueous phase are separated. The cobalt-containing organic phase is washed and then enriched by acid back-extraction. The cobalt salt solution is obtained (the enterprise produces corresponding cobalt-containing chemical products as needed, and the product quality should meet the corresponding product technical requirements), and the reaction... The organic phase after extraction is saponified and reused, while the raffinate is treated separately; industrial sulfuric acid or industrial hydrochloric acid can be used to prepare wash water and back-extraction acid, and industrial sulfuric acid can be used. Sodium hydroxide and industrial ammonia are used to prepare an alkaline solution for organic saponification.

5.4.4 The purification process flow is shown in Figure 2. Figure