Synergistic behavior between silica and alginate: Novel approach for removing silica scale from RO membranes

The formation of mineral scale deposits on membranes is a pervasive and expensive problem for the water treatment industry. A series of experiments run on a laboratory-scale reverse osmosis membrane system examined the fouling of membranes when the feed water was spiked with organic and inorganic foulants. Alginic acid was used as the organic foulant and silica was used as the inorganic foulant. Studies involving interactions of these two foulants have not previously been reported in literature. Experiments were run with each foulant individually to characterize fouling at different velocities and pressures. Experiments were then run using both foulants together to characterize the synergistic effects on membrane fouling. One set of experiments with both foulants demonstrated that alginic acid inhibits silica fouling on reverse osmosis membranes. Further experiments indicated that alginic acid added after silica fouling had already occurred was able to remove silica scale from the membrane and restore permeate flux.     

Membrane fouling and chemical cleaning in water recycling applications

Fouling and subsequent chemical cleaning are two important issues for sustainable operation of nanofiltration (NF) membranes in water treatment and reuse applications. Fouling strongly depends on the feed water quality, especially the nature of the foulants and ionic composition of the feed water. Consequently, appropriate selection of the chemical cleaning solutions can be seen as a critical factor for effective fouling control. In this study, membrane fouling and chemical cleaning under condition typical to that in water recycling applications were investigated. Fouling conditions were achieved over approximately 18 h with foulant cocktails containing five model foulants namely humic acids, bovine serum albumin, sodium alginate, and two silica colloids in a background electrolyte solution. These model foulants were selected to represent four distinctive modes of fouling: humic acid, protein, polysaccharide, and colloidal fouling. Three chemical cleaning solutions (alkaline solution at pH 11, sodium dodecyl sulphate (SDS), and a combination of both) were evaluated for permeate flux recovery efficiency. The results indicated that with the same mass of foulant, organic fouling was considerably more severe as compared to colloidal fouling. While organic fouling caused a considerable increase in the membrane surface hydrophobicity as indicated by contact angle measurement, hydrophobicity of silica colloidal fouled membrane remained almost the same. Furthermore, a mechanistic correlation amongst cleaning efficiency, characteristics of the model foulants, and the cleaning reagents could be established. Chemical cleaning of all organically fouled membranes by a 10 mM SDS solution particularly at pH 11 resulted in good flux recovery. However, notable flux decline after SDS cleaning of organically fouled membranes was observed indicating that SDS was effective at breaking the organic foulant—Ca²⁺ complex but was not able to effectively dissolve and completely remove these organic foulants. Although a lower permeate flux recovery was obtained with a caustic solution (pH 11) in the absence of SDS, the permeate flux after cleaning was stable. In contrast, the chemical cleaning solutions used in this study showed low effectiveness against colloidal fouling. It is also interesting to note that membrane fouling and chemical cleaning could permanently alter the hydrophobicity of the membrane surface.     

Characterization of EfOM Fraction Responsible for Short-Term Fouling in Ultrafiltration

Based on our earlier diagnosis that hydrophobic and hydrophilic (HPO/HPI) acids are the primary cause of short-term fouling in the ultrafiltration of secondary effluent, the HPO/HPI acids were extracted and subsequently characterized in comparison with commercial organic materials. HPO/HPI acids isolated from secondary effluent contained significantly fewer complex mixtures than humic substances that have been implicated as the dominant foulants in the filtration of surface water using porous membranes. The physicochemical and spectroscopic characterization demonstrated that the aromaticity and apparent molecular weight of HPO/HPI acids were lower than that observed for other humic materials, while the oxygenated functional groups were relatively higher.     

Fouling effects of humic and alginic acids in nanofiltration and influence of solution composition

The objectives of this research were to investigate the combined and individual influence of hydrophobic and hydrophilic fractions of NOM on the fouling of thin-film composite nanofiltration (NF) membranes, and also the roles of solution chemistry on the permeate flux and fouling. Combined fouling is compared to the individual fouling behaviors (i.e., alginate or humic acid alone).Experiments were conducted using a “cross-flow” pilot-scale membrane unit with a full circulation mode. Fouling experiments were performed with individual and combined humic acid and alginate.The results demonstrated that increasing organic concentration increased greatly the rate and extent of flux reduction. Individual alginate fouling was more detrimental than individual humic acid fouling, and alginate exhibited greater flux decline than humic acid fouling alone at the same conditions. A higher flux decline was observed with increasing proportions of aliginate in combined fouling. In other word, there are antagonistic effects during combined fouling because the charge functional groups of two above foulants are negative and increase electrostatic repulsion between two foulants and also foulant-membrane. The flux reduction increased with increasing ionic strength, foulant concentrations, and with lower pH. This observation implies the importance of interaction between various foulants for deeper understanding of fouling phenomena. The membrane fouling was largely dependent on organic properties and fractions.     

Mechanisms underlying the effects of membrane fouling on the nanofiltration of trace organic contaminants

The influence of membrane fouling on the retention of four trace organic contaminants - namely sulfamethoxazole, ibuprofen, carbamazepine, and triclosan - by nanofiltration membranes was investigated in this study. Humic acid, alginate, bovine serum albumin, and silica colloids were selected as model foulants to simulate various organic fractions and colloidal matter that are found in secondary treated effluent and surface water. The effects of membrane fouling on the separation process was delineated by comparing retention values of clean and fouled membranes and relate them to the membrane properties (under both clean and fouled conditions) as well as physicochemical characteristics of the trace organic contaminants. Membrane fouling was dependent on the physicochemical properties of the model foulants. Initial foulant-membrane interaction could probably be a major factor governing the process of membrane fouling particularly by the organic foulants. Such membrane-foulant interaction was also a dominating factor governing the effects of membrane fouling on the membrane separation efficacy. In good agreement with our previous study (Nghiem and Hawkes, 2007 [1]), the effects of fouling on retention were found to be membrane pore size dependent. In addition, results reported here suggest that these effects could also be foulant dependent. It was probable that the influence of membrane fouling on trace organic retention could be governed by four distinctive mechanisms: modification of the membrane charge surface, pore blocking, cake enhanced concentration polarisation, and modification of the membrane hydrophobicity. The presence of the fouling layer could affect the retention behavior of charged solutes by altering the membrane surface charge density. While the effect of surface charge modification was clear for inorganic salts, it was less obvious for the negatively charged pharmaceutical species (sulfamethoxazole and ibuprofen) examined in this investigation, possibly due to the interference of the pore blocking mechanism. Evidence of the cake enhanced concentration polarisation effect was quite clear, particularly under colloidal fouling conditions. In addition, organic fouling could also interfere with the solute-membrane interaction, and therefore, exerted considerable influence on the separation process of the hydrophobic trace organic contaminant triclosan.     

Surface characterization and performance evaluation of commercial fouling resistant low-pressure RO membranes

This paper describes the characterization and evaluation of various RO/NF membranes for the treatment of seasonally brackish surface water with high organic contents (TOC ≈21 mg/L). Twenty commercially available RO and NF membranes were initially evaluated by performing controlled bench-scale flat-sheet tests and surface characterization. Based on the results, four low pressure RO membranes were selected for use in the pilot study. The surface characterization revealed that each of four selected membranes had unique surface characteristics to minimize membrane fouling. Specifically, the LFC1 membrane featured a neutral or low negative surface to minimize electrostatic interactions with charged foulants. The X20 showed a highly negatively charged surface, and thus, was expected to perform well with feed waters containing negatively charged organics and colloids. The BW30FR1 exhibited a relatively neutral and hydrophilic surface, which could be beneficial for lessening organic and/or biofouling. The SG membrane had a smooth surface that made it quite resistant to fouling, particularly for colloidal deposition. In the large-scale pilot study using single element, all of the four membranes experienced a gradual increase in specific flux over time, indicating no fouling occurred during the pilot study. The deterioration of permeate water quality such as TDS was also observed over time, suggesting that the integrity of the membranes might be compromised by the monochloramine used for biofouling control.     

Interactions controlling biopolymer fouling of reverse osmosis membranes

Laboratory experiments and model calculations were performed to elucidate the fundamental interactions that control organic fouling in reverse osmosis (RO) processes. Bovine serum albumin and alginic acid were selected as model aquatic organic macromolecules (organic foulants). An extended Derjaguin-Landau-Verwey-Overbeek (DLVO) characterization analysis was used to elucidate mechanisms of organic matter fouling on a commercial, polyamide composite RO membrane. Surface tension parameters derived from contact angle analyses are used to demonstrate that the apparent thermodynamic stability of macromolecules determines and adhesive free energy between membranes and macromolecules explained the observed differences in flux decline. Further, foulant–membrane and foulant–foulant interfacial forces helped explain why hydrophilic macromolecules formed polarization layers causing minimal flux decline, while hydrophobic macromolecules formed gel (or cake) layers that led to severe flux decline.     

Characterization of cation‐exchange membrane fouling during bipolar membrane electrodialysis of monosodium glutamate isoelectric supernatant

BACKGROUND: A novel procedure that involved regeneration and recycling of ammonia and sulfuric acid from monosodium glutamate isoelectric supernatant with bipolar membrane electrodialysis (BMED) was proposed. As the performance of the membranes deteriorated during the batch runs, fouling of the cation‐exchange membrane (CEM) in contact with the base cell was studied. RESULTS: During ten consecutive batches of BMED, some operating parameters deteriorated gradually. Using scanning electron microscopy observations, fouling deposits were found on the CEM surface on the base cell side. Using Fourier transform infrared spectroscopy and reversed‐phase high‐performance liquid chromatography (RP‐HPLC), the organic fouling fraction of the CEM foulants was found to contain eight amino acids. Using X‐ray energy‐dispersive analysis, the mineral fouling fraction was shown to be mainly O and Ca elements, and a little Mg. Using X‐ray diffraction, the inorganic foulant was identified as CaCO₃, mainly in the form of calcite and a little aragonite. CONCLUSION: The CEM was subject to membrane fouling consisting of an organic fouling fraction and a mineral fraction. The organic fraction occurred as ions with some positive charges from the isoelectric supernatant and probably existed in the form of amino acids or their peptides. The mineral fraction was mainly CaCO₃ calcite and aragonite, and probably a little amorphous Ca and Mg hydroxides. Copyright © 2011 Society of Chemical Industry     

Irreversible Fouling in MF/UF Membranes Caused by Natural Organic Matters (NOMs) Isolated from Different Origins

Abstract

For more efficient use of membrane technology in water treatment, it is essential to understand more about the fouling that requires chemical cleaning to be eliminated (i.e., irreversible fouling). In this study, five different MF/UF membranes and four types of organic matter collected from different origins were examined in terms of the degree of irreversible membrane fouling. Experimental results demonstrated that the extent of irreversible fouling differed significantly depending on the properties of both the membrane and organic matter. Among the tested membranes, UF membranes made of polyacrylonitrile (PAN) exhibited the best performance in terms of prevention of irreversible fouling. In contrast, MF membranes, especially one made of polyvinylidenefluoride (PVDF), suffered significant irreversible fouling. Conventional methods for characterization of organic matter such as specific ultraviolet absorption (SUVA), XAD fractionation, and excitation‐emission matrix (EEM) were found to be inadequate for prediction of the degree of irreversible fouling. This is because these analytical methods represent an average property of bulk organic matter, while the fouling was actually caused by some specific fractions. It was revealed that hydrophilic fraction of the organic matter was responsible for the irreversible fouling regardless of the type of membranes or organic matter.     

Foulants analyses for NF membranes with different feed waters: coagulation/sedimentation and sand filtration treated waters

Two different NF membranes were operated to remove natural organic matter (NOM) originating from Dongbok Lake in Korea. Coagulation/sedimentation and sand filtration treated waters as membrane feed waters were used. The tested NF membranes were autopsied to compare the fouling propensity from different feed waters using pure water and a NaOH solution. Organic/inorganic foulants onto membrane surface were analyzed in terms of molecular weight (MW) distribution, structure, and IR analysis, and fouled membranes were also characterized in terms of pore size distribution, surface charge, and SEM–EDS analysis. Polysaccharides and/or N-acetyl aminosugar groups with MW ranging from 30,000 to 50,000 g/mol were identified using HP-SEC and IR analysis. Inorganic foulants (i.e., Si and Al) were also fouled onto the membrane surface and/or pores, and it is effectively removed by caustic cleaning, not pure water. Caustic cleaning was proven to be effective to remove both fouled NF membranes as a basis of flux recovery, and it could efficiently desorb the hydrophobic NOM constituents or protein-like substances from the relatively hydrophilic and less negatively charged NF membranes.     

Fouling and cleaning of polymer-entwined graphene oxide nanocomposite membrane for forward osmosis process

In this study, we have characterized membrane fouling of polymer-entwined graphene oxide membranes with a simulated feed solution containing organic foulants for wastewater treatment applications, as well as with a simulated inorganic wastewater with high iron and silicon concentrations relevant to steel industry wastewater reclamation. Membrane cleaning processes by cross-flow surface flushing with water were then applied to demonstrate water flux recovery for long-term application. Salt rejection property was retained constant during fouling process, whereas water flux was found to be reduced continuously due to fouling but was readily recoverable following surface flushing.     

Reduced Fouling of Ultrafiltration Membranes Via Surface Fluorination

Abstract

The fouling resistance of a polysulfone membrane can be improved by fluorination. In the filtration of potato waste streams, fluorination of polysulfone membranes has improved both the initial flux and fouling rates of the treated membranes. Selectivities of the membranes as measured by COD and total organic nitrogen rejection were not affected by the fluorination process.

The fluorination process adds both fluorine and oxygen to the surface, and the increased oxygen and fluorine on the surface of the membrane increase the hydrophilic nature of the membrane. This increase of hydrophilicity reduces the rate of adsorption of hydrophobic foulants to the surface, decreasing the fouling rate. Increased hydrophilicity also decreases the capillary pressure and permits permeate flow through smaller pores.     

Investigation of combined fouling behavior in nano-filtration process under various feed conditions

Despite the great advance in nano-filtration (NF) process development in various applications, its performance in water treatment is still impeded by the undesired fouling phenomenon, which is not yet fully understood nowadays. In this study, a comprehensive investigation on the fouling behavior, more specifically the combined fouling behavior with the presence of more than one type of foulant was carried out under various solution chemistries and feed hydraulic pressures. The interaction between the model organic foulant (alginate) and inorganic foulant (silica colloid) was systematically studied with nano-filtration membranes, with a more severe fouling observed in the combined fouling than individual foulants. However, the results also revealed that the commonly observed synergistic effect of combined fouling in the forward osmosis process was not present in the nano-filtration process. In addition, the solution chemistries (pH and calcium ions) and feed hydraulic pressure were also found to have certain influence on the combined fouling, especially the feed hydraulic pressure which exhibited a more pronounced impact on the flux decline than the other factors, thus in turn, affecting more on the reversibility of the membrane fouling.     

基于膜表面与界面作用的膜污染控制方法

膜污染控制是膜技术能否成功应用的关键因素之一。讨论了膜面粗糙度、亲水性和荷电性等性质对膜分离性能的影响,介绍了膜表面性质参数的表征方法,分析了颗粒污染物团聚、颗粒与胶体吸附、胶体大分子的变形等对膜污染形成的影响。最后对面向应用过程的陶瓷膜材料表面与界面控制方法进行了总结。膜污染的研究已从操作参数调节发展到表面与界面作用的控制,对提高膜分离性能,促进膜过程在更多领域的推广应用有重要意义。     

Chemical control of colloidal fouling of reverse osmosis systems

Fouling of membranes by colloidal organic and inorganic particles continues to be documented as the most common and challenging obstacle in attaining stable continuous operation of reverse osmosis (RO) and ultrafiltration (UF) systems. Much current research is being conducted on physical parameters to mitigate such fouling. The focus has been on membrane synthesis and element design; microfiltration and ultrafiltration pretreatment; electromagnetic devices; correlation with physical factors such as Silt Density Index, zeta potential and critical flux; technique of direct observation of fouling process through a membrane; and classification of macromolecular organics for correlation with fouling characteristics. We report initial successes with chemical control of colloidal fouling. Through screening with a large number of observable coagulations of natural colloids, we have developed a group of proprietary anticoagulants and dispersants that would, at less than 10 ppm dosage to the RO feedwater, control various classes of colloidal foulants. Case studies of the control of humic matter, elemental sulfur and colloidal silicate in problematic RO systems that became stabilized are briefly presented. We conclude that a great need and potential exists in economically controlling the myriads of fouling interactions of colloidal particles during concentration within the brine channels of RO membrane elements. Low dosages of antifoulants can in many cases obviate the need for installation and maintenance of pretreatment unit or operations designed to remove such colloidal foulants from the process stream.     

Facile modification of aliphatic polyketone-based thin-film composite membrane for three-dimensional and comprehensive antifouling in active-layer-facing-draw-solution mode

The application of “active-layer-facing-draw-solution” (AL-DS) mode, which allows a considerably high water flux in forward osmosis (FO) processes, is hindered by severe fouling occurring within the porous support of the FO membranes. We designed a series of “three-dimensionally” antifouling FO membranes by an extremely convenient and scalable approach, by using in situ reduced aliphatic polyketone (PK) membranes (rPK) and the silver-nanoparticles-immobilized rPK-Ag membranes as the substrates for thin-film composite (TFC) FO membrane preparation. This modification imparted enhanced hydrophilicity compared with the original PK-TFC membrane, without affecting the morphology and transport properties. Benefiting from the three-dimensional antifouling structure, the modified TFC membranes (i.e., rPK-TFC and rPK-Ag-TFC membranes) demonstrated excellent and comprehensive fouling resistance towards a variety of organic foulants, as well as biofouling resistance towards Escherichia coli. These results provide useful insights into the fabrication of antifouling FO membranes for water purification purposes and pressure retarded osmosis (PRO) process.     

Tris(hydroxymethyl)aminomethane polyamide thin‐film‐composite antifouling reverse osmosis membrane

For the applications of reverse osmosis (RO) process, membrane fouling caused by organic molecule adsorption is still a serious problem which significantly decreases membrane lifespan and increases operation costs. In this present article, we report the thin film composite (TFC) RO membrane functionalized with tris(hydroxymethyl)aminomethane (THAM) using one‐step method for improved antifouling property. The results of surface characterization indicated that THAM was successfully grafted onto the active layer of membrane by covalent linkage. Mult‐hydroxyl‐layer was generated and remained steadily on TFC membrane surface after modification. The contact angle decreased from 75.9 ± 3.0° to 46.9 ± 2.3°, which showed a distinct improvement of membrane surface hydrophilicity after modification. The grafted THAM improved water flux by 28.3%, while salt rejection was almost unchanged in membrane property tests. The modified membranes presented preferable antifouling property to foulants of bovine serum albumin, sodium alginate, and dodecyl trimethyl ammonium bromide than that of pristine membranes during dynamic fouling experiments. The method in this study provided an effective way to improve antifouling property of the polyamide thin‐film‐composite RO membrane. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45891.     

Phosphorylcholine‐Substituted ROMP Polyolefin Coatings Provide Fouling Resistance to Membrane Materials

The design and synthesis of new fouling‐resistant coating materials, specifically PC‐substituted polyolefins, and their application to water purification membranes is described. Greatly improved fouling resistance is found for coated membranes subjected to environmentally relevant emulsified oil foulants. The coating method proves effective for reducing fouling on both UF and RO membranes, and for maintaining high rejection of organic material and salt. Providing membranes of various types with a coating that simultaneously gives high flux, fouling resistance, and foulant rejection represents a significant advance in membrane materials, and a promising route to extend membrane applications beyond what has been possible using conventional, known materials.

     

Analysis of deposition mechanism during ultrafiltration of glycerin-rich solutions

Clarification of glycerin-rich solution is one of the potential applications of membrane within the oleochemical industry. However, one of the barriers in successfully utilizing the use of membranes such as ultrafiltration (UF) has been due to the fouling. In this work, flux decline during ultrafiltration of the glycerin-rich solutions was studied by using commercialized polymeric polyethersulphone (PES) membrane. Influence of fatty acids as foulants model (palmitic acid, stearic acid and oleic acid), pH of feed solution (3-10) and molecular weight cut-off (5 kDa, 20 kDa and 25 kDa) were analyzed. All the experiments were performed at constant pressure (2 bar) and temperature (40 °C). The Hermia's model was used to analyze the fouling mechanism during the flux decline which involve cake layer model due to adsorption of solute as well as pore blocking model. All the different types of flux decline kinetics were found to occur during the permeation of glycerin-rich solutions. However, the contribution of resistance due to cake layer formation was small for all the conditions studied. The fouling mechanisms were found to depend on the hydrophobicity of the PES membrane itself as well as the nature of foulants used in the study.     

Performance of RC and PES ultrafiltration membranes in filtration of pulp mill process waters

Issues of fouling and effective cleaning limit the adoption of UF in pulp and paper mill applications. The choice of an optimal membrane for a specific filtration application is a challenging task due to the fact that fouling is a complex phenomenon. This study compares regenerated cellulose (RC) and polyethersulphone (PES) membranes in UF of two chemithermomechanical pulp mill process waters. The process waters originated from hardwood and softwood pulping. Based on their flux recovery, PES membranes sustained greater fouling than RC membranes even though the hydrophobicity of RC membranes was increased remarkably by adsorptive fouling. The process water affected the performance of the membranes. The membrane characteristics were more important in determining fouling when softwood process water was used than when hardwood process water was used. Hydrophilicity and morphology of the membranes were seen to have a clear influence on fouling.