Development, dilemma and potential strategies for the application of nanocatalysts in wastewater catalytic ozonation: A review.

With the continuous development of nanomaterials in recent years, the application of nanocatalysts in catalytic ozone oxidation has attracted more and more researchers' attention due to their excellent catalytic properties. In this review, we systematically summarized the current research status of nanocatalysts mainly involving material categories, mechanisms and catalytic efficiency. Based on summary and analysis, we found most of the reported nanocatalysts were in the stage of laboratory research, which was caused by the nanocatalysts defects such as easy aggregation, difficult separation, and easy leakage. These defects might result in severe resource waste, economic loss and potentially adverse effects imposed on the ecosystem and human health. Aiming at solving these defects, we further analyzed the reasons and the existing reports, and revealed that coupling nano-catalyst and membrane, supported nanocatalysts and magnetic nanocatalysts had promising potential in solving these problems and promoting the actual application of nanocatalysts in wastewater treatment. Furthermore, the advantages, shortages and our perspectives of these methods are summarized and discussed.

A thorough observation of an ozonation catalyst under long-term practical operation: Deactivation mechanism and regeneration.

Heterogeneous catalytic oxidation, as an efficient advanced treatment technology, has been gradually applied in industrial wastewater treatment. The fixed bed technique is one of the most popular catalytic ozonation methods. However, few studies have concentrated on the long-term operation effects on catalysts. In this study, we conducted long-term (~5 years) observations of the operation of the largest petrochemical wastewater treatment plant (treatment capacity 120,000 m3/d) with catalytic ozonation technology in China. A commercial catalyst, which uses Al2O3 pellets supporting copper oxide was applied in this plant. The results showed that the catalytic efficiency gradually decreased from 60.65% to 25.98% since 2018, and the ozone dosage to COD removal ratio (ozone/COD) also increased from 0.82 to 1.93 mg/mg as the running time continued. By means of the comparison and characterization of fresh catalyst and used catalyst, a "mucus layer" was formed by the adsorption of negatively charged extracellular polymeric substances on the positively charged catalyst surface and the interception of the catalyst layer. The mucus layer significantly reduced the catalytic efficiency by isolating ozone with catalytic active sites and releasing extra organic contaminants during the catalytic process resulting in 53.97% TOC increase in the batch test. Meanwhile, regeneration experiments revealed that the TOC removal efficiency was 4.76% and 43.48% in presence of washed catalysts and calcinated catalysts, respectively. Compared with the fresh catalyst, 73% of the catalytic activity was recovered for calcinated catalyst. Consequently, this study provides much practical information, showing positive effects on the promotion of catalytic ozonation application in actual wastewater treatment.

Iron foam coupled hydrolysis acidification for trichloroacetaldehyde treatment: Strengthening characteristics and mechanism.

This research studied transformative characteristics and enhanced mechanism of trichloroacetaldehyde (TCAL), one of chlorinated acetaldehydes (CAAs), by coupled-type iron foam enhanced hydrolysis acidification (HA) reactor. Main results were given that better dechlorination and aldehyde removal were achieved at this process than coupled-type iron foam enhanced HA, alone iron foam and HA reactor. The reasons were due to better strengthening effects of iron foam and HA, iron foam reduced TCAL toxicity to microbes caused an improvement of microbial activity, therefore, volatile fatty acids (VFAs) content and acetate acid (Ac) ratio were increased compared with HA. Moreover, it promoted the enrichment of Actinobacteriota and Firmicutes, and more extracellular polymeric substance (EPS) and enzymes enhanced dechlorination and aldehyde removal. Certainly, microbes reduced iron foam passivation and facilitated its oxidation further improved the strengthening effect.

Acidification inhibition, biodechlorination, and biotransformation of chlorinated acetaldehydes on acidogenic sludge and microbial community changes.

Chlorinated acetaldehydes (CALs) are typical chlorinated organic compounds that posing a great threat to biological wastewater treatment plants. In this study, volatile batch acid (VFA) tests were employed to investigate the acidification inhibition, biodechlorination, and biotransformation of high-strength CALs on hydrolytic acidification. The results indicated that the optimum parameters were 4 g/L sludge, pH = 8, and glucose as an electron donor. Moreover, the acidification inhibition and biodechlorination showed a strongly positive correlation with the degree of chlorination and CAL concentrations. Extracellular polymeric substances (EPS) decreased dramatically, while DNA increased sharply under higher CAL concentrations, which was the result of cell death caused by the toxicity of the CALs. Additionally, the relative toxicities of the CALs were as follows: trichloroacetaldehyde > dichloroacetaldehyde > chloroacetaldehyde. Furthermore, Excitation-Emission-Matrix (EEM) spectra of EPS revealed that aromatic protein-like substances I interacted with CALs to achieve a slight removal of CALs. The detected products revealed that some of the chlorine atoms and aldehyde groups in the CALs were removed by microbes to certain degree. Moreover, microbial community analysis indicated that the dominant phyla were Actinobacteria, Bacteroidetes, and Synergistetes, which had a stronger tolerance to CALs. Notably, biodechlorination was closely related to a remarkable increase in members of the genus Trichococcus.

A magnetic-void-porous MnFe2O4/carbon microspheres nano-catalyst for catalytic ozonation: Preparation, performance and mechanism.

Wastewater treatment is essential to guarantee human health and ecological security. Catalytic ozonation with nanocatalysts is a widely studied and efficient treatment technology. However, this method has always been limited by nanocatalysts disadvantages such as easily loss, difficult to separate and reuse, and catalytic ability decay caused by aggregation, which could cause severe resources waste and potential risk to human health and ecosystem. To remedy these challenges, a magnetic-void-porous MnFe2O4/carbon microsphere shell nanocatalyst (CMS-MnFe2O4) was successfully synthesized using renewable natural microalgae. The separation test showed CMS-MnFe2O4 was rapidly separated within 2 min under an external magnetic field. In catalytic ozonation of oxalic acid (OA), CMS-MnFe2O4 showed efficient and stable catalytic efficiency, reaching a maximum total organic carbon removal efficiency of 96.59 % and maintained a 93.88 % efficiency after 4 cycles. The stable catalytic efficiency was due to the supporting effects of the carbon microsphere shell, which significantly enhanced CMS-MnFe2O4 chemical stability and reduced the metal ions leaching to 10-20 % of MnFe2O4 through electron transfer. To explore the catalytic mechanism, radical experiments were conducted and a new degradation pathway of OA involving superoxide anions rather than hydroxyl radicals was proposed. Consequently, this study suggests that an efficient, recyclable, stable, and durable catalyst for catalytic ozonation could be prepared.

Inhibition and removal of trichloroacetaldehyde by biological acidification with glucose co-metabolism.

Biological acidification plays a crucial role in biological removal of organic compounds during petrochemical wastewater treatment. Trichloroacetaldehyde is a typical organic pollutant in petrochemical wastewater, however, no studies have been conducted on its effect on biological acidification. In this study, batch bioassays of volatile fatty acids were conducted to explore the inhibitory effect of trichloroacetaldehyde on biological acidification, the variations of key enzymes and extracellular polymeric substances under trichloroacetaldehyde shock, and the mechanism of trichloroacetaldehyde removal. The results of these bioassays indicated that trichloroacetaldehyde inhibited the acid yield at higher concentrations (EC50 112.20 mg/L), and butyric fermentation was predominant. Moreover, the contents of extracellular polymeric substances and several key acidifying enzymes greatly decreased when the trichloroacetaldehyde concentration exceeded 100 mg/L, which was due to the toxicity that trichloroacetaldehyde poses to the microbes involved in biological acidification. The trichloroacetaldehyde mechanism was as follows: first, trichloroacetaldehyde was adsorbed by extracellular polymeric substances and anaerobic granular sludge, and then transformed into trichloroethanol, trichloroethane, dichloroacetaldehyde, and dichloroethanol under the combined action of the aldehyde reductase and reductive dehalogenases secreted from the microbial consortium. The ability of biological acidification to remove trichloroacetaldehyde was limited; therefore, trichloroacetaldehyde should be pretreated before it enters biological treatment systems.

Recent development of recycling lead from scrap CRTs: A technological review.

Cathode ray tubes (CRTs) contain numerous harmful substances with different functions. Lead is found in the funnel glass of CRTs. Improperly treated toxic lead may pose significant risks to human health and the environment. This paper reviews and summarizes existing technological processes on the recycling of lead from waste CRTs, including pyrometallurgy, hydrometallurgy, and product-regeneration. The present situation, advantages, and disadvantages of these techniques are described in detail. Generally, pyrometallurgy shows better practicability in recovery lead from waste CRT than hydrometallurgy and hydrometallurgy, in view of environmental impact, energy-consumption, product formats and safety and maturity of technology. Moreover, the gaps in the existing technologies were identified and recommendations for future research were provided.