Efficient removal of heavy metals in water utilizing facile cross-link conjugated linoleic acid micelles.

Micellar-enhanced ultrafiltration (MEUF) technology is an effective method to treat low-concentration heavy metal wastewater. However, the leakage of surfactants in the ultrafiltration (UF) process will inevitably cause secondary pollution. In this study, a biosurfactant of conjugated linoleic acid (CLA) with conjugated double bonds was selected to bind its micelles by simple thermal crosslinking to obtain morphologically stable stearic acid (SA) nanoparticles. The pure SA nanoparticles were obtained by repeated dialysis. The stability of the SA nanoparticles was verified by comparing the particle size distribution and solubility of the materials before and after crosslinking at different pH levels. The effectiveness of SA nanoparticle-enhanced UF in removing heavy metals was verified by exploring the adsorption performance of SA nanoparticles. The dialysis device was used to simplify the UF device, wherein SA nanoparticles were assessed as adsorbents for the elimination of Cu2+, Pb2+, and Cd2+ ions from aqueous solutions under diverse process parameters, including pH, contact time, metal ion concentration, and coexisting ions. The findings indicate that the SA nanoparticles have no evidence of secondary contamination in UF and exhibit compatibility with a broad pH range and coexisting ions. The maximum adsorption capacities for Cu2+, Pb2+, and Cd2+ were determined to be 152.77, 403.56, and 271.46 mg/g, respectively.

Removal of Nutrients from Water Using Biosurfactant Micellar-Enhanced Ultrafiltration.

The removal of NH4+, NO3-, and NH3- from wastewater can be difficult and expensive. Through physical, chemical, and biological processes, metals and nutrients can be extracted from wastewater. Very few scientific investigations have employed surfactants with high biodegradability, low toxicity, and suitability for ion removal from wastewater at different pH and salinity levels. This research employed a highly biodegradable biosurfactant generated from yeast (sophorolipid) through micellar-enhanced ultrafiltration (MEUF). MEUF improves nutrient removal efficiency and reduces costs by using less pressure than reverse osmosis (RO) and nanofiltration (NF). The biosurfactant can be recovered after the removal of nutrient- and ion-containing micelles from the filtration membrane. During the experiment, numerous variables, including temperature, pH, biosurfactant concentration, pollutant ions, etc., were evaluated. The highest amount of PO43- was eliminated at a pH of 6.0, which was reported at 94.9%. Maximum NO3- removal occurred at 45.0 °C (96.9%), while maximum NH4+ removal occurred at 25.0 mg/L (94.5%). Increasing TMP to 200 kPa produced the maximum membrane flow of 226 L/h/m2. The concentrations of the contaminating ion and sophorolipid were insignificant in the permeate, demonstrating the high potential of this approach.

Mixed micellar solubilization for procion blue MxR entrapment and optimization of necessary parameters for micellar enhanced ultrafiltration.

In this study, micellar enhanced ultrafiltration, MEUF, being an active methodology, has been employed to remove Procion Blue MxR (PBM) from synthetic effluent. MEUF is being applied to reduce the toxicity level of aqueous system using the micellar media of cationic surfactants i.e. Cetyl trimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC). Subsequently, the effect of addition of nonionic surfactant, Triton X-100 (TX-100), on solubilizing power of cationic surfactants is investigated. The values of partition coefficient and free energy of partition reflect the extent of interaction of the dye with the surfactants. Initially molecules of pollutants i.e. dye form ion pairs with ionic surfactants and, later on, the same is incorporated within micelle. Maximum value of free energy of partition ΔGp has been found to be -55.49 kJmol-1 and -50.43 kJmol in the presence of CPC and CTAB, respectively. The size of pollutant, thus, increases and, consequently, can be easily filtered. The effect of various factors i.e. concentration of surfactant, concentration of electrolyte (NaCl), transmembrane pressure, revolutions per minute (RPM) and pH, have been investigated to find the optimum conditions for maximum removal of PBM from aqueous system. The efficiency of MEUF has been assessed by calculating the values of rejection percentage and permeate flux. Both the surfactants were observed as strong candidates for PBM encapsulation but overall, maximum rejection percentage (R%) of 96.90% was attained by CPC.

Highly Selective Methodology for Entrapment and Subsequent Removal of Cobalt (II) Ions under Optimized Conditions by Micellar-Enhanced Ultrafiltration.

Micellar-enhanced ultrafiltration (MEUF), being a separation technique, was used to remove cobalt metal ion (Co2+) from their aqueous solutions in an application to reduce the toxicity level from industrial effluents using a micellar solution of anionic and cationic surfactants. The metal ions were first adsorbed by using anionic surfactants, i.e., sodium dodecyl sulfate (SDS) and sodium oleate (SO). The calculations for partition (Kx) and binding constants (Kb) and their respective free energy of partition and binding (ΔGp and ΔGb kJmol-1) helped significantly to find out the extent of binding or interaction of Co2+ with the surfactant and ΔGp and ΔGb were found to be -29.50 and -19.38 kJmol-1 for SDS and -23.95 and -12.67 kJmol-1 in the case of SO. MEUF work was also performed to find out the optimal conditions to remove metal pollutants from the aqueous system. For the said purpose, various factors and concentrations effect were studied, such as the concentration of the surfactant, concentration of the electrolyte (NaCl), transmembrane pressure, RPM, and pH. The efficiency of this process was checked by calculating various parameters, such as rejection percentage (R%) and permeate flux (J). A maximum rejection of 99.95% with SDS and 99.99% with SO was attained.

MEUF for removal and recovery of valuable organic components present in effluents: A process intensified technology.

In recent years, the domain of the research space in novel separation process has been led by membrane systems as a panacea providing multifarious benefits of high separation efficiency, elimination of extreme process conditions, sustainability, and environment friendliness coupled with high operational flexibility. In this niche area, often, ultrafiltration is touted as a robust separation technique due to its high separation efficiency, membrane stability, and lower operating costs. The only drawback of relatively large pore size can be overcome by combining surfactant addition, leading to development of integrated processes termed as Micellar Enhanced Ultrafiltration. MEUF processes isolate and selectively separate valuable organics present in effluent streams. The process characteristics fit the bill as a typified example for process intensification Technology interventions for recycling of surfactants can enhance the cost-competitiveness of the process. This has the potential to develop into a broad-spectrum effluent treatment option with a change of surfactants for target contaminants. Here, in this review, we attempt to critically examine the unique features of this technology, development of spin-offs with wide-ranging applications. Specifically applications in removal of hazardous, and persistent components like dissolved organics have been critically studied. The focus was to highlight the crux of the novel technologies highlighting the efficacy and the underlying concept of process intensification. PRACTITIONER POINTS: Role of MEUF as a sustainable process intensifying separation technique for removal and recovery of organics. Novel process development using MEUF. Comparative performance analysis to assess efficacy. Discussions on future integrative process development. Sustainability aspect of MEUF with possibility of byproduct recovery.

Separation of rare earth elements from mixed-metal feedstocks by micelle enhanced ultrafiltration with sodium dodecyl sulfate.

Micelle enhanced ultrafiltration (MEUF) is a surfactant-based membrane separation process that may be used to separate target ions from mixed metal aqueous solutions, such as leachates of coal ash and other geological wastewaters. The ability of MEUF to separate rare earth elements (REEs) was evaluated using sodium dodecyl sulfate (SDS) as the sorbent in surfactant micelle phase, which was subsequently separated using ultrafiltration, acidification, and ferricyanide precipitation. Separation experiments were performed with a synthetic coal ash leachate feedstock as an example mixed-metal feedstock. Experiments tested the influence of surfactant concentration, pH, and co-existing competitive ions on REE recoveries, and also tested methods for SDS recovery and reuse. Membrane rejection efficiencies of REEs were 97% and 71% respectively for synthetic and real leachate under optimized operating conditions. A two-step process of precipitation with CaCl2 and Na2CO3 following membrane separation was the best for recovering SDS with a yield of 99.7%.

Determining binding of polycyclic aromatic hydrocarbons to micelles formed by SDS and SOL using semi-equilibrium dialysis.

Micellar enhanced ultra-filtration (MEUF) is a modified ultrafiltration (UF) method that can remove small molecules that are not effectively removed by UF alone. In this work we used a similar semi-equilibrium dialysis (SED) method to characterize two anionic surfactants, sodium dodecyl sulfate (SDS) and sodium laurate (SOL), as MEUF candidates to remove several polycyclic aromatic hydrocarbon (PAH) compounds. These anionic surfactants have low toxicity and are more biodegradable compared to the fairly toxic and persistent cetyltrimethylammonium bromide (CTABr) and similar cationic surfactants, which is important as MEUF surfactants may be present in the treated effluent. The log binding constants (Log KB) of the PAHs naphthalene, phenanthrene, pyrene and fluorene to SDS ranged from 3.07 to 4.48, which compared well with the previous results for CTABr and indicated that SDS is an excellent candidate for MEUF. The log binding constants for the same PAHs with SOL micelles ranged from 2.11 to 3.53, which suggested that SOL might be adequate for stronger-binding PAH like pyrene and fluorene but less suitable for naphthalene and phenanthrene. The results demonstrated a strong correlation between the Log KB with one micelle type and the Log KB with the other, suggesting a common set of properties and interactions are responsible for the binding. Similar to the previous results for CTABr, a significant correlation between Log KB and Log KOW values indicates that hydrophobic character is the main driving force for PAH binding with these anionic micelles. This may also be useful for predicting MEUF performance for various compound/surfactant combinations where Log KB is not known.

Sulfate removal using colloid-enhanced ultrafiltration: performance evaluation and adsorption studies.

Colloid-enhanced ultrafiltration (CEUF), i.e., micellar-enhanced ultrafiltration (MEUF) and polymer-enhanced ultrafiltration (PEUF), was investigated to remove sulfate ions from aqueous solution in batch experiments, using cetyltrimethylammonium (CTAB) and poly(diallydimethylammonium chloride) (PDADMAC) as colloids, respectively. Ultrafiltration performance was evaluated under different initial concentrations of sulfate (0-20 mM) and CTAB/PDADMAC (0-100 mM). The highest retention rate (> 99%) was found in dilute sulfate solutions. At high sulfate concentrations (e.g., 10 mM), a dosage of 50 mM CTAB or PDADMAC can retain approximately 90% of sulfate ions. Though concentration polarization behavior was observed, membrane characterization indicated that the fouling was reversible and membranes can be reused. Furthermore, adsorption equilibrium and kinetics studies show that Freundlich isotherm and pseudo-second-order kinetics can describe the sulfate-colloid interaction, indicating that the surface of absorbents are heterogeneous and the rate-controlling step is chemisorption. Both MEUF and PEUF show potential as effective separation techniques in removing sulfate from aqueous solutions. Under the same conditions examined, PEUF shows advantages over MEUF in its higher retention at lower polymer-to-sulfate ratios, cleaner effluent, and higher adsorption capacity, but compromises on severer flux decline and a tendency of membrane fouling. To overcome this disadvantage, membranes with higher molecular weight cut-off can be used.

Determining binding of polycyclic aromatic hydrocarbons to CTABr micelles using semi-equilibrium dialysis techniques.

Micellar enhanced ultrafiltration (MEUF) has been shown to be an effective removal technique for a variety of trace contaminants in wastewater, especially for water soluble low molecular weight organic contaminants. In MEUF, contaminants first partition into surfactant micelles prior to removal by ultrafiltration, where the contaminants are below the molecular weight cut-off of the ultrafiltration membrane but the micelles are above the cut-off. Binding constants of selected Polycyclic aromatic hydrocarbons (PAHs) such as naphthalene, phenanthrene, pyrene and fluorene have been determined in order to examine the removal efficiency of MEUF for PAHs with Cetyltrimethylammonium bromide (CTABr) using a semi equilibrium dialysis method. PAHs show strong binding with CTABr because of hydrophobic interactions. Our results enabled us to develop a relationship between binding constant (log KB) and log KOW for neutral compounds, which will be useful for predicting MEUF performance for PAHs removal from waste water. The range of our reported binding constant values are from 2.61 to 5.07.

Modeling arsenic (V) removal from water by micellar enhanced ultrafiltration in the presence of competing anions.

With increasing arsenic (As) contamination incidents reported around the world, better processes for As removal from industrial wastewater and other contaminated waters are required to protect drinking water sources. Complexation of As with cetylpyridinium chloride (CPC) cationic surfactant micelles, coupled with ultrafiltration (UF), has the potential to improve As removal, but competition from other anions could be a limiting factor. Using a binary-system ion-exchange model, the selectivity coefficients for binding of the monovalent and divalent forms of arsenate (As (V)) to cationic cetylpyridinium (CP+) micelles, relative to Cl-, were determined to be 0.55 for H2AsO4- and 0.047 mol L-1 for HAsO42-, respectively. The affinity sequence for binding of commonly occurring monovalent anions by CP+ micelles was found to be NO3- > Cl- > HCO3- > H2AsO4-, and for divalent anions, SO42- > HAsO42-. Distribution of As (V) between the micellar and aqueous phases was explored using ion exchange isotherms, with higher pH and lower concentrations of competing anions increasing rejection of As (V) across UF membranes. A model accounting for these effects, based on mass balances across UF membranes and selectivity coefficients for binding of anions to the CP+ micelles, was used to predict As (V) removal during micellar-enhanced ultrafiltration (MEUF) of mixtures of competing anions. Model predictions agreed well with experiment results for both artificial and spiked natural river water samples. Arsenic (≈0.1 mM) removals of 91% and 84% were achieved from artificial waters and spiked natural river waters, respectively, by adding 20 mM CPC prior to UF.

Simultaneous removal of Cd (II) and p-cresol from wastewater by micellar-enhanced ultrafiltration using rhamnolipid: Flux decline, adsorption kinetics and isotherm studies.

Flux decline due to membrane fouling by surfactant micelles is the major problem limiting the use of micellar enhanced ultrafiltration (MEUF) for the treatment of wastewater. Understanding of underlying mechanisms of membrane fouling, adsorption kinetics and adsorption isotherm are very important for the successful application of MEUF studies. In the present study, an unsteady state model considering sequential occurrence of complete pore blocking and gel layer formation was proposed for explaining flux decline behavior during rhamnolipid based MEUF for simultaneous removal of Cd+2 and p-cresol from aqueous solution under batch concentration mode. The model was developed based on the Hermia's complete pore blocking model and resistance-in-series model coupled with gel layer theory incorporating the effects of feed temperature, variation of viscosity and retentate concentration with time, and pressure dependent mass transfer coefficient. A good agreement between the experimental data and model predictions was demonstrated. The effects of operating conditions were found to have a significant effect on the flux decline behavior and onset of gel layer formation. The use of ultrafiltration membrane for the study of adsorption kinetics and adsorption isotherm was demonstrated. Kinetic studies disclosed that both Cd+2 and p-cresol adsorption was better described by the pseudo-second order model for both single and binary solution. The results of isotherm studies revealed that adsorption of both Cd+2 and p-cresol was spontaneous in nature and equilibrium data was best fitted by Langmuir model with the maximum adsorption capacity of RHL vesicles of 208.33 and 53.27 mg g-1 for Cd+2 and p-cresol, respectively at 299 K. The model parameters of membrane fouling, adsorption kinetics and adsorption isotherm evaluated in this study could be useful in designing and scale up of RHL based MEUF process.

Purification of residual leach liquors from hydrometallurgical process of NiMH spent batteries through micellar enhanced ultra filtration.

Hydrometallurgical processes for the treatment and recovery of metals from waste electrical and electronic equipment produce wastewaters containing heavy metals. These residual solutions cannot be discharged into the sewer without an appropriate treatment. Specific wastewater treatments integrated with the hydrometallurgical processes ensure a sustainable recycling loops of the electrical wastes to maximize the metals recovery and minimize the amount of wastes and wastewaters produced. In this research activity the efficiency of ultrafiltration combined with surfactant micelles (micellar-enhanced ultrafiltration) was tested to remove metals form leach liquors obtained after leaching of NiMH spent batteries. In the micellar-enhanced ultrafiltration, a surfactant is added into the aqueous stream containing contaminants or solute above its critical micelle concentration. When the surfactant concentration exceeding this critical value, the surfactant monomers will assemble and aggregate to form micelles having diameter larger than the pore diameter of ultrafiltration membrane. Micelles containing contaminants whose diameter is larger than membrane pore size will be rejected during ultrafiltration process, leaving only water, unsolubilized contaminants and surfactant monomers in permeate stream. The experiments are carried out in a lab-scale plant, where a tubular ceramic ultrafiltration membrane is used with adding a surfactant to concentrate heavy metals in the retentate stream, producing a permeate of purified water that can be reused inside the process, thus minimizing the fresh water consumption.

Treatment of WEEE industrial wastewaters: Removal of yttrium and zinc by means of micellar enhanced ultra filtration.

In this paper, the efficiency of micellar enhanced ultrafiltration technique (MEUF) was tested for the removal of yttrium and zinc ions from synthetic industrial liquid wastes. UF membranes (monotubular ceramic membranes of 210 kDa and 1 kDa molecular weight cut-off) were used with adding an anionic surfactant, sodium dodecyl sulfate (SDS). A two - level full factorial design was performed in order to evaluate the effect of molecular weight cut-off, sodium dodecyl sulfate concentration and pressure on the permeate flux and rejection yields. It was found that the single factors presented the largest influence on the permeate flux: the membrane pore size and the pressure had positive effect, instead the SDS had negative effect. Regarding the metal rejection yields the main relevant factors were the membrane pore size with a negative effect, followed by the surfactant concentration with a positive effect. The effect of the pressure seemed to be almost negligible, for zinc removal experiments had a positive effect in the interactions with the surfactant and membrane pore size. The results showed that very good removal percentages up to 99% were achieved for both metals under the following conditions: 1 kDa membrane MWCO, in the presence of the surfactant at a concentration above CMC independently of the investigated pressure.

Oleylethoxycarboxylate--an efficient surfactant for copper extraction and surfactant recycling via micellar enhanced ultrafiltration.

The nonaoxyethylene oleylether carboxylic acid Akypo RO90 VG, a surfactant with ionic character at high pH and non-ionic character at low pH, has been investigated with respect to copper removal from aqueous streams via micellar enhanced ultrafiltration (MEUF) with subsequent copper and RO90 separation using the method of cloud point extraction (CPE). Almost quantitative Cu2+ removal is obtained in MEUF and more than 90% Cu2+ is separated from RO90 in CPE. The investigation of Cu(2+)/RO90 complexes with small-angle neutron scattering (SANS) shows almost no structural change of RO90 micelles in the presence of Cu2+. These results show the importance of the surfactant head group for optimizing the specific interaction with the ion to be extracted. This optimization and the ability to recycle the surfactant by a temperature variation and using the cloud point phenomenon is an elegant approach to achieve efficient metal ion extraction.

Adsorptive removal of phenolic compounds using cellulose acetate phthalate-alumina nanoparticle mixed matrix membrane.

Mixed matrix membranes (MMMs) were prepared using alumina nanoparticles and cellulose acetate phthalate (CAP) by varying concentration of nanoparticles in the range of 10 to 25wt%. The membranes were characterized by scanning electron micrograph, porosity, permeability, molecular weight cut off, contact angle, surface zeta potential, mechanical strength. Addition of nanoparticles increased the porosity, permeability of the membrane up to 20wt% of alumina. pH at point of zero charge of the membrane was 5.4. Zeta potential of the membrane became more negative up to 20wt% of nanoparticles. Adsorption of phenolic derivatives, catechol, paranitrophenol, phenol, orthochloro phenol, metanitrophenol, by MMMs were investigated. Variation of rejection and permeate flux profiles were studied for different solutes as a function of various operating conditions, namely, solution pH, solute concentration in feed and transmembrane pressure drop. Difference in rejection of phenolic derivatives is consequence of interplay of surface charge and adsorption by alumina. Adsorption isotherm was fitted for different solutes and effects of pH were investigated. Catechol showed the maximum rejection 91% at solution pH 9. Addition of electrolyte reduced the rejection of solutes. Transmembrane pressure drop has insignificant effects on solute rejection. Competitive adsorption reduced the rejection of individual solute.

Impact of selected wastewater constituents on the removal of sulfonamide antibiotics via ultrafiltration and micellar enhanced ultrafiltration.

To better understand the environmental mobility of sulfonamide antibiotics and develop improved processes for their removal during wastewater treatment, stirred cell ultrafiltration (UF) experiments were conducted using both synthetic and real wastewater effluent. The interactions between selected sulfonamides (sulfaguanidine, sulfathiazole and sulfamerazine), solids and dissolved organic matter were systematically explored. The further impact of micellar enhanced ultrafiltration (MEUF), a process in which surfactants are added at micellar concentrations to enhance removal of various trace contaminants from aqueous streams, was then explored by using a cationic surfactant, cetyltrimethylammonium bromide (CTAB). Ultrafiltration of sulfonamides in the absence of other materials generally removed only 15-20% of the antibiotics. The presence of micellar solutions of CTAB generally improved removal of sulfonamides over UF alone, with rejections ranging from 20 to 74%. Environmental solids (sediment) further increased retention of sulfonamides using both UF and MEUF, but the presence of DOM did not influence rejection. Similar trends were observed on UF and MEUF of real effluent samples that had been spiked with the sulfonamides, confirming the environmental relevance of the observed interactions between sulfonamides, surfactant, and wastewater constituents. The results demonstrate that MEUF processes can be designed for the selective removal of such trace contaminants as sulfonamide antibiotics.