During the extraction of fossil fuels, a complex waste stream is produced simultaneously, also known as produced water (PW). Membrane filtration is a promising technology that can successfully enable the treatment and reuse of PW. Silicon carbide (SiC) membranes are preferred for PW treatment, due to their low (ir)reversible fouling compared to other ceramic membranes. However, full SiC membrane is expensive and thus economically less feasible. Therefore, we established a method for coating SiC on alumina (Al₂O₃) ultrafiltration membranes, based on low-pressure chemical vapor deposition at 860 °C. In the presented study the fouling resistance and behavior of these novel membranes, with various pore sizes and under different operating conditions, including flux and crossflow velocity, were evaluated. We also used Al₂O₃ membranes and SiC-coated Al₂O₃ membranes in constant flux mode to treat real oilfield PW with high salinity (142 mS/cm) and COD (22670 mg/L). Additionally, the fouling mechanisms in the SiC-coated and Al₂O₃ membranes were analyzed with the help of Focused Ion Beam-Scanning Electron Microscopy imaging. The major findings were that pore blockage served as the initial (irreversible) fouling mechanism and that the (reversible) cake layer, a mixture of organic and inorganic components, dominated the rest of the filtration cycle, where the SiC coated membrane performed better than the original alumina membrane. In addition, it was found that the application of the SiC coating, and the selection of the appropriate pore size (62 nm) and crossflow velocity (0.8 m/s) increased the fouling mitigation, potentially advancing the utilization of ultrafiltration in treating saline PW for reuse purposes.

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A large decrease in permeability is often observed during the filtration of nano-sized colloids, while fouling is widely regarded as the main explanation for this phenomenon. The osmotic pressure or concentration polarization (CP) of colloids can also contribute to the flux decline. However, the contribution of CP to flux loss cannot be determined by the traditional CP model. In this study, the effect of fouling and CP/osmotic pressure on flux was distinguished. The CP values of polyethylene glycol (PEG) and silica-colloids were determined by the osmotic pressures near the membrane surface and in the feed. The CP induced by colloids accounted for 43–95% of the flux loss in our experiments. Silica exhibited higher CP values (127–460), compared to 7–71 for PEG. This was attributed to the slower back diffusion caused by the larger colloids, as evidenced by the diffusion coefficients of 4.30 × 10⁻¹¹ m²/s for silica (10 nm) and 1.45 × 10⁻¹⁰ m²/s for PEG (2.9 nm). Although the CP was mitigated by increasing the cross-flow velocity, CP values of 31 and 250 were observed for PEG and silica at high Reynolds number of 7317, respectively. The experimentally obtained CP values were also compared with those calculated by the film diffusion model.

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Membrane technology presents an effective solution for treating oily wastewater, a significant environmental hazard stemming from industries such as food processing, metalworking, and oil extraction. Compared to polymeric membranes, ceramic ones exhibit superior mechanical, chemical, and thermal stability, enabling more effective oil removal and easier cleaning. Despite their advantages, membrane fouling remains a challenge, impacting the efficiency of oily wastewater treatment. This review explores oily wastewater characteristics and ceramic membrane applications in treatment processes. It examines the factors influencing ceramic membrane fouling, including wastewater properties (e.g., oil concentration, pH), membrane characteristics (e.g., surface hydrophilicity, charge), and operational parameters (e.g., cross-flow velocity, permeate flux). Strategies to mitigate fouling, such as pretreatment, backpulsing/backwashing for sustained operation, and chemical cleaning for fouling removal, are discussed. By using pretreatment, membrane fouling can be reduced. Backpulsing/backwashing is effective to maintain a long-term operation. Chemical cleaning is effective in removing irreversible fouling and restoring the performance of the ceramic membranes. Moreover, membrane modification techniques that enhance performance are highlighted. Ultimately, the review identifies that effective fouling control is crucial for optimizing ceramic membrane use in oily wastewater treatment, underscoring the need for ongoing research in this area.

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Ceramic nanofiltration is a potential one-step treatment for industrial waste streams. It can remove colloidal particles, oil droplets and some organic molecules. The drawback of the technology is that backwash cannot be applied to remove the accumulated cake layer from the membrane surface. At the moment only chemical cleaning with aggressive oxidizing agents like chlorine are effective to restore the permeability of the membranes after fouling. However, calcium carbonate (CaCO3) precoating has shown potential benefits in preliminary research, but have only been executed at laboratory scale, under a constant pressure and with a limited number of experimental cycles. In the presented work, the CaCO3 precoat/acid cleaning method was comprehensively studied under varying operational conditions. Dead-end filtration of a CaCO3-dispersion was used to precoat the membrane surface. Three different acids were tested to partly dissolve the precoat and remove the cake layer from the membrane surface. It was found that citric acid performed the best to recover the permeability of the membrane, probably due to the chelating properties, capturing the calcium ions, with a good removal of the cake layer during forward flush as a result. The size of precoat particles influenced the efficacy of permeability recovery. The smaller the deposited precoating particles on the membrane surface were, the better the cleaning effect was. It is expected that, when filtering real sewage water, these membranes can operate with one precoat during about 25 days with five consecutive citric acid cleaning cycles before a chlorine-based chemical treatment should thoroughly clean the membrane module.@en

This study investigated the performance of direct hollow fiber nanofiltration (dNF40) membranes from NX Filtration BV on a pilot scale for the treatment of pre-treated IJsselmeer water from Waterwinstation Prinses Juliana (WPJ) in Andijk, as well as the direct treatment of raw IJsselmeer water. The objective was to evaluate the long-term fouling potential and the retention of ions and natural organic matter (NOM) using both WPJ pre-treated IJsselmeer water and raw IJsselmeer water. Additionally, the rejection of organic micropollutants (OMPs) under artificially elevated conditions, referred to as ‘spiked solution’, using WPJ pre-treated IJsselmeer water was investigated. Limited to no fouling was observed on the dNF40 membrane during stable operation when treating both WPJ pre-treated IJsselmeer water and raw IJsselmeer water, even under changing process conditions. NOM removal consistently exceeded 90% regardless of process conditions or water type. The retention of per- and polyfluoroalkyl substances (PFAS) was above 80%, with even higher retention observed for higher molecular weight values. Low molecular weight pharmaceuticals, all below the molecular weight cut-off (MWCO) of the dNF40 membrane (400 Da), exhibited approximately 30% retention. The dNF40 membrane showed better retention of negatively charged pharmaceuticals in the spiked solution compared to positively charged and neutral pharmaceuticals. A total cost of ownership (TCO) analysis unveiled that operational expenditures (OPEX) were three times higher than capital expenditures (CAPEX) for a 5-stage full-scale dNF40 system. Among the components, membrane replacement costs constituted the majority of OPEX (68%), followed by energy costs (31%) and chemical costs (<1%). Overall, the study showcased the suitability of the dNF40 membranes for treating IJsselmeer water, achieving effective removal of NOM and PFAS.

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Worldwide, a considerable amount of oily wastewater is generated, with oil droplets from 2 to 200 nm that are difficult to separate because of their size and colloidal stability. This study presents a novel approach for effectively separating microemulsions via cubic silicon carbide (3C-SiC)-coated alumina (Al ₂O ₃) membranes fabricated based on low pressure chemical vapor deposition (LPCVD). SiC was deposited at a relatively low temperature at 860 °C on 100 nm Al ₂O ₃ membranes using two precursors: SiH ₂Cl ₂ and C ₂H ₂. With the increase in deposition time, up to 25 min, the pore size decreased from 41 nm to 33 nm, which is a smaller pore size of a SiC membrane than previously used for oil/water separation. The polycrystalline 3C-SiC-coated membranes showed improved hydrophilicity (water contact angle of 15°) and highly negatively charged surfaces (−65 mV). Microemulsion filtration experiments were carried out at a constant permeate flux (80 Lm ⁻² h ⁻¹) for six cycles with varying deposition time, pH, surfactant types, and pore sizes. The fouling of the SiC-coated membrane was, compared to the Al ₂O ₃ membrane, effectively mitigated due to the enhanced electrostatic repulsion and hydrophilicity. Surfactant adsorption mainly occurred when the surface charge of the microemulsion and the membranes were opposite. Therefore, the surface charge of the alumina membrane changed from positive to negative when soaked in negatively charged microemulsions, whereas SiC-coated membranes remained negatively charged regardless of surfactant type. The membrane fouling was alleviated when the membrane and oil droplets had the same charge. Lastly, the 62 nm SiC-coated membrane with 20 min coating time was the best choice for the filtration of the microemulsion, because of the high rejection of the oil droplets and low fouling tendency.

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Ceramic nanofiltration (NF) is a promising alternative for direct surface water treatment, but is hampered for full-scale applications by fouling and a lack of eco-friendly cleaning regimes. In this work, an innovative reactive pre-coat layer, consisting of an iron oxychloride catalyst, was constructed on top of commercial ceramic NF membranes, for segregating a large-sized colloid fraction in canal water and Fenton cleaning with a hydrogen peroxide (H₂O₂) solution. The large-sized colloids (3−30 μm) were identified as dominant substances fouling the TiO₂ separation layer of the pristine membranes, leading to a fast increase in their filtration resistance, in contrast to the small-sized colloids (<0.04 μm) and natural organic matter (NOM). As a consequence, the catalyst pre-coat layer with a pore size of 0.1–0.5 μm was able to segregate the large-sized colloids from the TiO₂ separation layer during direct filtration of the raw water. Moreover, filtration under an acceptable flux of around 23 L m⁻² h⁻¹ did not cause pore clogging in the catalyst pre-coat. In addition, Fenton oxidation initiated by the catalytic pre-coat efficiently restored the filtration resistance, whereas sole H₂O₂ flush of the pristine membrane was not effective. In the meantime, the TiO₂ separation layer of the membrane exerted a high NOM rejection of approximately 90%, measured as dissolved organic carbon, while the catalyst pre-coat on the membrane remained active in Fenton cleaning, over five one-day cycles. The findings of this work may provide guidance on the structural and functional design of a catalytic pre-coat layer for a dual purpose of foulant segregation and oxidative removal, particularly in response to key fouling-causing substances, during membrane-based treatment of real water matrices.

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Sodium hypochlorite (NaClO) is widely used for the chemical cleaning of fouled ultrafiltration (UF) membranes. Various studies performed on polymeric membranes demonstrate that long-term (>100 h) exposure to NaClO deteriorates the physicochemical properties of the membranes, leading to reduced performance and service life. However, the effect of NaClO cleaning on ceramic membranes, particularly the number of cleaning cycles they can undergo to alleviate irreversible fouling, remains poorly understood. Silicon carbide (SiC) membranes have garnered widespread attention for water and wastewater treatment, but their chemical stability in NaClO has not been studied. Low-pressure chemical vapor deposition (LP-CVD) provides a simple and economical route to prepare/modify ceramic membranes. As such, LP-CVD facilitates the preparation of SiC membranes: (a) in a single step; and (b) at much lower temperatures (700–900 °C) in comparison with sol-gel methods (ca. 2000 °C). In this work, SiC ultrafiltration (UF) membranes were prepared via LP-CVD at two different deposition temperatures and pressures. Subsequently, their chemical stability in NaClO was investigated over 200 h of aging. Afterward, the properties and performance of as-prepared SiC UF membranes were evaluated before and after aging to determine the optimal deposition conditions. Our results indicate that the SiC UF membrane prepared via LP-CVD at 860 °C and 100 mTorr exhibited excellent resistance to NaClO aging, while the membrane prepared at 750 °C and 600 mTorr significantly deteriorated. These findings not only highlight a novel preparation route for SiC membranes in a single step via LP-CVD, but also provide new insights about the careful selection of LP-CVD conditions for SiC membranes to ensure their long-term performance and robustness under harsh chemical cleaning conditions.@en

Catalytic ceramic nanofiltration (NF) is a promising technology for direct wastewater reclamation, given its high separation selectivity and reactive surfaces for oxidative removal of fouling. A better understanding of the relation between fouling types and oxidative cleaning efficacy under high organic loading conditions is of practical importance for realizing stable filtration/cleaning performance in long-term water reclamation operations. In this work, Fenton cleaning, using a hydrogen peroxide solution and an iron oxychloride catalyst pre-coat layer on top of commercially available ceramic NF membranes, was studied with respect to high organic loaded fouling, simulated by a concentrated sodium alginate solution in the presence of calcium. Adsorption (in the absence of a permeate flow) and constant-pressure filtration (with a permeate flow) experiments were performed to distinguish between permeance decreases as a result of either adsorptive or cake layer fouling. The results show that the flux evolution could be divided into an initial sharp flux decline, due to rapid adsorption of the foulants, and a subsequent gradual flux decrease, resulting from progressive cake build-up on the membrane. The two-stage flux decrease was enhanced during the constant-pressure filtration experiments, because they start at a high flux with a high fouling rate, while the flux gradually decreases as fouling proceeds. During multiple adsorption/cake filtration/Fenton cleaning cycles, the cake layer fouling was sufficiently removed by Fenton cleaning in contrast to the adsorptive fouling. However, the total permeate production during ceramic NF was not influenced by the remaining adsorptive fouling (after cleaning), since the adsorptive fouling always only occurs at the beginning of each cycle. The findings provide new insights into the criteria for evaluating and optimizing the efficacy of oxidative (Fenton) cleaning during ceramic NF in water treatment.

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Verwijdering van organische microverontreinigingen uit huishoudelijk afvalwater, waaronder medicijnresten, staat sterk in de belangstelling om de oppervlaktewater kwaliteit te verbeteren, de drinkwaterbronnen te beschermen en te voldoen aan toekomstige EU richtlijnen. In minder dan vijf jaar is AdOx, een technologie waarin adsorptie en oxidatie word en gecombineerd, ontwikkeld tot een veelbelovende techniek. Ten opzichte van referentietechnieken zijn de CO2-voetafdruk klein en de kosten laag. De Nederlandse richtlijn van 70% verwijdering wordt gehaald. Ondanks het gebruik van ozon resulteert AdOx niet in bromaat vorming en oxidatiebijproducten in het behandelde afvalwater. Er is nog veel ruimte voor verdere optimalisatie.@en

This work investigates the enhancement of antifouling properties of ceramic nanofiltration membranes by surface modification via atomic layer deposition (ALD) of TiO₂. Feed solutions containing bovine serum albumin (BSA), humic acid (HA) and sodium alginate (SA) were used as model foulants. The classic fouling mechanism models and the modified fouling indices (MFI) were deduced from the flux decline profiles. Surface roughness values of the ALD coated and uncoated membranes were 63 and 71 nm, respectively, while the contact angles were 34.2 and 59.5°, respectively. Thus, coating increased the water affinity of the membrane surfaces and consequently improved the anti-fouling properties. The MFI values and the classic fouling mechanism correlation coefficients for cake filtration for the ALD coated and the uncoated membrane upon SA fouling were 42,963 (R ² = 0.82) and 143,365 sL⁻² (R ² = 0.98), respectively, whereas the correlation coefficients for the combined foulants (SA + BSA + HA) were 267,185 (R ² = 0.99) and 9569 sL⁻² (R ² = 0.37), respectively. The study showed that ALD can effectively enhance the antifouling properties of ceramic membranes.

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The type and loading level of oxygen-containing functional groups on graphene oxide (GO) nanosheets significantly affect the size and alignment of nanochannels formed between the GO nanosheets and the separation performance of laminar GO membranes. Here, we demonstrate how double-oxidation of GO leads to the higher surface charge of GO nanosheets, the formation of highly stable water-based GO solution, more-ordered deposition of GOs on the polyethersulfone membrane through the pressure-assisted self-assembly method, and the formation of highly durable GO membranes possessing smoother surface morphology and higher antifouling properties. A multi-technique investigation was applied to follow the physicochemical difference between GO and double-oxidized GO, and the physical stability and separation performance of the corresponding membranes using experimental and computational studies. The double-oxidized GO-based membranes provided a significantly high water flux of 230 L/(m².h) in 2.5 bar transmembrane pressure, excellent rejection of 99.9% for methylene blue (MB) dye, and outstanding separation performance stability over time. In contrast, GO membranes showed rejection of 81.5% for MB, and their separation performance diminished significantly over time. The antifouling properties of double-oxidized GO membranes were substantially higher (∼ four times) due to their higher negative surface charge and smoother surface morphology. The density functional theory (DFT) was used to gain insight into the interactions between the functional groups and the reasoning for the higher mechanical stability of double-oxidized GO membranes. Results revealed that the formation energy of GO decreases by increasing the number density of functional groups. It was also found that a higher number of carboxyl groups at the edges of the double-oxidized GO leads to higher hydrogen bonding, higher binding energy, and a more stable GO-membrane structure.

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This work presents the first comprehensive investigation of natural organic matter (NOM) fraction removal using ceramic membranes in South Africa. The rate of removal of bulk NOM (measured as UV₂₅₄ and DOC % removal), the biodegradable dissolved organic carbon (BDOC) fraction, polarity-based fractions, and fluorescent dissolved organic carbon (FDOM) fractions was investigated from water abstracted from drinking water treatment plants (WTPs) in South Africa. Further, mechanisms of ceramic membrane fouling by waters of South Africa were studied. Ceramic membranes removed more than 80% DOC from samples from coastal WTPs, whereas for inland plants, the removal was between 60% and 75% of DOC. FDOM was removed to at least 80% regardless of the site of the plant. The BDOC removal by the ceramic membranes was above 85%. The hydrophobic fraction was the most amenable to removal by ceramic membranes regardless of the site of sample abstraction (above 60% for all sites). The freshness index (β:α) correlated strongly to UV₂₅₄ removal (R² = 0.96), thus UV₂₅₄ removal can serve as a proxy for the susceptibility to removal of such class of NOM by ceramic membranes. This investigation demonstrated that ceramic membranes could be a valuable technology if integrated into the existing WTPs. Practitioner Points: The removal of bulk parameters by ceramic membrane was greater than unit conventional processes used in all the sampled water treatment plants. The hydrophobic polarity-based fraction of NOM was the most amenable to removal by ceramic membranes regardless of the site of the WTP. Polarity-based fractions, aromaticity, and initial DOC had a combined influence on the removal of organic matter by ceramic membranes as explained by principal component three.

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Ceramic membranes have drawn increasing attention in oily wastewater treatment as an alternative to their traditional polymeric counterparts, yet persistent membrane fouling is still one of the largest challenges. Particularly, little is known about ceramic membrane fouling by oil-in-water (O/W) emulsions in constant flux filtration modes. In this study, the effects of emulsion chemistry (surfactant concentration, pH, salinity and Ca²⁺) and operation parameters (permeate flux and filtration time) were comparatively evaluated for alumina and silicon carbide (SiC) deposited ceramic membranes, with different physicochemical surface properties. The original membranes were made of 100% alumina, while the same membranes were also deposited with a SiC layer to change the surface charge and hydrophilicity. The SiC-deposited membrane showed a lower reversible and irreversible fouling when permeate flux was below 110 L m⁻² h⁻¹. In addition, it exhibited a higher permeance recovery after physical and chemical cleaning, as compared to the alumina membranes. Increasing sodium dodecyl sulfate (SDS) concentration in the feed decreased the fouling of both membranes, but to a higher extent in the alumina membranes. The fouling of both membranes could be reduced with increasing the pH of the emulsion due to the enhanced electrostatic repulsion between oil droplets and membrane surface. Because of the screening of surface charge in a high salinity solution (100 mM NaCl), only a small difference in irreversible fouling was observed for alumina and SiC-deposited membranes under these conditions. The presence of Ca²⁺ in the emulsion led to high irreversible fouling of both membranes, because of the compression of diffusion double layer and the interactions between Ca²⁺ and SDS. The low fouling tendency and/or high cleaning efficiency of the SiC-deposited membranes indicated their potential for oily wastewater treatment.

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There is a global need for optimizing the use of water that has resulted from increased demand due to industrial development, population growth, climate change and the pollution of natural water resources. One of the solutions is to use reclaimed water in industrial applications that do not require water of potable quality, such as cooling water. However, for cooling water, (treated) wastewater’s hardness is too high, apart from having a high load of suspended solids and organic matter. Therefore, a combination of softening with ceramic micro-filtration was proposed for treating wastewater treatment effluent containing fouling agents for potential use in industrial cooling systems. The effectiveness of the softening process on model-treated wastewater with calcium hydroxide in the presence of phosphate and sodium alginate was first evaluated using jar tests. Furthermore, membrane fouling was studied when filtering the softened water. The results showed that the inhibition of calcium carbonate precipitation occurred when inorganic substances, such as phosphate and organic compounds, were present in the water. The fouling of the membranes due to sodium alginate in water was only slightly negatively affected when combined with softening and phosphate. Therefore, this combination of treatments could be potentially helpful for the post-treatment of secondary effluent for cooling systems.@en

AdOx is een combinatie van een adsorptieproces en een oxidatietechniek. Een veelbelovende technologie om medicijnresten uit afvalwater te halen. En winnaar van
de Waterinnovatieprijs 2021, categorie Gezond Water en Gezonde Bodem.@en

Silica scaling is one of the major scaling challenges in Reverse Osmosis (RO). The safe operation practice is to keep the silica concentration below 150 mg/L in RO concentrate. This study addresses the effects of divalent cations such as calcium and magnesium on silica scaling in a seawater RO installation used as a pretreatment to Eutectic Freeze Crystallisation (EFC). Results showed that in the absence of antiscalant and divalent cations a sustained silica concentration of approximately 280 mg/L in concentrate is possible without declining membrane permeability. At a higher concentration of divalent cations, the membrane permeability decreased. Membrane autopsy and analysing destructed membrane showed a relatively low magnesium and a high calcium concentration on the membrane after adding divalent ions into the solutions. It is concluded that in absence of divalent cations and without antiscalant the limits of 150 mg/L silica can be extended to 280 mg/L for 6–8 h.

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Organic micropollutants (OMPs) that occur in the aquatic environment are an emerging concern. Adsorption by granular zeolites and regenerating exhausted zeolites by gaseous ozone is an innovative and advanced treatment technology for removing OMPs from wastewater treatment plant (WWTP) effluent. In this study, WWTP effluent spiked with eleven OMPs at 4–5 µg/L was treated by this combined technology, which included five steps in each cycle. The five steps comprised 1) selective adsorption of OMPs from WWTP effluent for five days by a zeolite granules fixed-bed column, 2) pre-backwash of the column, 3) drying of the column, 4) in-situ regeneration of the column with gaseous ozone 5) post-backwash of the column. The removal efficiency of eight OMPs (sotalol, metoprolol, propranolol, trimethoprim, clarithromycin, carbamazepine, methyl-benzotriazole, and benzotriazole) reached between 70 % and 100 % in six cycles. The adsorption of sulfamethoxazole and diclofenac was less favourable. In each cycle, less than 8 % of dissolved organic carbon (DOC) was removed from the WWTP effluent. The effect of the natural organic matter (NOM) on the adsorption of OMPs was negligible. Ozone consumption during regeneration was reduced by around 70 % by increasing pre-backwash duration from 30 min to 1 h. Ozonation directly with ozone gas can effectively regenerate the zeolite granules in the column under low ozone consumption.@en

A novel sol-gel method was employed in this study to efficiently synthesize SnO2 nanoparticles to catalyze the ozonation of acetaminophen (ACT) from aqueous solutions. The influence of various parameters including Sn source, type of capping and alkaline agents, and calcination temperature on the catalytic activity of the SnO2 preparations was investigated. The SnO2 nanoparticles prepared by tin tetrachloride as Sn source, NaOH as gelatin agent, CTAB as capping agent and at calcination temperature of 550 °C (SnNaC-550) exhibited the maximum performance in the catalysis of ACT. The optimized catalyst (SnNaC-550) had spherical-homogeneous and cubic-shaped nanocrystalline particles with 5.5 nm mean particle size and a BET surface area of 81 m2/g, which resulted in 98% degradation and 84% mineralization of 50 mg/L ACT at 20 and 30 min reaction time, respectively when combined with ozonation (COP). Based on the radical scavenger experiments, •OH was the major oxidizing agent involved in the removal of ACT. LC/MS analysis showed that short-chain carboxylic acids were the main intermediates. Furthermore, the SnNaC-550 catalytic activity was preserved after four successive cycles. Collectively, the new method has the potential to efficiently synthesize stable and reusable SnO2 nanoparticles to catalyze the ozonation of ACT from aquatic environments.@en

Ceramic nanofiltration (NF) is a newly-developed technology for water recycling, but is still limited to pilot-scale applications. Lacking efficient and eco-friendly strategies for cleaning ceramic NF membrane impedes its scaling-up in industries. Forward flush, backwash and acidic/caustic cleaning are not efficient enough. In this work, a novel oxalic acid-aided Fenton process was proposed for synergistic relaxation/oxidation of persistent Ca²⁺-mediated gel-like fouling of ceramic NF membrane. A reactive catalyst layer was online pre-coated on top of the membrane via a pressure-driven cross-flow pre-filtration of Fe₃O₄ hydrosols. The gel-like fouling was simulated by alginate in the presence of Ca²⁺ ions. Results show that the Fe₃O₄ loading could be readily tuned from 0.16 to 1.34 g m⁻² by altering the permeate flux during the pre-coating. The membrane permeability loss due to the pre-coating was minimal (<10%). The combination of oxalic acid chelation and Fenton-based oxidation resulted in high flux recovery (85.07%) for the iron-oxide pre-coated membrane, whereas the single treatment by hydrogen peroxide (H₂O₂) or oxalic acid was inefficient. This synergistic effect was attributed to relaxation of the Ca²⁺-mediated gel layer via oxalic acid/Ca²⁺ chelation, which presumably facilitated H₂O₂ diffusion at the Fe₃O₄/foulant interface. The iron-oxide pre-coated membrane maintained stable initial normalized fluxes (83.33–90.15%) through the oxalic acid/H₂O₂ cleaning over five cycles, with no need of refreshing the iron-oxide pre-coat. Additionally, the leaching of iron from the iron-oxide pre-coat by oxalic acid was suppressed by the oxalic acid/H₂O₂ combination, owing to a reactive shielding by competitive sorption of H₂O₂ onto the Fe₃O₄ surface. Overall, the synergistic relaxation/oxidation method, demonstrated in this study, provides new insights into improving reactivity of Fenton-based processes on hybrid catalytic ceramic membranes for water treatment or fouling control.

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