Purification of highly concentrated cyanide-containing wastewater via stepwise recovering of valuable components

Abstract

This study develops an efficient technique to purify the highly concentrated cyanide-containing industrial wastewater by recovering the valuable components. Firstly, sodium sulfide, sodium polysulfide and ferrous sulfate were respectively used as the precipitating agents to retrieve zinc, copper and iron from wastewater stepwise. In the meantime, cyanide presented as free cyanide and copper–cyanide complexes were transformed into thiocyanate by polysulfide. Afterwards, the solvent extraction of thiocyanate was systematically conducted with trioctylamine (TOA) as the extraction agent and sodium hydroxide solution as the stripping agent. The results showed that the contents of zinc, copper and iron in the solution after precipitation were less than 1 mg·L−1. Focusing on the reaction between copper–cyanide complex and polysulfide, three stages were established for the first time. In the first stage, Cu(CN)32− was gradually converted to CuCN0 and thiocyanate was rapidly generated. In the second stage, in addition to the formation of thiocyanate, Cu(I) was oxidized by polysulfide and precipitated as CuS ultimately. With an apparent activation energy of 70.9 kJ∙mol−1, kinetic analysis of the second stage suggested a significant effect of temperature on the copper–cyanide complex conversion rate. The apparent reaction orders of zero-valent sulfur and cyanide was 1.34 and 2.33, respectively. After the extraction and stripping process, the extraction efficiency of thiocyanate was nearly 100 % and the concentration of it can be enriched to 125 g·L−1 in the stripping solution. TOA and thiocyanic acid formed an extraction complex in a 1:1 ratio. This approach achieves the simultaneous recovery of valuable metallic ions (zinc, copper and iron) and cyanide conversion under the alkaline condition, which provides a new idea for the treatment of highly concentrated cyanide-containing wastewater with a complicated composition.