Additonal authors: Wei, Yao. Book title: Proceedings of the 58th Conference of Metallurgists Hosting Copper 2019. Chapter: . Chapter title:
Black copper sludge, which mainly contains copper, arsenic and a little antimony, bismuth, selenium, tellurium, is an important recyclable secondary resource. In this paper, selective removal of arsenic from black copper sludge by alkaline oxidative pressure leaching was studied. The influences of alkali concentration, leaching time, leaching temperature, oxygen pressure, liquid-solid ratio and other variables on the leaching rate of arsenic, copper and tellurium were investigated. The results were as follows: when the leaching process was conducted at initial alkali concentration of 1mol/L, liquid-solid ratio of 10, stirring rate of 500r/min, leaching temperature of 140°C for 5 h and oxygen pressure of 2.5MPa, the leaching rates of arsenic and tellurium were 85.43% and 59.7% respectively, and copper, antimony, bismuth were not leached. Hence, arsenic has been removed effectively from black copper sludge, while the valuable metals such as copper, antimony and bismuth remained in the residue that can be further recovered easily.
Black copper sludge is a byproduct in the purification process of copper electrolyte. Arsenic, antimony and bismuth are major harmful impurities in copper electrolytic refining system. The accumulation of these impurities will cause adverse effects, such as the increase of electrolyte resistance and power consumption and deterioration of cathode copper quality (Wang, Liu, & Zhang, 2001). Hence, electrolyte purification is an essential part of the electrolysis process (Liang, Chen, & Guo, 2009). Electrolyte purification methods include electrowinning (Davenport, King, Schlesinger, & Biswas, 2002), solvent extraction (Navarro, Simpson, & Alguacil, 1999), ion exchange (Arroyo et al., 2017), coprecipitation (Wang et al., 2003, 2018; Xiao et al., 2007; Xiao, Cao, Mao, Shen, & Ren, 2014), activated carbon adsorption (Navarro & Alguacil, 2002), electrodialysis (Cifuentes et al., 2015), redox process (Zhou, Peng, Zheng, Ma, & Cui, 2011; Peng, Zheng, Zhou, & Chen, 2012; Zheng, Peng, Ke, & Chen, 2013), among which the electrowinning method is simple in operation and effective in impurities removal, making it the main process for current electrolyte purification. Some copper ions can react with harmful impurities to form complex black copper sludge by controlling the operation conditions of electrowinning process. Based on the estimated data provide by Davenport et al. (2002), an annual output of 400,000 tons cathode copper could produce 432-2168 tons of black copper sludge by electrowinning method. Black copper sludge contains 30~50% copper, 15~30% arsenic and a small amount of rare elements such as selenium and tellurium. Thus, recovery of valuable metals can bring huge economic interests. Moreover, arsenic in these sludges could cause significant environmental pollution. Therefore, effective removal of arsenic from these sludges is urgent and significant.