S.G.J. Heijman
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Analysis of fouling control strategies in ceramic nanofiltration membranes
CaCO₃ precoating versus continuous dosing
Ceramic membrane filtration is increasingly applied in water reclamation and purification, demonstrating particular efficacy in treating challenging industrial wastewater streams and non-potable water sources. During precoating, a removable filtration layer can be deposited on the membranes to enhance particle retention and reduce fouling, although it requires periodic renewal. The continuous dosing strategy is implemented by premixing calcium carbonate (CaCO₃) with the feed solution at the onset of each cycle, prior to the start of filtration. Both methods address membrane fouling but differ fundamentally in longevity and modification mechanisms. In this study, dead-end filtration was employed to deposit a CaCO₃ coating, with particular focus on fouling mitigation using citric acid treatment. Compared to the precoating method, the continuous dosing method enabled the addition of CaCO₃ throughout the fouling experiment, followed by citric acid cleaning. Experimental results demonstrated that, although the continuous dosing method also showed good permeability recovery, the precoated membrane exhibited better permeability recovery than the continuous dosing method, with consistent observations across both model wastewater and surface water. This performance difference likely results from the protective CaCO₃ layer on the membrane, while the continuous dosing method allowed for partial foulant deposition before sufficient CaCO₃ coverage was achieved. The precoated membrane exhibited the lowest irreversible fouling (3 × 1010 m−1 after the second cycle, versus 21 × 1010 m−1 for continuous dosing and 72 × 1010 m−1 for the uncoated membrane). The precoated membrane also performed better in treating Schie Canal water. The treatment system showed better performance in bulk water quality improvement, achieving a 94% removal of dissolved organic carbon and a 65% reduction in electrical conductivity. The process exhibited high ion selectivity, rejecting divalent cations (Ca2+, Mg2+ > 68%) and specific anions, with particularly high removal rates for fluoride and phosphate (F−, PO₄3− > 98%).
Fouling remains a critical challenge for ceramic ultrafiltration membranes, limiting their long-term performance for water treatment. Fenton-like reactions have been widely used for fouling removal due to the formation of strong radicals. Integrating these reactions into backwash offers a promising strategy for fouling control. However, it has been unclear how Fenton-like backwash is influenced by operational parameters and fouling structures. Here we reveal the key factors influencing Fenton-like backwash by systematically studying its performance under varying conditions, such as backwash pressure (0.3–1 bar), duration (18–36 min), fouling structure (caused by 1–5 mM Ca) and the long-term operation, to provide an effective and practical cleaning. CuFe2O4 was grown on ceramic ultrafiltration membranes due to its stability and high catalytic efficiency in activating Fenton-like reactions. We found that Fenton-like backwash achieved the highest cleaning efficacy of approximately 70 % over three cycles at a low backwash pressure of 0.3 bar, while hydraulic backwash remained ineffective under all conditions. Backwash pressure, rather than duration, was identified as the dominant factor governing the Fenton-like cleaning, due to its impact on the residence time of Fenton-like agents (H2O2). The presence of a high Ca concentration (3 and 5 mM) altered the fouling behaviour, and reduced the cleaning efficacy of Fenton-like backwash. This reduction was attributed to the formation of rigid alginate clusters that were resistant to Fenton-like reactions. The contribution of •OH to the enhanced Fenton-like backwash was confirmed by the quenching experiments. Furthermore, the CuFe2O4-coated membranes exhibited stable flux recovery (83 %–94 %) in the long-term treatment of a concentrated alginate (800 mg/L), showed low or negligible leaching in hash environments (30 mM H2O2, 0.1 % NaClO or 10 mM NaOH), and maintained comparable performance after 96 h aging by 30 mM H2O2. This study clarifies the factors governing Fenton-like backwash, and demonstrates that a robust and effective strategy for fouling removal can be achieved by coupling this cleaning method with catalytic ceramic membranes.
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.
Oil and Water Recovery from Palm Oil Mill Effluent
A Comparative Study of PVDF and α-Al2O3 Ultrafiltration Membranes
Impact of ionic strength and surface charge on ceramic membrane fouling by oil-in-water emulsions
A quantitative analysis using DLVO and XDLVO models
Large amounts of oily wastewater, which can be defined as produced water, are generated in oilfields. Ultrafiltration (UF) serves as an effective and economical method to purify produced water. Unfortunately, membrane fouling during produced water treatment is severe. In this paper, the effects of the ionic strength (1, 20, and 100 mM) as well as different surfactants on the membrane fouling are investigated. Four surfactants, including SDS (anionic), APG (non-ionic), CTAB (cationic) and DDAPS (zwitterionic), were selected for this study. The Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended DLVO (XDLVO) models were used to quantify interactions between the membrane-oil droplet and deposited oil layer-oil droplet surfaces and to compare these interactions with the fouling experiments. The (X)DLVO interaction energies of the membrane-oil droplet exhibited a strong agreement with the fouling tendencies at 1 mM salinity. The SiC-deposited (B20) membrane showed less reversible and irreversible membrane fouling than the Al2O3 (B0) membrane when filtering negatively charged O/W emulsions stabilized with SDS, APG, or DDAPS. The DLVO model predicted a higher fouling tendency at higher salinity levels during the filtration of SDS, APG, or DDAPS-stabilized O/W emulsions and a decreased fouling tendency for CTAB-stabilized emulsion with the B20 membrane. However, at higher salinity levels, the XDLVO energy barrier was affected by both the repulsive electrostatic double layer (EL) interaction and attractive Lewis acid-base (AB) interaction. By comparing both experiments and (X)DLVO modeling, this study improves the fundamental understanding of the effect of ionic strength and surfactant types on reversible and irreversible fouling of the Al2O3 and SiC-coated membranes fouling by O/W emulsions.
Evaluation of membrane fouling at constant flux and constant transmembrane pressure conditions
Implications for membrane modification
Membrane modification is commonly applied in water purification and wastewater treatment to reduce fouling of membranes. However, the influence of fouling test methods on evaluating pristine and modified membranes is often overlooked. This study investigates fouling behavior of alumina and SiC-deposited alumina membranes during oil-in-water emulsion filtration under both constant flux and constant transmembrane pressure conditions. Threshold flux was first determined using flux-stepping experiments, with the 90-min SiC-deposited membrane showing the highest value at 95 L m− 2 h− 1. In single-cycle constant flux tests, fouling trends aligned with threshold flux data. However, when backwash was included, fouling characteristics shifted and depended on the permeate flux. Enhanced hydrophilicity and surface charge improved backwash efficiency in modified membranes. Yet, extensive modification negatively affected performance due to significant permeance loss (>57 %). Under constant pressure, fouling was dominated by internal pore blocking, and backwash efficiency was solely linked to membrane permeance, regardless of surface properties. Thus, constant flux filtration with backwash best reflects operational conditions and is recommended for evaluating membrane modifications.
Oil and Water Recovery from Palm Oil Mill Effluent
A Comparative Study of PVDF and α-Al2O3 Ultrafiltration Membranes
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.
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.
Ceramic membrane filtration for oily wastewater treatment
Basics, membrane fouling and fouling control
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.
Operation and performance analysis of direct hollow fiber nanofiltration
A pilot study at IJsselmeer
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.
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.
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.