Arsenic sulfide residue (ASR), a by-product from the treatment of arsenic-bearing acidic wastewater, is abundantly generated but not properly disposed of in China. The utilization of such high-content arsenic waste residue is limited by the market. The traditional methods of stabilization/solidification (S/S) by lime cement or iron salt have a large mass/volume addition, high dumping cost and secondary pollution risk. In this paper, hydrothermal technology was used to treat three kinds of ASRs obtained from different smelters to minimize waste. The leaching toxicity and chemical speciation of the generated products was also evaluated by TCLP and BCR analyses. It was found that the hydrothermal treatment could greatly reduce the volume and moisture content of the ASRs. TCLP tests showed that the leachability of arsenic and heavy metals significantly decreased after the treatment. According to the BCR analysis, most of the unstable As, Cd and Cr transformed into a residual fraction. Finally, XRD, SEM, Raman and XPS techniques were carried out to reveal the mechanism. As a result, hydrothermal treatment can efficiently achieve the dehydration, volume reduction and stabilization/solidification of ASRs.
Non-ferrous metal smelting enterprises produce hundreds of thousands of tons of arsenic sulfide sludge (ASS) each year in China. Most of the ASS are stored at the companies without enough preventive measures. During the storage and natural drying process, arsenic sulfide is easily oxidized, thereby causing secondary pollution and increasing environmental risks. In this paper, experiments of simulated storage were used to study the release characteristics of heavy metals. During the simulated storage, the release concentrations of As, Pb, and Cd increased rapidly at first and then slowly. Although the total amount of arsenic released was the largest, the release ratio was in the order of Cd > Pb > As. The effects of different atmospheres and conditions on the release of arsenic and heavy metals were explored. The more the H2SO4 in the sludge, the higher the release concentration, and the addition of an appropriate amount of Ca(OH)2 is beneficial for reducing the release of heavy metals. Finally, SEM, XRD and TG-DTG techniques were carried out to confirm that the release of heavy metals was caused by the oxidation process resulting from the residual H2SO4 in the ASS and the air.
The current paper explored the directly reductive decomposition of waste sodium arsenate by roasting it with charcoal powder to volatilize less toxic As0 and to simultaneously obtain sodium salts with potential commercial value, serving the purpose of developing a more sustainable route to deal with the environmental issues faced by the antimony production industry in China. The process was firstly evaluated by thermogravimetric (TG) analysis and thermochemical calculations. The effects of N2 flow rate, roasting temperature, dosage of charcoal powder, and roasting time were then investigated. The results showed that the arsenic extraction could reach 99.84% under optimal conditions. The roasting residue, containing arsenic as low as 0.0598%, was a promising source for the production of Na2CO3 as expected. In addition, X-ray diffraction (XRD), scanning electron micrograph (SEM), and X-ray photoelectron spectroscopy (XPS) were conducted to reveal the roasting mechanism and formation of metal arsenic was thereby confirmed.