Utilizing fly ash to prepare ceramsite is a promising way to immobilize heavy metals and recycle industrial solid waste. However, traditional preparation method of fly ash ceramsite has the disadvantages of large ignition loss. Therefore, the present study applied the pressure molding method to enhance solid content and improve the strength of ceramsite. The optimal preparation conditions of ceramsite were suggested as preheating at 450 °C for 25 min followed by sintering at 1050 °C for 30 min. Under such conditions, ceramsite with high compressive strength of 10.8 Mpa, bulk density of 878 kg m−3, and 1-h water absorption of 18.5% was fabricated, in compliance with Chinese standard (GB/T 1743.1–2010). The arsenic leaching concentration from the resulting product was considerably lower than Chinese standard (GB 5085.3–2007). Moreover, arsenic volatilization during ceramsite calcination was insignificant, and the vast majority of arsenic remained in resulting ceramsite. A geochemical speciation model developed for the multiple component system in ceramsite suggested that FeAsO4, Ca5(OH) (AsO4)3, and hydrous ferric oxide adsorption are the primary mechanisms retaining arsenic in ceramsite. Additionally, based on density functional theory calculations and biotoxicity test, the binding site of arsenic atom on mineral components and the environmental safety of ceramsite was determined and evaluated.
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