On-line production of ferrate with an electrochemical method and its potential application for wastewater treatment – A review

A number of studies on the oxidation of various organic/inorganic contaminants by ferrate(VI) were reported in the 1980s and 1990s. The exploration of the use of ferrate(VI) for water and wastewater treatment has been well addressed recently. However, challenges have existed for the implementation of ferrate(VI) technology in practice due to the instability of a ferrate solution or high production cost of solid ferrate products. The research has been carried out aiming at the generation and application of ferrate(VI) in situ. This paper thus reviews ferrate chemistry and its overall performance as a water treatment chemical, discusses the factors affecting the ferrate yield efficiency using the electrochemical method, and finally, summarises the work on the production and use of ferrate in situ which is currently under study.     

Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe(VI) systems

The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO₂ suspension under UV illumination has been investigated using oxygen (O₂) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O₂ for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO₂–UV–O₂ system, while in contrast phthalic acid was found to be the main intermediate product in the TiO₂–UV–Fe(VI) system. These findings indicate that DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO₂–UV–O₂ reaction system and an unknown radical species (most likely an iron–oxo species) is suspected to exist in the TiO₂–UV–Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO₂–UV–O₂ reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO₂–UV–Fe(VI) reaction systems attack the alkyl chain of DMP.     

Degradation of sulfonamides and formation of trihalomethanes by chlorination after pre-oxidation with Fe(VI)

Sulfonamides are used in human therapy, animal husbandry and agriculture but are not easily biodegradable, and are often detected in surface water. Sulfamethazine (SMZ) and sulfadiazine (SDZ) are two widely used sulfonamide antibiotics that are used heavily in agriculture. In this study, they were degraded in an aqueous system by chlorination after pre-oxidation with ferrate(VI) (Fe^VIO₄^2 ?, Fe(VI)), an environmentally friendly oxidation technique that has been shown to be effective in degrading various organics. The kinetics of the degradation were determined as a function of Fe(VI) (0–1.5 mg/L), free chlorine (0–1.8 mg/L) and temperature (15–35°C). According to the experimental results, SMZ chlorination followed second-order kinetics with increasing Fe(VI) dosage, and the effect of the initial free chlorine concentration on the reaction kinetics with pre-oxidation by Fe(VI) fitted a pseudo-first order model. The rate constants of SDZ and SMZ chlorination at different temperatures were related to the Arrhenius equation. Fe(VI) could reduce the levels of THMs formed and the toxicity of the sulfonamide degradation systems with Fe(VI) doses of 0.5–1.5 mg/L, which provides a reference for ensuring water quality in drinking water systems.     

高铁酸盐在水和废水处理中的应用进展

本文综述了高铁酸盐用于饮用水的消毒、杀菌、除藻，有机废水的氧化混凝，恶臭物质的氧化去除，重金属离子及放射性废水的混凝沉淀，以及色度浊度的去除等领域的最新进展。并对今后的研究进行了展望。     

On-line batch production of ferrate with an chemical method and its potential application for greywater recycling with Al(III) salt

Ferrate(VI) salt is an oxidant and coagulant for water and wastewater treatment. It is considered as a possible alternative method in greywater treatment. However, challenges have existed in putting ferrate(VI) technology into full-scale practice in water and wastewater treatment due to the instability of ferrate solution and high production cost of solid ferrate products. This study demonstrated a new approach of greywater treatment with on-line batch production of Fe(VI) to which Fe(III) salt was oxidized at a weak acidity solution. A series of experiments were conducted to investigate the effect of Fe(VI) on light greywater (total organic carbon (TOC) = 19.5 mg/L) and dark greywater (TOC = 55 mg/L) treatment under different conditions with varying pH and Fe(VI) doses. In addition, the combination use of Fe(VI) and Al(III) salts was proved to be more efficient than using the Fe(VI) salts alone at greywater recycling. The optimum dosage of Fe(VI)/Al(III) salts was 25/25 mg/L for light greywater, 90/60 mg/L for dark greywater, respectively. The TOC values of both light greywater and dark greywater were reduced to less than 3 mg/L with the dosages. The cost for treating greywater was 0.06–0.2 $/ton at ferrate(VI) dosage of 25–90 mg/L and 0.008–0.024 $/ton at AlCl₃ dosage of 25–60 mg/L. The full operating cost needs further assessment before the Fe(VI)/Al(III) technology could be implemented in greywater treatment.     

Application of Fe(VI) in abating contaminants in water: State of art and knowledge gaps

• The properties of Fe(VI) were summarized. • Both the superiorities and the limitations of Fe(VI) technologies were discussed. • Methods to improve contaminants oxidation/disinfection by Fe(VI) were introduced. • Future research needs for the development of Fe(VI) technologies were proposed. The past two decades have witnessed the rapid development and wide application of Fe(VI) in the field of water de-contamination because of its environmentally benign character. Fe(VI) has been mainly applied as a highly efficient oxidant/disinfectant for the selective elimination of contaminants. The in situ generated iron(III) (hydr)oxides with the function of adsorption/coagulation can further increase the removal of contaminants by Fe(VI) in some cases. Because of the limitations of Fe(VI) per se, various modified methods have been developed to improve the performance of Fe(VI) oxidation technology. Based on the published literature, this paper summarized the current views on the intrinsic properties of Fe(VI) with the emphasis on the self-decay mechanism of Fe(VI). The applications of Fe(VI) as a sole oxidant for decomposing organic contaminants rich in electron-donating moieties, as a bi-functional reagent (both oxidant and coagulant) for eliminating some special contaminants, and as a disinfectant for inactivating microorganisms were systematically summarized. Moreover, the difficulties in synthesizing and preserving Fe(VI), which limits the large-scale application of Fe(VI), and the potential formation of toxic byproducts during Fe(VI) application were presented. This paper also systematically reviewed the important nodes in developing methods to improve the performance of Fe(VI) as oxidant or disinfectant in the past two decades, and proposed the future research needs for the development of Fe(VI) technologies.     

Ferrate(VI) oxidation of ibuprofen: A kinetic study

The kinetics of ferrate(VI) (Fe^VIO₄ ²⁻, Fe(VI)) oxidation of an antiphlogistic drug, ibuprofen (IBP), as a function of pH (7.75–9.10) and temperature (25–45°C) were investigated to see the applicability of Fe(VI) in removing this drug from water. The rates decrease with an increase in pH and the rates are related to protonation of ferrate(VI). The rates increase with an increase in temperature. The E _a of the reaction at pH 9.10 was calculated as 65.4±6.4 kJ mol⁻¹. The rate constant of the HFeO₄ ⁻ with ibuprofen is lower than with the sulphur drug, sulfamethoxazole. The use of Fe(VI) to remove ibuprofen is briefly discussed.