From waste to catalyst: Growth mechanisms of ZSM-5 zeolite from coal fly ash & rice husk ash and its performance as catalyst for tetracycline degradation in fenton-like oxidation

Abstract

Coal fly ash (CFA), an industrial solid waste, can be utilized to synthesize Zeolite Socony Mobil-5 (ZSM-5) by incorporating an external silica source. In this study, a series of ZSM-5 zeolites were synthesized using rice husk ash (RHA) as the primary silica source and CFA as the primary aluminum source under controlled hydrothermal reaction conditions, and the growth mechanism of ZSM-5 was investigated. The process of ZSM-5 growth was featured by the transformation of hyperpoly silico-aluminate in CFA and RHA into monomers. These monomers formed crystal nuclei connected in a five-membered ring structure under the influence of Tetrapropyl ammonium hydroxide (TPAOH). The surplus monomeric silica-aluminate grew on the nucleus surface due to the addition of the silica source within RHA (RHA-SiO₂), ultimately resulting in the development of ZSM-5 zeolite. Characterization results demonstrated that RHA-SiO₂ exhibited favorable physical and chemical properties during the ZSM-5 synthesis, with a crystallinity of 99.03%, a specific surface area of 321.19 m²/g, a weight loss of only 3.06% at 800 °C and a total acidity of 0.65 mmol/g. To evaluate the catalytic performance of ZSM-5, Fe/Cu-modified ZSM-5 was developed and used as the catalyst for the degradation of tetracycline (TC) in Fenton-like oxidation. The results indicated that Fe/Cu-ZSM-5 exhibited excellent activity and stability as the catalyst for TC degradation and mineralization. The maximum TC degradation rate reached 99.02% in 10 min and the TOC removal could be up to 69.32% in 2 h. Characterization results indicated that the Fe/Cu ions redox cycle accelerated the generation of active species (¹O₂ and ˙OH) in Fenton-like systems. The ZSM-5 zeolite synthesized from solid waste demonstrated superb stability and catalytic activity, leading to the effective removal of TC. Since real wastewater generally contains various pollutants, future research efforts should focused on multi-pollutant treatment.

Keywords: Coal fly ash; Fenton-like reaction; Iron-copper modification; Tetracycline degradation; ZSM-5 zeolite.