Coagulation-ultrafiltration Process Research Articles

Unveiling the role of cake layer in coagulation-ultrafiltration on membrane fouling and emerging application as dynamic membrane before ultrafiltration

Cake layer is considered to play a crucial role in membrane fouling during the coagulation-ultrafiltration process. However, the contribution of the cake layer on membrane fouling and probable natural organic matter (NOM) removal in this process is unclear, leading to a limited understanding of cake layer and potential secondary utilization. Here, ultrafiltration (UF) membrane fouling contribution, NOM removal, and dynamic membrane application of the cake layer were investigated. Results showed reversible fouling was dominated by cake layer, whereas irreversible fouling was determined by both cake layer and residual NOM in coagulation effluent. Compared with direct UF, the cake layer improved approximately by 15 % of HA removal with molecular weight (MW) of 2000–4000 Da. By optimizing membrane material, HA removal and membrane fouling alleviation were synchronously achieved by cake layer deposition-UF. According to mechanisms analysis, HA removal was attributed to the adsorption or interception of HA with larger MW by the cake layer. Zeta potential and fractal dimension of flocs, and contact angle of the cake layer were closely related to HA removal by cake layer, whereas reversible and irreversible fouling were positively correlated with cake layer thickness and floc fractal dimension respectively. Compared with other dynamic membranes, the cake layer had the best economic performance, which provided application potential on NOM removal in micro-polluted surface water.

Magnetic nanoparticle loading and application of weak magnetic field to reconstruct the cake layer of coagulation-ultrafiltration process to achieve efficient antifouling: Performance and mechanism analysis

Abandoning the costly development of new membrane materials and instead directly remodeling the naturally occurring cake layer constitutes a dynamic, low-cost, long-lasting, and proactive strategy to "fight fouling with fouling". Several optimization strategies, including coagulation/modified magnetic seed loading and applying a weak magnetic force (0.01T) at the ultrafiltration end, improved the anti-fouling, retention, and sieving performances of conventional ultrafiltration process during the treatment of source water having complex natural organic matter (NOMs) and small molecule micropollutants. Two modified magnetic seeds we prepared were composite nano-seed particles (Fe3O4@SiO2-NH2 (FS) and Fe3O4@SiO2@PAMAM-NH2 (FSP)). Aim of the study was to regulate the formation of cake layer via comprehensive testing of the antifouling properties of optimized processes and related mechanistic studies. It was found to be essential to enhance the interception of xanthate and tryptophan proteins in the cake layer for improving the anti-fouling performance based on the correlation and redundancy analyses, while the use of modified magnetic seeds and magnetic field showed a significant positive impact on water production. Blockage modeling demonstrated the ability to form a mature cake layer during the initial filtration stage swiftly. This mitigated the risk of irreversible fouling caused by pore blockage during the early stage of coagulation-ultrafiltration. Morphologically, the reconstructed cake layer exhibited elevated surface porosity, an internal cavity channel structure, and enhanced roughness that can promote increased water flux and retention of water impurities. These optimized the maturity of the cake layer in both time and space. Density Functional Theory (DFT), Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, and Modified Extended Derjaguin-Landau-Verwey-Overbeek (MDLVO) calculations indicated aggregation behavior of matter on the cake layer to be enhanced effectively due to magnetic seed loading. This is mainly due to the strengthening of polar interactions, including hydrogen bonding, π-π* conjugation, etc., which can happen between the cake layer loaded with FSP and the organic matter. Under the influence of a magnetic field, magnetic force energy (VMF) significantly impacts the system by eliminating energy barriers. This research will provide innovative strategies for effectively purifying intricate source water through ultrafiltration while controlling membrane fouling.

Effect of nano Fe3O4-(CMC-Na)-PFS coagulant on coagulation–ultrafiltration process for treatment of algae -rich water

A novel composite flocculant (PCNF) was prepared using nano Fe3O4 as the condensed core, sodium carboxymethyl cellulose (CMC-Na) as the binder, and polyferric sulfate (PFS). The results indicate that the mass ratio of Fe3O4 to PFS is the key factor determining the flocculation effect of PCNF. When the mass ratio of Fe3O4 to PFS is 1:3, the Zeta potential value is approximately − 1.5 mV, indicating better removal of algae through adsorption electroneutralization. The resulting floc, characterized by negative charge and a loose structure, forms a filter cake layer that is easily backwashed on the surface of the ultrafiltration membrane. This floc also creates strong electrostatic repulsion with the membrane surface. Experimental results demonstrate that the specific flux decreased to 0.69, the total relative pollution was 0.33, and the proportion of irreversible pollution was only 34.65%, all of which were superior to traditional flocculant like PACl. Through microinterface mechanism analysis, it is concluded that the new PCNF flocculant, in combination with algal matter, forms a floc structure critical for mitigating ultrafiltration membrane pollution caused by high algal content in natural surface water.

Continuation of a cleaning process: Application of MNBs-coagulation process to mitigate ultrafiltration membrane fouling

The MNBs-coagulation process as a novel and cleaning enhanced coagulation process has been demonstrated to enhance the removal efficiency of hydrophilic organics. In this study, while continuing the concept of cleaning production, the MNBs-coagulation process was first applied to the ultrafiltration process and was expected to alleviate the ultrafiltration membrane fouling. This study investigated the effect of the involvement of MNBs in coagulation-ultrafiltration process (the MC-UF process) on the fouling behaviour of ultrafiltration membrane based on the calculation of membrane resistance distribution and the fitting of membrane fouling model. In addition, the NOM removal efficiency, floc characteristics analysis and membrane hydrophilicity analysis were used to illustrate the mechanism of mitigating ultrafiltration mebrane fouling by the MC-UF process. The experimental results showed that the involvement of MNBs in the coagulation-ultrafiltration process was able to reduce the irreversible fouling and TMP by 43.1 % and 41.6 % respectively. This phenomenon could be attributed to the involvement of MNBs in the coagulation process to improve the removal efficiency of hydrophilic organics and to enhance the characteristics of flocs, thus reducing the possibility of hydrophilic organics and broken flocs entering and blocking the membrane pores. In addition, the FT-IR spectral changes before and after the floc breakage were analyzed by 2D-COS technique in this study, and it was found for the first time that the participation of MNBs in the coagulation process could change the sequence of functional group transformation within the floc, and promote the generation of hydrogen bonds between flocs by hindering the generation of hydroxyl groups (-OH), and improve the shear resistance and regrowth capacity of flocs while reducing the possibility of broken flocs entering and blocking membrane pores. In summary, the MC-UF process proposed in this study can significantly mitigate ultrafiltration membrane fouling while meeting cleaning production, providing theoretical support for the application of the process to practical engineering.

Application of a novel zirconium coagulant in the coagulation-ultrafiltration process: Fluoride removal and membrane fouling alleviation

Groundwater fluoride pollution is a worldwide problem that threatens human health and drinking water. Economical and efficient coagulation is the most widely used defluorination technology. The fluoride removal efficiency depends on the complexation and adsorption capacities of the hydrolyzed metal salt coagulant, so the development of new metal coagulants is the key to coagulation defluorination technology. In this study, novel polymeric zirconium salt coagulants (ZXCs) were prepared by the sol-gel method. Their capabilities in coagulation and coagulation-ultrafiltration processes were evaluated and compared with those of the traditional polyaluminum chloride (PAC) and polyferric sulfate (PFS) coagulants. ZXC exhibited more effective fluoride removal than PAC and PFS, and the fluoride removal rates of ZXC, PAC and PFS were 81.0 %, 24.7 % and 5.4 % with the optimized dosages of 0.30 mM and pHs of 5.0, 6.0 and 5.0, respectively. With an initial fluoride concentration of 4.0 mg/L, 0.30 and 1.5 mM doses of ZXC reduced the fluoride concentrations to 0.76 and 0.13 mg/L. The structures and properties of ZXC and the flocs were characterized with Fourier Transform Infrared spectroscopy (FT-IR), X-ray Diffraction (XRD), X-ray photoelectron Spectroscopy (XPS), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area determinations. The series characterization and hydrolysis precipitation area map showed that adsorption onto hydroxyl groups and ion exchange with surface hydroxyl groups were the main pathways for fluoride removal by ZXC. In the coagulation-ultrafiltration defluorination process, the highly polymerized ZXC was fully hydrolyzed under acidic conditions to form larger and looser flocs with almost no dissolved residue, which substantially reduced membrane fouling. This work provides new insights into the development of materials and technologies for fluoride removal from drinking water.

New insights into membrane fouling in coagulation-ultrafiltration by cake characteristics analysis: A case study with PACl-Al13 and PACl

Membrane fouling is a bottleneck issue that hindered the further application of ultrafiltration technology. To alleviate membrane fouling, coagulation-ultrafiltration (C-UF) process using polyaluminum chloride (PACl) and PACl-Al13 with high proportion of Al13O4(OH)247+ as coagulants, respectively, were investigated at various pH conditions. Results indicated that an increase in solution pH contributed to larger floc size and looser floc structure for both PACl and PACl-Al13. It was conducive to the formation of more porous cake, as evidenced by mean pore area and pore area distribution of cake, leading to lower reversible fouling. Furthermore, humic acid (HA) removal presented a trend of first increasing and then decreasing with the increase of pH. The optimal HA removal was achieved at pH 6 regardless of coagulant type, suggesting that the slightest irreversible fouling should be occurred at this point. Interestingly, the irreversible fouling with PACl coagulant achieved a minimum value at pH 9, while the minimal irreversible fouling with PACl-Al13 was observed at pH 6. We speculated that the cake formed by PACl could further intercept HA prior to UF process at alkaline pH. Furthermore, compared with PACl, PACl-Al13 had a stronger charge neutralization ability, thus contributing to more compact floc structure and higher HA removal at various pH conditions. By UF fractionation measurement, higher HA removal for PACl-Al13 was due to higher removal of HA with molecular weight less than 50 kDa.

A strategy to alleviate membrane fouling by optimizing the structure of the cake layer formed by flocs deposited directly on the membrane in the ultrafiltration process through coagulation and nanoscale Fe3O4/Fe3O4@SiO2 load

Membrane fouling has always been a problem hindering the practicability of ultrafiltration. Direct regulation of the structure of the cake layer formed by rapid deposition of flocs as a “secondary barrier” in the in-line coagulation ultrafiltration (C-UF) process has acquired importance as a research topic in comparison to membrane modification and standard coagulation ultrafiltration. In this study, membrane fouling was controlled in the C-UF process via coagulation/nano-scale Fe3O4 load (C/FL-UF) and coagulation/nano-scale Fe3O4@SiO2 load (C/FSL-UF). The promotion effects of these two processes (C/FL-UF and C/FSL-UF) on the reduction of membrane fouling and improvement of water quality were systematically studied employing simulated surface water. Floc characteristics, XDLVO theory, and the Hermia model, etc were employed to explain the optimization of cake layer. For coagulation/Fe3O4 load, the floc size was large and loose, whereas, for coagulation/Fe3O4@SiO2 load with high recoverability., the floc size was slightly loose. The newly constructed cake layer had improved porosity, structural stability and capacity of water transport. Meanwhile, decrease of unit adhesion free energy and secondary minimum depth along with the substantial increase of energy barrier between the reconstructed cake layers and membranes or colloids explained the mechanism of reduced membrane fouling from the surface energetics. The gradual decrease of water contact angle and the optical images proved that the affinity of the cake layer was significantly reduced. Hermia model further validated the accuracy of this study in controlling membrane fouling by regulating the formation of the cake layer. Finally, the study concluded by analyzing the practicability and efficacy of the procedure to further elucidate the applicability of this research.

Removal behaviors and mechanism of polystyrene microplastics by coagulation/ultrafiltration process: Co-effects of humic acid

Microplastics (MPs) have been detected in drinking water, which could absorb or accumulate humic acid (HA) and threaten the water quality. Coagulation-ultrafiltration (CUF) is a common drinking water treatment technology, but its behavior and mechanism of removing MPs and MPs-HA remain unclear. In this study, the removal mechanism of polystyrene (PS)-MPs coagulated by Al- and Fe-based salts with or without HA was investigated to optimize the CUF process. The results showed that Al-based salt (92.7 %) was better than Fe-based salt (91.2 %) in the removal efficiency of PS or HA, and the optimal coagulants dosage of PS-HA composite system (12 mg·L−1) was higher than that of the individual PS system (9 mg·L−1). Moreover, the coagulation mechanism was studied by Fourier transform infrared spectroscope (FTIR) and X-ray photoelectron spectroscopy (XPS). The oxygen group in PS and PS-HA was the main binding site of Al and Fe hydrolysate, and the effects of charge neutralization, adsorption bridging, and sweep flocculation became weaker in turn at the optimal dosage. In addition, the cake layer formed by coagulation and the presence of HA alleviated the irreversible membrane fouling by intercepting flow and re-adsorption. This study guides the improvement of the traditional drinking water treatment process to remove MPs.

Cake layer 3D structure regulation to optimize water channels during Al-based coagulation-ultrafiltration process

The variation in cake layer three-dimensional (3D) structures and related water channel characteristics induced by coagulation pretreatment remains unclear; however, gaining such knowledge will aid in improving ultrafiltration (UF) efficiency for water purification. Herein, the regulation of cake layer 3D structures (3D distribution of organic foulants within cake layers) by Al-based coagulation pretreatment was analyzed at the micro/nanoscale. The sandwich-like cake layer of humic acids and sodium alginate induced without coagulation was ruptured, and foulants were gradually uniformly distributed within the floc layer (toward an isotropic structure) with increasing coagulant dosage (a critical dosage was observed). Furthermore, the structure of the foulant-floc layer was more isotropic when coagulants with high Al13 concentrations were used (either AlCl3 at pH 6 or polyaluminum chloride, in comparison with AlCl3 at pH 8 where small-molecular-weight humic acids were enriched near the membrane). These high Al13 concentrations lead to a 48.4% higher specific membrane flux than that seen for UF without coagulation. Molecular dynamics simulations revealed that with increasing Al13 concentration (Al13: 6.2% to 22.6%), the water channels within the cake layer were enlarged and more connected, and the water transport coefficient was improved by up to 54.1%, indicating faster water transport. These findings demonstrate that facilitating an isotropic foulant-floc layer with highly connected water channels by coagulation pretreatment with high-Al13-concentration coagulants (having a strong ability to complex organic foulants) is the key issue in optimizing the UF efficiency for water purification. The results should provide further understanding of the underlying mechanisms of coagulation-enhancing UF behavior and inspire precise design of coagulation pretreatment to achieve efficient UF.

Impacts of Calcium Addition on Humic Acid Fouling and the Related Mechanism in Ultrafiltration Process for Water Treatment.

Humic acid (HA) is a major natural organic pollutant widely coexisting with calcium ions (Ca2+) in natural water and wastewater bodies, and the coagulation-ultrafiltration process is the most typical solution for surface water treatment. However, little is known about the influences of Ca2+ on HA fouling in the ultrafiltration process. This study explored the roles of Ca2+ addition in HA fouling and the potential of Ca2+ addition for fouling mitigation in the coagulation-ultrafiltration process. It was found that the filtration flux of HA solution rose when Ca2+ concentration increased from 0 to 5.0 mM, corresponding to the reduction of the hydraulic filtration resistance. However, the proportion and contribution of each resistance component in the total hydraulic filtration resistance have different variation trends with Ca2+ concentration. An increase in Ca2+ addition (0 to 5.0 mM) weakened the role of internal blocking resistance (9.02% to 4.81%) and concentration polarization resistance (50.73% to 32.17%) in the total hydraulic resistance but enhanced membrane surface deposit resistance (33.93% to 44.32%). A series of characterizations and thermodynamic analyses consistently suggest that the enlarged particle size caused by the Ca2+ bridging effect was the main reason for the decreased filtration resistance of the HA solution. This work revealed the impacts of Ca2+ on HA fouling and demonstrated the feasibility to mitigate fouling by adding Ca2+ in the ultrafiltration process to treat HA pollutants.

Molecular insights into membrane fouling caused by polysaccharides with different structures in polyaluminum chloride coagulation-ultrafiltration process

In this study, mechanisms of membrane fouling caused by polysaccharides with different molecular structures in polyaluminum chloride (PACl) coagulation-ultrafiltration (C-UF) process were explored. Carrageenan and xanthan gum were chosen for model foulants of straight chain and branched chain polysaccharides, respectively. Filtration experiments showed that, with PACl dosage of 0–5 mM, specific filtration resistance (SFR) of carrageenan and xanthan solution showed a unimodal pattern and a continuous decrease pattern, respectively. A series of experimental characterizations indicated that the different SFR pattern was closely related to structure of foulants layer. Density functional theory (DFT) calculation suggested that Al3+ preferentially coordinating with the terminal sulfonyl groups of carrageenan chains to promote gel layer formation at low PACl concentration (0.15 mM). There existed a chemical potential gap between bound water in gel layer and free water in the permeate, so that, filtration through gel layer corresponded to rather high SFR for overcoming this gap. In contrast, Al3+ coordinating with the non-terminal sulfonyl groups of carrageenan at high PACl concentration caused transition from gel layer to cake layer, leading to SFR decrease. However, xanthan gum itself can form a dense gel layer with a complex polymer network by virtue of the interlacing of main chains and branches. Al3+ coordinating with the carboxyl groups on branched chains of xanthan gum resulted in clusters of polymer chains and flocculation, corresponding to the reduced SFR. This proposed molecular-level mechanism well explained membrane fouling behaviors of polysaccharides with different molecular structure, and also facilitated to optimize C-UF process for water treatment.

Ultrafiltration membrane fouling control by two-stage coagulant dosing with moderate pH adjustment

For the coagulation-ultrafiltration process, it has been recognized that coagulation under acidic condition could greatly alleviate membrane fouling, but the high chemical consumption for pH adjustment and the diminished alkalinity of effluent severely restrict the practical application of this operation. In this study, it was found that two-stage coagulant dosing (separate dosing during rapid mixing and medium speed mixing) with pH adjusted to 6.5 could alleviate membrane fouling as that by one-time coagulant dosing at pH 5.5, which could significantly lower the chemical consumption for pH adjustment. Both the favorable aluminum hydrolysis speciation on the floc surface and the reduced interface interaction between membrane and foulant at pH 6.5 contributed to the effectiveness of this method on membrane fouling control. Compared with the scenarios at pH 5.5 and 7.5, the two-stage dosing at pH 6.5 could promote more aluminum species transformation to amorphous Al(OH)3 on the surface of flocs, resulting in less residual Al in the effluent. The acid-base interaction between foulant and membrane dominated membrane fouling. The degree of membrane fouling by separate dosage ratio of 3:7 at pH 6.5 was as low as that by one-time dosing at pH 5.5 because of the similarly low acid-base interaction energy.

Enhanced removal of extracellular microcystin-LR using chitosan coagulation-ultrafiltration: Performance and mechanisms

Although many studies have proposed different drinking water treatment strategies to cope with harmful algal blooms (HABs), the removal of dissolved cyanotoxins remains a technical challenge. In this study, well-controlled laboratory experiments were performed to investigate the performance of chitosan as an alternative to traditional metallic coagulants in a hybrid coagulation-ultrafiltration (UF) process for addressing multiple HABs impacts in drinking water treatment. Compared to aluminum chlorohydrate (ACH), chitosan induced the formation of much larger and compact flocs, resulting in about 50% of M. aeruginosa cells removal after simple straining. While coagulation with ACH slightly reduced the rate and extent of UF permeate flux decline, chitosan coagulation at low doses (up to 0.25 mg/L) significantly reduced membrane fouling by 33%. At optimal dose (0.25 mg/L), chitosan coagulation showed a remarkable enhancement effect on the extracellular microcystin-LR (MC-LR) removal by UF membrane, up to 50% higher than those achieved with ACH (20%) coagulation and control condition (15%). However, excessive chitosan dosing would lead to severe membrane fouling. Molecular dynamic simulation results confirmed that chitosan exhibited affinity towards MC-LR via electrostatic interactions and weaker yet prevalent hydrogen bonding. The binding between chitosan and MC-LR would lead to toxin encapsulation within the flocs structure and thus an increased level of toxin retention by UF membrane based on the mechanism of size exclusion.

Investigation of fluoride and silica removal from semiconductor wastewaters with a clean coagulation-ultrafiltration process

Fluoride and silica contamination in water is a worldwide issue due to the wastewater discharge from semiconductor industry. Coagulation-ultrafiltration (UF) process is commonly used to treat semiconductor wastewaters, but it requires excessive amounts of coagulant/flocculant. In this study, a clean coagulation-UF process using chemical mechanical polishing (CMP) wastewater as a coagulant to treat fluoride-containing wastewater was firstly proposed. The fluoride-containing wastewater, CMP wastewater, mixed fluoride-containing wastewater and CMP wastewater, and mixed fluoride-containing wastewater and polyaluminium chloride/polyacrylamide were compared to investigate turbidity removal efficiency, fluoride removal efficiency and membrane fouling resistance. The negatively charged SiO2 particles in CMP wastewater were found to be adsorbed on the positively charged CaF2 particles surface through electrostatic interaction. Results indicated that CMP wastewater provided a superior turbidity removal efficiency and a minimal membrane fouling resistance compared to conventional coagulant. After UF filtration, the fluoride concentration and turbidity were 2.09 mg L−1 and 0 NTU, respectively, which met the median fluoride effluent standard. The extended Derjaguin-Landau-Verwey-Overbeek theory showed that increasing molar ratio of SiO2 to CaF2 improved the interfacial free energy between membrane and suspended particles, thus mitigating membrane fouling. This clean design principle and strategy will broaden the sustainability of coagulation-UF process for wastewater treatment.

Molecular Insights into Membrane Fouling Caused by Polysaccharides with Different Structures in Polyaluminum Chloride Coagulation-Ultrafiltration Process

Molecular Insights into Membrane Fouling Caused by Polysaccharides with Different Structures in Polyaluminum Chloride Coagulation-Ultrafiltration Process

Biologically Enhanced Coagulation–Ultrafiltration Process for Healthy Water Production with Low Fouling Propensity

Coagulation combined with ultrafiltration (UF) is an effective drinking water treatment process. However, inefficient removal of natural organic matter (NOM) and membrane fouling problems, especially those initiated by the adhesion of biopolymers, greatly restrict the practical application of the UF process. Here, we investigated a biologically enhanced coagulation–ultrafiltration (CUF) process treating samples of a natural surface water, which demonstrated a superior NOM removal and antifouling performance. The membrane flux (under 1.0 bar constant pressure) of the biologically enhanced CUF [using polyaluminum chloride (PACl)] process scheme was approximately 4.4 and 8.4 times higher than that of a conventional CUF and direct UF process, respectively, and PACl was found to perform better than AlCl3. Characterization of the NOM showed that the biological pretreatment combined with the coagulation process significantly contributed to the reduction of hydrophobicity, aromaticity, and molecular weight of the dissolved organics. Analyses of biopolymers showed that the combined process can remove over 99% of the biopolymers (represented by proteins and polysaccharides), which are considered to be the main cause of membrane fouling. Results of X-ray photoelectron spectroscopy and FTIR analyses further elucidated the transformation and reduction of biopolymers during the combined process. With respect to the disinfection byproduct formation potential (DBP-FP), the results showed that the conventional CUF process had a limited impact on the DBP-FP, while the biologically enhanced CUF process had a substantial impact consistent with meeting the current EPA DBP standards. Overall, this study has highlighted the potential advantages of using a biologically enhanced CUF process for producing higher quality drinking water with a simultaneous low membrane fouling propensity.

Thermodynamic mechanisms of membrane fouling during filtration of alginate solution in coagulation-ultrafiltration (UF) process in presence of different ionic strength and iron(III) ion concentration

Effects of iron(III) ion level and ionic strength on membrane fouling in coagulation-ultrafiltration (UF) process were explored in this study. Two interesting filtration phenomena during the filtration process were observed: extremely reduced specific filtration resistance (SFR) of alginate solution complexed with iron (III) ions level from 0.1 to 2.0 mM (phenomenon I), and different change trends of alginate SFR with ionic strength between two iron(III) ion levels (remarkable increase trend of alginate SFR with ionic strength at 0.1 mM ions level while almost remaining unchanged trend at 2.0 mM ions level) (phenomenon II). Experimental characterizations indicated that the two phenomena were closely linked to changes of zeta potential, viscosity and morphology of the related foulants. It was proposed that iron(III) ions at low level (0.1 mM) preferentially coordinate the terminal carboxyl groups of alginate chains and form gel layer. The chemical potential gap described by Flory-Huggins lattice theory is responsible for the extremely high SFR of gel layer. Coordinating the non-terminal carboxyl groups at high iron(III) ion level (2.0 mM) causes transition from gel layer to cake layer formation during filtration, and lots of interstices in cake layer correspond to low SFR, well interpreting phenomenon I. Meanwhile, electrostatic double layer compression caused by the increased ionic strength makes the gel layer shrunk and denser for low iron(III) ion level, but less affects the number and size of interstices in the cake layer for high iron(III) ion level, reasonably explaining phenomenon II. This study revealed essential and comprehensive thermodynamic fouling mechanisms and facilitated to optimize coagulation-UF/MF process.

Membrane fouling performance of Fe-based coagulation-ultrafiltration process: Effect of sedimentation time

Pre-coagulation is commonly used with ultrafiltration (UF) to alleviate the membrane fouling. Compared to conventional coagulation-sedimentation-UF (CSUF) processes, the direct coagulation-UF (CUF) processes are widely believed to perform better due to the formation of a looser cake layer. It is however shown in this study that not only the density of a cake layer, but also its thickness as well, can affect the membrane fouling behavior, which therefore are influenced by both the sedimentation time and flocs characteristics. Herein, the membrane fouling performance of Fe-based coagulation-UF process was systematically investigated with different sedimentation times. A critical threshold of 30 min was observed at the lab-scale: if shorter than that, the membrane fouling depended mainly on the cake layer density, and thus CUF outperformed CSUF; but when the sedimentation time was over 30 min, the cake layer thickness turned to be the dominant factor, thereby resulting in CSUF performing better. Furthermore, it was shown that the critical sedimentation time was decided by flocs characteristics. A lower water temperature induced the formation of irregular flocs with a lower fractal dimension, and the corresponding cake layer exhibited an almost identical density with increasing sedimentation time. In this regard, CSUF processes were constantly superior to CUF as the cake layer thickness decreased. On the other hand, a critical sedimentation time reappeared because of the higher floc fractal dimension under acidic conditions. This work showed for the first time that the membrane fouling of CSUF was up to the sedimentation time, and it was possible to outperform CUF if the sedimentation time exceeded a critical threshold. Such a finding is crucial to the future development of coagulation integrated UF processes.

A modified coagulation-ultrafiltration process for silver nanoparticles removal and membrane fouling mitigation: The role of laminarin

Silver nanoparticles (AgNPs) in surface water are highly toxic to humans and difficult to remove due to their adsorption to humic acid (HA). In this study, laminarin (LA) was used as a coagulant aid in a coagulation-ultrafiltration (C-UF) system to improve AgNPs-HA removal efficiency. C-UF efficiency, membrane flux, and flocs properties were investigated to explore the AgNPs-HA removal mechanism and membrane fouling. Results showed that when poly aluminum chloride (PAC) was dosed with LA, AgNPs-HA removal was 10–15% higher than when using PAC alone. The C-UF system using only PAC improved the AgNPs-HA removal efficiency through increased coagulation but resulted in membrane fouling. LA application helped mitigate membrane fouling, and the highest normalized permeate flux and smallest resistance values (0.573 and 2.180 × 1010 m−1, respectively) were achieved when 0.1 mg/L of LA was applied with 5 mg/L of PAC. The alleviating mechanism was related to flocs with large sizes and small fractal dimension (Df) values, generating a cake layer with porous morphology. This cake layer was easily removed by flushing and backwashing, which resulted in minimal resistance and fouling of the UF membrane.

Synergistic fouling behaviors and mechanisms of calcium ions and polyaluminum chloride associated with alginate solution in coagulation-ultrafiltration (UF) process

Effects of calcium ions and polyaluminum chloride (PACl) on membrane fouling in coagulation-ultrafiltration (UF) process were investigated in this study. Filtration tests demonstrated three interesting filtration behaviors: 1) high specific filtration resistance (SFR) of alginate solution with low CaCl2 or PACl addition (e. g. 3.51×1015 m·kg -1 under the condition of 1.5 mM CaCl2 addition); 2) unimodal pattern of alginate SFR with PACl or CaCl2 addition alone; 3) synergistic effects between CaCl2 and PACl on alginate SFR. It was found that, the foulant morphological changes driven by the thermodynamic mechanisms based on Flory-Huggins lattice theory take the critical roles in these filtration behaviors. Density functional theory (DFT) calculations showed that initial coordination of Ca2+ and Al3+ ions with alginates tended to form tetrahedron geometry and geometry of coordinating three terminal carboxyl groups, respectively, which facilitated to elongate the alginate chains (without clustering the flocs) and form more stable gel, increasing SFR. Improving Ca2+ and Al3+ dosages triggered transition to other geometries for clustering polymeric network and flocculation, reducing SFR. Due to the higher binding affinity of Ca2+ over Al3+, Ca2+ and Al3+ sequentially take roles of enlarging polymeric network and clustering the coordination compounds, and then facilitate to form large size flocs and reduce SFR, causing the synergistic effects between CaCl2 and PACl additions. The proposed thermodynamic mechanisms satisfactorily explained these interesting fouling behaviors, allowing to further optimize coagulation-UF process.