Titanium-bearing blast furnace slag (TBBFS) is a solid waste generated by the iron and steel industry, rich in valuable components such as TiO2, SiO2, Al2O3, and CaO. Conventional utilization methods mainly involve low-value applications or direct landfill disposal, leading to resource waste and potential environmental risks. In this study, TBBFS was innovatively employed to construct a porous ceramic catalyst support (TC). By regulating sintering temperature, holding time, and pore-forming agent content, a synergistic optimization between porosity and mechanical strength was achieved. After acid leaching, Cu, Ce, and Mn oxides were sequentially loaded onto the support through a stepwise hydrothermal method to prepare a series of hierarchical porous ceramic catalysts. The samples were systematically characterized by XRD, SEM, EDS, BET, and H2-TPR analyses. The results show that the raw TBBFS catalyst exhibited negligible activity, with toluene conversion remaining below 10% within the tested temperature range. The acid-leached ceramic support (HNO3@TC) achieved a T50 of 411.6 °C but failed to reach T90. For the single-metal catalyst Cu@TC, the T50 and T90 were 403.9 °C and 499.1 °C, respectively. The bimetallic Cu–Ce@TC achieved T50 and T90 at 345.4 °C and 469.3 °C, respectively. Compared with the raw TBBFS and the single- or bimetallic catalysts, the ternary Cu–Ce–Mn@TC catalyst exhibited outstanding performance, with T50 and T90 reaching 285.6 °C and 396.4 °C, respectively, fully demonstrating the remarkable enhancement of catalytic activity due to the synergistic effect among multiple metals. Furthermore, even under high space velocity (150,000 mL g⁻1 h⁻1) and high toluene concentration (3000 ppm), the Cu–Ce–Mn@TC catalyst maintained high activity and stability. During a continuous 36 h reaction test, toluene conversion was consistently maintained between 97 and 100% with minimal deactivation, highlighting its excellent efficiency, durability, and adaptability under complex operating conditions. In addition, kinetic fitting based on the Mars–van Krevelen (MVK) model revealed that the catalytic oxidation followed a lattice oxygen participation mechanism, with the oxidation step identified as the rate-determining step. Therefore, this study demonstrates the efficient application of TBBFS-derived ceramic supports in VOCs abatement, not only expanding the resource utilization pathway of metallurgical solid waste but also providing a new technical route and theoretical foundation for the development of low-cost, efficient, and environmentally friendly catalyst systems.

Modified porous ceramic catalysts derived from titanium-bearing blast furnace slag for efficient toluene oxidation

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2025年11月28日

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He Tao,
Fanshu Kong,
Jiahua Li,
Shuaibo Huang,
Zehua Wang,
Shucheng Tian,
Xueqing Li,
Haiping Liu

摘要

Titanium-bearing blast furnace slag (TBBFS) is a solid waste generated by the iron and steel industry, rich in valuable components such as TiO₂, SiO₂, Al₂O₃, and CaO. Conventional utilization methods mainly involve low-value applications or direct landfill disposal, leading to resource waste and potential environmental risks. In this study, TBBFS was innovatively employed to construct a porous ceramic catalyst support (TC). By regulating sintering temperature, holding time, and pore-forming agent content, a synergistic optimization between porosity and mechanical strength was achieved. After acid leaching, Cu, Ce, and Mn oxides were sequentially loaded onto the support through a stepwise hydrothermal method to prepare a series of hierarchical porous ceramic catalysts. The samples were systematically characterized by XRD, SEM, EDS, BET, and H₂-TPR analyses. The results show that the raw TBBFS catalyst exhibited negligible activity, with toluene conversion remaining below 10% within the tested temperature range. The acid-leached ceramic support (HNO₃@TC) achieved a T₅₀ of 411.6 °C but failed to reach T₉₀. For the single-metal catalyst Cu@TC, the T₅₀ and T₉₀ were 403.9 °C and 499.1 °C, respectively. The bimetallic Cu–Ce@TC achieved T₅₀ and T₉₀ at 345.4 °C and 469.3 °C, respectively. Compared with the raw TBBFS and the single- or bimetallic catalysts, the ternary Cu–Ce–Mn@TC catalyst exhibited outstanding performance, with T₅₀ and T₉₀ reaching 285.6 °C and 396.4 °C, respectively, fully demonstrating the remarkable enhancement of catalytic activity due to the synergistic effect among multiple metals. Furthermore, even under high space velocity (150,000 mL g⁻¹ h⁻¹) and high toluene concentration (3000 ppm), the Cu–Ce–Mn@TC catalyst maintained high activity and stability. During a continuous 36 h reaction test, toluene conversion was consistently maintained between 97 and 100% with minimal deactivation, highlighting its excellent efficiency, durability, and adaptability under complex operating conditions. In addition, kinetic fitting based on the Mars–van Krevelen (MVK) model revealed that the catalytic oxidation followed a lattice oxygen participation mechanism, with the oxidation step identified as the rate-determining step. Therefore, this study demonstrates the efficient application of TBBFS-derived ceramic supports in VOCs abatement, not only expanding the resource utilization pathway of metallurgical solid waste but also providing a new technical route and theoretical foundation for the development of low-cost, efficient, and environmentally friendly catalyst systems.