An Wang,Kanggen Zhou,Xuekai Zhang,Dingcan Zhou,Changhong Peng,Wei Chen
Large amounts of waste acids with high acidity and arsenic levels are produced during pyrometallurgy of nonferrous metal sulfide ores, in which the treatment of arsenic remains a problem. In this study, copper powder was used as a reducing agent and synergized with iodine ions to effectively remove arsenic from waste acids. The influences of stirring speed, copper powder particle size, sodium iodide/copper powder dosages, and reaction temperature on the removal efficiency of arsenic were investigated. The results showed almost complete removal of arsenic under the optimal conditions: 600 rpm stirring speed, copper powder particle size <15 μm, molar ratio I:As = 5, molar ratio Cu:As = 8, reaction temperature 40 °C, and reaction time 90 min. The kinetics studies indicated that arsenic removal was controlled by chemical reaction with apparent activation energy of 42.39 kJ·mol −1 . The morphological and structural characterizations of dearsenization residues showed surface of copper particles with double covering-layers. The interior covering-layer constituted the formation region of As(0), the phases of which were As and As-Cu intermetallic compounds, while the main product formed in exterior covering-layer was identified as CuI.
Before steel can be utilized, pickling is necessary to remove surface oxidation products. However, as the ferrous ion concentration in the pickling solution increases, the pickling rate significantly diminishes, necessitating the treatment of spent pickling solution (SPS) to mitigate its hazardous effects prior to disposal. Current industrial methods predominantly rely on neutralization and precipitation techniques, which are cost-prohibitive and generate substantial by-products, thus failing to meet environmental protection standards. In this study, a new method, which is based on the formation of FeC2O4·2H2O precipitate in a strong acid solution, is proposed to treat the SPS. Initially, the SPS undergoes a two-step impurity removal process, followed by the controlled addition of oxalic acid dihydrate (H2C2O4·2H2O) to precipitate iron. The resulting precipitate is filtered, washed, and vacuum-dried, and the regenerated acid is recycled back into the pickling tank. When 1 g/10 mL of H2C2O4·2H2O is used, the iron removal rate achieves 60%, and the acidity of the regenerated acid increases by 11.3%. X-ray diffraction pattern (XRD) and thermogravimetric–differential scanning calorimetry (TG-DSC) characterization showed that the precipitate was α-FeC2O4·2H2O, with an average particle size of about 3.19 μm and a purity of 95.24%. This process innovatively achieves efficient recycling of acid and iron resources, offering a potential solution to the industrial challenge of difficult SPS treatment in the steel industry and meeting the urgent need for sustainable development.
Ya Gao,Tong Yue,Wei Sun,Dongdong He,Chenglong Lu,Xinzhuang Fu
Acid recovering and iron recycling from pickling waste acid are the desired goal of the steel mills for current ecological requirements and economic benefit. This study proposed a novel method to treatment the pickling waste acid using extraction separation of ferric chloride and hydrochloric acid , following by the spray pyrolysis of ferric chloride stripping liquor. Comparing the Ruthner method, the significant technical advantages of this method is the lower treatment load and operating costs for the spray pyrolysis process, attributing to the reuse of most hydrochloric acid without iron powder neutralizing. Different extractants (TBP, CYC, IA, OA, and PA) are compared to extract ferric ion from high-concentration hydrochloric acid solution and the optimum conditions are researched. Spectroscopic analysis is performed to characterize iron state in extractants. For the stripped solution, spray pyrolysis is employed to produce high-purity Fe 2 O 3 fine particles, meanwhile hydrochloric acid is recovered for following pickling procedure. The results showed that the effect of CYC under lower O/A ratio was better than that of TBP, and the opposite occurred at higher ratios. Three-stage extraction efficiency can reach over 80% at O/A = 2:1. The final O/A ratio of 1:1 was chosen for the stripping of iron-loaded extractants. Raman and UV–visible found that it was [FeCl 4 ] - anion that existed in Fe-loaded TBP and CYC. Spray pyrolysis at 1000 °C can obtain fine pure Fe 2 O 3 and hydrochloric acid. Eventually, a feasible technological process was put forward to recycle all chemicals and achieve zero emission of water and solid waste in the whole process.
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