Composition and Leaching Toxicity of Hydrochloric Acid Pickling Sludge Generated from the Hot-Dip Galvanized Steel Industry

Yane Xu; Yichen Zhang; Yuanfeng Shu; Huiyun Song; Xinqian Shu; Yuanxin Ma; Lulu Hao; Xize Zhang; Xiaoling Ren; Zhipu Wang; Xiaolei Zhang

doi:10.1021/acsomega.2c00121

Composition and Leaching Toxicity of Hydrochloric Acid Pickling Sludge Generated from the Hot-Dip Galvanized Steel Industry

ACS Omega. 2022 Apr 12;7(16):13826-13840. doi: 10.1021/acsomega.2c00121. eCollection 2022 Apr 26.

Authors

Affiliations

¹ School of Chemistry and Environmental Engineering, China University of Mining and Technology Beijing, Beijing 100083, China.
² State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing at Karamay, Karamay 834000, China.

Abstract

Steel hydrochloric acid pickling sludge (SHPS), containing the heavy metals Fe, Zn, and Ni and a high chloride salt content, is considered a type of hazardous solid waste because of its potential harm to human health and the environment. In addition, the SHPS yield is large, but the main treatment currently used is only safe for landfills. Although studying the composition and leaching toxicity of SHPS is of great importance, only a small amount of related literature is available. This paper can help compensate for this deficiency. SHPS is analyzed from the aspects of its formation mechanism, pH, moisture content, elemental concentration, phase composition, microstructure, and leaching toxicity. The results show that its pH ranges from 2.25 to 11.11, and the moisture content ranges from 45.47% to 83.34%. Additionally, the concentration of Fe is the highest, with values from 29.80% to 50.65%, while other alkali metal elements, namely, Ca, K, and Na, have values of 0.36% to 23.07%, 0.02% to 19.82%, and 0.38% to 3.31%, respectively. Heavy metal elements, namely, Zn, Ni, Mn, Cr, and Pb, have values of 0.02% to 14.88%, 0.001% to 0.05%, 0.03% to 0.38%, 0.01% to 0.09%, and 0.02% to 0.19%, respectively. Anions, namely, SO₄ ^2-, Cl^-, F^-, and NO₃ ^-, have contents of 0.09% to 0.34%, 0.54% to 5.73%, 0.001% to 0.04%, and 0.01% to 0.15%, respectively. X-ray diffraction (XRD) analysis shows that Fe and Zn are mainly present in oxides, Ca is present as CaO and CaCO₃, and chlorine is present in NaCl. Moreover, scanning electron microscopy (SEM) analysis shows that the microscopic structure consists mainly of bright and fluffy irregular spheres; stripes; flakes; and dark, very small irregular particles. The leaching toxicity test based on HJ/T 299-2007 (China) was performed, where SHPS samples were treated with a mixed solution of sulfuric acid, nitric acid, and pure water (pH = 3.20 ± 0.05) at a liquid-to-solid ratio of 10:1 for a period of 18 h. The leachate was filtered and analyzed for Cr, Ni, Mn, Zn, etc. The leaching results indicate that Zn and Ni are the main elements that cause SHPS to be hazardous to the environment. These research results can provide a reference for later researchers studying the effective treatment of SHPS, such as more effective treatments for reducing toxicity and resource utilization.