Liya Fu

Due to its highly developed pore structure and large specific surface area, activated carbon is often used as a catalyst or catalyst carrier in catalytic ozonation. Although the pore structure of activated carbon plays a significant role in the treatment of wastewater and the mass transfer of ozone molecules, the effect is complicated and unclear. Because different application scenarios require catalysts with different pore structures, catalysts with appropriate pore structure characteristics should be developed. In this review, we systematically summarized the current adjustment methods for the pore structure of activated carbon, including raw material, carbonization, activation, modification, and loading. Then, based on the brief introduction of the application of activated carbon in catalytic ozonation, the effects of pore structure on catalytic ozonation and mass transfer are reviewed. Furthermore, we proposed that the effect of pore structure is mainly to provide catalytic active sites, promote free radical generation, and reduce mass transfer resistance. Therefore, large external surface area and reasonable pore size distribution are conducive to catalytic ozonation and mass transfer.

The petrochemical secondary effluent (PSE) is typical refractory wastewater derived from the petrochemical industries, which requires advanced treatment due to the strict environmental protection policies. Catalytic ozonation is one of the most widely used advanced oxidation technologies in wastewater treatment because of its high mineralization rate, in which the alumina-based catalyst usually plays an important role. Extrusion-spheronization is a promising technique for the preparation of alumina spheres because the synthesized alumina particles have high sphericity, high specific surface aera and narrow particle size distribution. In this paper, two kinds of alumina-based catalysts (catalyst A: manganese nitrate added after alumina granulation and catalyst B: manganese nitrate added into alumina powder before granulation) were prepared by the extrusion-spheronization method and used for PSE treatment by catalytic ozonation. The prepared alumina samples were characterized by Brunauer–Emmett–Teller (BET) method, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM), while the wastewater samples were analyzed for Total organic carbon (TOC), UV₂₅₄ and fluorescence spectroscopy. Results showed that manganese was uniformly distributed in both catalysts, and the specific surface area of two catalysts was 318.36 m²/g and 354.95 m²/g, respectively. Catalytic ozonation experiments were repeated nine times with each catalyst under the same conditions. The TOC removal rates for catalysts A and B in the first run were 48.88% and 49.06%, respectively, then it dropped to 28.05% for catalyst A but remained 47.81% for catalyst B after using for nine times. This implied that the long-term performance of catalyst B would be more stable than catalyst A. Similar result were found in three-dimensional fluorescence analysis. UV₂₅₄ results indicated that the removal efficiency of aromatic and unsaturated substances by catalyst B was higher than catalyst A. A possible explanation is that the active component manganese oxide formed a catalyst skeleton in catalyst B, which makes it hard to dissolve. Graphical abstract Effect of extrusion-spheronization granulation and manganese loading on advanced oxidant treatment of petrochemical wastewater

Acetaldehyde is a typical toxic substance of the petrochemical industry. Dissolved organic carbon (DOC) plays an important role in wastewater treatment. Therefore, the molecular weight, hydrophilicity, and chemical composition of DOC in acetaldehyde wastewater were evaluated. First, the molecular weight (MW) distribution was investigated; the results showed that acetaldehyde wastewater was mainly composed of components with a MW less than 1 kDa, and possessed higher proportion of protein-like substances that were dominant contributors to membrane fouling. Then, the distribution of hydrophobicity was evaluated; hydrophobic bases were reported to be slowly biodegradable fractions due to the high humic content. Finally, gas chromatography–mass spectrometry (GC-MS) was utilized to determine chemical composition, and 30 pollutants were detected. Aldehydes, hydrocarbons, ketones, alcohols, furans, phenols, and organic acids were the dominant pollutants. Most of them were moderately toxic compounds. The comprehensive characterization of acetaldehyde wastewater will contribute to control strategies and sustainable development.

Advanced oxidation (e.g., fenton-like reagent oxidation and ozone oxidation) is a highly important technology that uses strong oxidizing free radicals to degrade organic pollutants and mineralize them. The fenton-like reactions have the characteristics of low cost, simple operation, thorough reaction and no secondary pollution. Fenton-like reagents refer to a strong oxidation system composed of transition metal ions (e.g., Fe³⁺, Mn²⁺ and Ag⁺) and oxidants (hydrogen peroxide, potassium persulfate, sodium persulfate, etc). Graphene and carbon nanotube possess a distinctive mechanical strength, flexibility, electrical and thermal conductivity and a very large specific surface area, which can work as an excellent carrier to disperse the catalyst and prevent its agglomeration. Fullerene can synergize with iron-based materials to promote the reaction of hydroxyl groups with organic pollutants and enhance the catalytic effect. Fenton-like catalysts influence the catalytic behavior by inducing electron transfer under strong interactions with the support. Due to the short lifespan of free radicals, the treatment effect is usually enhanced with the assistance of external conditions (ultraviolet and electric fields) to expand the application of fenton-like catalysts in water treatment. There are mainly light-fenton, electro-fenton and photoelectric-fenton methods. Fenton-like catalysts can be prepared by hydrothermal method, impregnation and coordination-precipitation approaches. The structures and properties of the catalysts are characterized by a variety of techniques, such as high-resolution transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption near-edge structure spectroscopy. In this paper, we review the mechanisms, preparation methods, characterizations and applications status of fenton-like reagents in industrial wastewater treatment, and summarize the recycling of these catalysts and describe prospects for their future research directions.

The combination of ozone and biological aerated filter (O₃/BAF) has been widely studied and applied in polishing different biological secondary effluents. O₃/BAF has the advantages of high pollutants removal rate, low operating cost, and flexible combination types. The principle and combination, effect of ozone dosage and influent suspended solids (SS) on O₃/BAF, applications, current research focuses, and development are discussed. The ozone can break refractory macromolecules into small and biodegradable fragments, increasing the biodegradation. It benefits the operation of BAF. The coupling of ozonation and BAF is efficient in the removal of refractory organic pollutants from different wastewaters. Ozonation can also be used as the post-treatment option after BAF to guarantee the effluent qualities. Normally, the ozone dosage varied from 5 to 125 mg/L with the contact time of 4 to 60 min, while the hydraulic retention time (HRT) of BAF is usually between 2 to 5 h when treating different biological effluents. The effluent COD is normally lower than 50 mg/L. Most of the organic micropollutants (OMPs) in the biological effluent, such as antibiotics, pharmaceuticals, personal care products, steroid hormones, and industrial chemicals, can be efficiently removed by O₃/BAF. More importantly, the O₃/BAF can obviously reduce the toxicity of the wastewater. The residual ozone of about 0.2 mg/L in the ozonation effluent benefits the performance of BAF. The future trends of O₃/BAF are also discussed in the paper.