Sintering Behavior and Chlorine Volatilization Mechanism of Cl-Containing Solid Waste in Clay Brick Production: Implications for Tunnel Kiln Applications

The use of tunnel kiln firing in clay brick production offers a promising approach for disposing of Cl-containing solid waste, with lower chlorine (Cl) and heavy metal volatilization compared to cement kiln processes. However, the effects of Cl salts on brick properties and the volatilization mechanisms remain unclear. This study investigates the behaviors of NaCl, KCl, and CaCl2 during sintering. Adding 15 wt% Cl salts significantly alters pore structure, increasing water absorption by 80–100% and reducing compressive strength by 70–80%. At 1050 °C, 10.8–16.4% of Cl volatilizes mainly as HCl (g), 24.4–26.2% remains in original salt form, and over half is immobilized within the brick matrix. Thermodynamic and TG-MS analyses reveal Cl salts are stable below 800 °C but release HCl (g) at higher temperatures due to lower reaction energy barriers than Cl2 (g). Density functional theory (DFT) calculations show that H+ for HCl (g) formation primarily originates from water vapor (H2O), with organic decomposition having minimal effect. The presence of Cl salts promotes feldspar and silicate phase formation, enhancing densification but increasing porosity from HCl release. To reduce HCl emissions, a two-stage temperature control strategy is proposed: organic decomposition and moisture removal below 600 °C, followed by sintering at 800–1000 °C. This work clarifies the volatilization mechanisms of Cl salts and provides guidance for optimizing industrial brick production using Cl-containing waste.