Additonal authors: Desai, Bhavin. Book title: Proceedings of the 58th Conference of Metallurgists Hosting Copper 2019. Chapter: . Chapter title:
Gases rich in sulfur dioxide generated as a by-product of smelting and converting operations of copper concentrate contain selenium apart from zinc, lead, copper, cadmium, bismuth, antimony, and arsenic. The gaseous stream is heat exchanged in waste heat boiler, dust collected in electrostatic precipitator followed by cleaning in reverse jet scrubber to remove fumes, halogens and fine dust before passing to DCDA Monsanto catalytic converter to produce commercial grade sulfuric acid. The gas cleaning section of the acid plant uses water to scrub the smelting gases. During scrubbing, precipitated solids, known as sludge, settles at the bottom of the reverse jet scrubber containing 30 to 40 wt% copper and selenium up to 40 wt% selenium. In the existing process, the sludge collected during scrubber cleaning process is directly recycled to the smelter for copper recovery. However, the selenium is expected to again vaporize due to high oxidation potential during smelting and converting, causing accumulation of selenium in sludge.
In present investigation, a roasting process has been developed to recover the selenium from acid plant sludge before charging it to smelter for copper recovery. Selenium is associated with copper in acid plant sludge as copper selenide, as determined by X-ray diffraction and electron microscopy. Thermodynamic and thermo-gravimetry study revealed that the copper selenide phase present in the sludge was amenable to oxidation at 600°C forming oxides of copper and selenium (Cu-Se-O). However, the dissociation of selenium from the copper oxide was made possible by sulfatation using sulfur dioxide between 450°C to 600°C, resulting into the formation of CuSO4(s) and SeO2(g). Lab scale experiments were carried out in vertical tubular furnace to determine the optimum roasting conditions with respect to roasting time, temperature and molar ratio of O2:SO2. Using these optimum conditions, selenium up to 90 wt. % in the form of SeO2 vapors could be recovered from the acid plant sludge in a large scale commercial roaster. Roasted sludge free from selenium and containing oxides and sulfates of copper could now be recycled in the smelter for copper recovery.
There is an increasing demand for minor metals due to their use in innovative technologies. Similarly, the increase in demand for selenium is expected due to disruption in sectors related to renewable energy and photovoltaic battery. Selenium is a chalcogen and a non-metal with black or red crystalline appearance. Selenium is used in the glass industry to decolorize glass and to make red-colored glasses and enamels. It is also used in solar cells and as a photographic toner. Selenium is used as a brasses in stainless steel to improve its machinability. Selenium sulfide is used in anti-dandruff shampoos. In spite of the toxicity of its compounds, selenium is also an essential trace element for humans and animals. Selenium occasionally occurs free in nature, but more often occurs as selenides of iron, lead, silver and copper. There is an urgent need for the development of new methods for selenium recovery from the existing resources. Commercially, selenium is obtained only from anode mud produced during electrolytic refinery of copper.