Reactive dye removal in dye/salt mixtures by nanofiltration membranes containing vinylsulphone dyes: effects of feed concentration and cross flow velocity

In this study, DS5 DK type nanofiltration membranes were tested to recycle the reactive dye bath effluents. Reactive black 5 (RB5), reactive orange 16 (RO16), reactive blue 19 (RB19) and NaCl were used in the experiments to prepare the synthetic dye and salt mixtures. Effects of feed concentration, pressure and cross flow velocity on the permeate flux and color removal were investigated. Permeate flux increased with increasing pressure for all NaCl solutions. Dye concentration had a significant effect on flux values. Under the fixed NaCl concentrations the flux decreased with increasing dye concentrations. Dye rejections greater than 99% were achieved. Permeate was almost colorless. A gel layer formed by the rejected dye on membrane surface operates as a resistance to the permeation of dyes due to complete rejection of high molecule weight dyes, especially for the low salt concentrations. The presence of salt concentration has an interesting effect on color removal. Color removal decreased with increasing salt concentration. Cross flow velocities had also a significant effect on flux values. The dye formed agglomerates at high NaCl concentrations. High cross flow velocities decreased this effect.     

Treatment of effluents from textile-rinsing operations by thermally stable nanofiltration membranes

Thermally stable nanofiltration membranes were used to recover hot water from rinsing effluents from acid and reactive dyeing operations. Two types of flat-sheet membranes, MPF-34 (MWCO 200) and MPF-36 (MWCO 1000), were tested at 60°C and 10 bar. Experiments carried out with the made-up feeds containing acid dye and acetic acid showed that both membranes were able to retain more than 99% of dye. MPF-36 suffered from substantial flux decline due to the dye and acid in the feeds but still provided higher fluxes than MPF-34. Furthermore, reactive dye rejection of MPF-36 was acceptable, ranging from 97 to 99.5%, while the fluxes, 105-140 1/m².h, were exceptionally high. MPF-36 was then further tested with the wastewater from industrial processes. The membrane could recover hot water by removing more than 98% of acid dye and 90% of reactive dyes. Despite severe fouling by acid dye, the membrane was still able to provide 40-50 1/m².h of permeate fluxes. For the reactive dye rinsing effluents, remarkably high fluxes of 120-1501/m2.h were obtained. Chemical cleaning of the used membrane with 0.2% wt. HNO₃ and subsequently 0.5% wt. NaOH recovered 80-100% of the flux.     

Thin-film composite nanofiltration membranes prepared by electropolymerization

A novel approach to preparation of composite asymmetric nanofiltration membranes is reported based on a thin selective layer deposited by electropolymerization (EP) on top of an asymmetrically porous and electronically conductive porous support. Support films with ultrafiltration characteristics were cast from a concentrated dispersion of carbon black particles, a few tens of nanometers large, in a solution of polysulfone followed by precipitation in a non-solvent bath (phase inversion). Composite membranes with poly(phenylene oxide) and polyaniline thin top layers were prepared by EP deposition from solutions of phenol and aniline, respectively, of which polyaniline film demonstrated a dense uniform structure and water flux and rejection to sucrose and magnesium sulfate in the nanofiltration range.     

Treatment of a textile effluent: application of a combination method involving adsorption and nanofiltration

A combination of adsorption and nanofiltration (NF) was adopted for the treatment of a textile dyehouse effluent containing a mixture of two reactive dyes. The effluent stream was first treated in a batch adsorption process with sawdust as an adsorbent to reduce the dye concentration of the effluent by about 83% for Dye 1 and 93% for Dye 2. The effluent from the adsorption unit was passed through an NF unit for the removal of the remaining small amount of dyes and to recover the associated chemicals (mainly salt) in the effluent stream. The dyes remaining after this step were less than 1 ppm. The percentage removal of COD was greater than 99%, and the salt recovery was on the order of 90%. Equilibrium studies were carried out with synthetic solutions of the dyes (both single component as well as two-component systems) at room temperature. The adsorption rates were studied in detail using varying amounts of the adsorbent. NF of the effluent was performed in a cross-flow system using a 400 molecular weight cut-off membrane. A detailed study was carried out to observe the effect of the process parameters, namely applied pressure and bulk velocity on the process outputs such as dye rejection, COD removal, permeate flux and salt recovery. Finally, direct NF of the effluent (with the original high concentration) was undertaken, and the performance of the process was compared with the combination method. The permeate flux for the proposed combined method was found to be about twice that for the direct NF method. The dye rejection improved significantly compared to adsorption.     

Fouling of nanofiltration and ultrafiltration membranes applied for wastewater regeneration in the textile industry

Textile effluents usually contain high concentrations of inorganics as well as organics, and the therefore difficult to treat. Membrane processes can be used for many of these wastewaters in the textile industry. Two typical examples are discussed: (1) the use of nanofiltration for the treatment of exhausted dye baths, in view of water recycling, and (2) the use of ultrafiltration for the removal of spin finish from waste water resulting from rinsing of textile fibres. Both applications are in principle feasible, but in practice the process is negatively influenced by membrane fouling. In the first application, fouling is assumed to be caused by (ad)sorption of organic compounds, which has a large influence because of the high concentrations used in textile dyeing. Furthermore, the high salt concentrations result in a decrease of the effective driving force because of the high osmotic pressures obtained for typical dye baths. Experimental results are discussed, and the applicability of nanofiltration is related to the characteristics of the dye baths for different dyeing methods. In the second application, the concentration of organic compounds is relatively low, but because of the hydrophobic nature of the spin finish compounds, a significant effect of membrane fouling is expected. An improvement is suggested by using nanofiltration membranes instead of ultrafiltration membranes.     

Correlation between retention and adsorption of phenolic compounds in nanofiltration membranes

Equilibrium adsorption experiments of phenol, 3-chlorophenol, 4-chlorophenol, and 3-nitrophenol aqueous solutions on NF90 membrane were conducted to obtain the corresponding adsorption isotherms at 25 ºC. Single-compound solutions with concentration ranging from 0.1 to 8 mmol L^− 1 were used. Freundlich and Langmuir models were compared to the experimental isotherms and their characteristic parameters were obtained from linear fits. In addition, the adsorptive behaviour of twelve aqueous phenolic compounds on the NF90 membrane was studied in order to investigate the relationship between adsorption and retention of selected solutes. An inverse correlation between the adsorbed amount, at the same equilibrium concentration (1 mmol L^− 1), and retention was found. The influence of the molecular hydrophobicity and dipole moment of phenolic compounds on membrane adsorption, solute retention and water flux decline was also investigated.     

Polymer-based membranes for solvent-resistant nanofiltration:A review

Separation of organic mixture is an inevitable process in most modern industrial processes. In the quest for a more sustainable and efficient separation, solvent-resistant nanofiltration (SRNF) has emerged as a promising answer. This is because SRNF is a membrane-based process which offers the key advantages of high efficacy and lowenergy intensity separation. In particular, polymer-based membranes can offer compelling opportunities for SRNFwith unprecedented cost-effectiveness.As a result, intensive research efforts have been devoted into developing novel polymer-based membraneswith solvent-resistant capacities as well as exploring potential applications in different types of industries. In this review, we aim to give an overview of the recent progress in the development of the state-of-the-art polymer-based membranes for SRNF in the first section. Emerging nanomaterials for mixed matrix and thin film nanocomposite membranes are also covered in this section. This is followed by a discussion on the current status ofmembrane engineering and SRNFmembrane commercialization. In the third section,we highlight recent efforts in adopting SRNF for relevant industrial applications such as food, bio-refinery, petrochemical, fine chemical and pharmaceutical industries followed by separations of enantiomers in stereochemistry, homogeneous catalysis and ionic liquids. Finally, we offer a perspective and provide deeper insights to help shape future research direction in this very important field of SRNF.     

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.     

Novel nanofiltration membranes with tunable permselectivity by polymer mediated phase separation in polyamide selective layer

Microstructure in selective layer has played a decisive role in permselectivity of nanofiltration (NF) membranes, and nanomaterials were well-known additives that had been applied to mediate the microstructure and permeability of polyamide NF membranes. However, nanoadditives generally displayed a poor dispersion in membranes or in fabrication process. To solve this problem, we showed an interesting concept that novel NF membranes with hybrid selective layer consisting of flexible polyisobutylene (PIB) and rigid polyamide could be fabricated from wel-defined interfacial polymerization. The hydrophobic polymer mediated phase separation and microdomains formation in polyamide layer were found. The immiscibility between the rigid polyamide and flexible PIB as well as the resultant interface effect was interpreted as the reason for the polymer enhanced permselectivity, which was similar with the well-known thin film nanocomposite (TFN) membranes that nanoparticles incorporated contributed significantly to membrane permeability and rejection performance. Our results have demonstrated that novel NF membranes with enhanced performance can be prepared from im-miscible polymers, which is a new area that has not been extensively studied before.     

A comprehensive review of nanofiltration membranes:Treatment, pretreatment, modelling, and atomic force microscopy

Nanofiltration membranes (NF) have applications in several areas. One of the main applications has been in watertreatment for drinking water production as well as wastewater treatment. NF can either be used to treat all kinds of water including ground, surface, and wastewater or used as a pretreatment for desalination. The introduction of NF as a pretreatment is considered a breakthrough for the desalination process. NF membranes have been shown to be able to remove turbidity, microorganisms and hardness, as well as a fraction of the dissolved salts. This results in a significantly lower operating pressure and thus provides a much more energy-efficient process. Similar to other membrane processes, a major problem in NF membrane applications is fouling. Several studies have investigated the mechanisms of fouling in NF membranes and suggested methods to minimize and control the fouling of NF membranes. For NF membrane characterizations and process prediction, modeling of NF processes and the use of atomic force microscopy (AFM) are very important. The ability to predict the performance of NF processes will lead to a lower number of experiments, saving of time and money, and help to understand the separation mechanisms during NF. A comprehensive review of NF in water treatments is presented including a review of the applications of NF in treating water as well as in the pretreatment process for desalination; the mechanism as well as minimization of NF membrane fouling problems; and theories for modelling and transport of salt, charged and noncharged organic compounds in NF membranes. The review will also address the application of AFM in studying the morphology of membrane surfaces as part of the NF membrane characterization.     

Application of membrane processes in closing of water cycle in a textile dye-house

In this study, investigations were made to close water cycle in dye-houses. At the first stage, optimum operation conditions of a membrane nanofiltration were determined. Experiments were carried out for DL membranes (Osmonics, USA). The effect of temperature, pressure and pH was investigated. Investigations were performed for different types of real wastewater produced in a laboratory-scale Pyrotec S dyeing apparatus (Roaches) for various types of reactive dyes. An over 90% dye hold-up was obtained for all dye baths.At the final stage of the experiments, dyeing processes were carried out with the use of a filtrate from nanofiltration as water applied for dyeing, rinsing and washing after dyeing. In cooperation with the Technical University of Lodz, we have managed to apply biological degradation of the concentrate, carried out in two different reactor systems.     

Dual layer composite nanofiltration hollow fiber membranes for low-pressure water softening

Nanofiltration (NF) membrane process has become increasingly attractive due to their unique characteristics to selectively remove specific compounds or ions. The most commonly NF membranes are negatively charged which is unsuitable for hardness removal. Therefore, the development of novel NF membranes with a positively charged skin has become a key issue for low pressure water softening.     

Removal of hexavalent chromium by nanofiltration

Removal of chromate CrO₄²⁻ from water was investigated using nanofiltration as a possible alternative to the conventional methods of CrVI removal from aqueous solution. Retention measurements with single reference salt revealed that Donnan exclusion plays an important role. The phenomenological parameters σ and P were calculated using the Spiegler-Kedem equation. The rejection rate depends on the ionic strength and pH. The increasing of ionic strength decreases the retention. The effect of pH was clarified by using a stable diagram of the CrVI---H₂O system. Better retention was obtained at basic pH.     

Negatively charged organic–inorganic hybrid silica nanofiltration membranes for lithium extraction

Effective extraction of lithium from high Mg~(2+)/Li+ratio brine lakes is of great challenge. In this work, organic–inorganic hybrid silica nanofiltration(NF) membranes were prepared by dip-coating a 1,2-bis(triethoxysilyl)ethane(BTESE)-derived separation layer on tubular TiO_2 support, for efficient separation of LiC l and MgCl_2 salt solutions. We found that the membrane calcinated at 400 °C(M1–400) could exhibit a narrow pore size distribution(0.63–1.66 nm) owing to the dehydroxylation and the thermal degradation of the organic bridge groups. All as-prepared membranes exhibited higher rejections to LiCl than to MgCl_2, which was attributed to the negative charge of the membrane surfaces. The rejection for LiCl and MgCl_2 followed the order: LiCl N MgCl_2, revealing that Donnan exclusion effect dominated the salt rejection mechanism. In addition, the triplecoated membrane calcined at 400 °C(M3–400) exhibited a permeability of about 9.5 L·m~(-2)·h~(-1)·bar~(-1) for LiCl or MgCl_2 solutions, with rejections of 74.7% and 20.3% to LiCl and MgCl_2,respectively, under the transmembrane pressure at 6 bar. Compared with the previously reported performance of NF membranes for Mg~(2+)/Li+separation, the overall performance of M3–400 is highly competitive. Therefore, this work may provide new insight into designing robust silica-based ceramic NF membranes with negative charge for efficient lithium extraction from salt lakes.     

Potential use of nanofiltration like-forward osmosis membranes for copper ion removal

The discharge of industrial effluent containing heavy metal ions would cause water pollution if such effluent is not properly treated. In this work, the performance of emerging nanofiltration(NF) like-forward osmosis(FO)membrane was evaluated for its efficiency to remove copper ion from water. Conventionally, copper ion is removed from aqueous solution via adsorption and/or ion-exchange method. The engineered osmosis method as proposed in this work considered four commercial NF membranes(i.e., NF90, DK, NDX and PFO) where their separation performances were accessed using synthetic water sample containing 100 mg·L~(-1) copper ion under FO and pressure retarded osmosis(PRO) orientation. The findings indicated that all membranes could achieve almost complete removal of copper regardless of membrane orientation without applying external driving force.The high removal rates were in good agreement with the outcomes of the membranes tested under pressuredriven mode at 1 MPa. The use of appropriate salts as draw solutes enabled the NF membranes to be employed in engineered osmosis process, achieving a relatively low reverse solute flux. The findings showed that the best performing membrane is PFO membrane in which it achieved N 99.4% copper rejection with very minimum reverse solute flux of 1 g·m~(-2)·h~(-1).     

Nanofiltration of textile wastewater for water reuse

The textile industry produces a large amount of wastewater that is highly coloured with high loading of inorganic salt. Crossflow nanofiltration using thin film composite polysulfone membrane was used to recover the electrolyte solution and reject the colour. Using a synthetic textile effluent of reactive dye and NaCl solution, the study focused on the mechanism controlling flux and rejection by varying four main parameter; crossflow velocity, initial dye concentration, feed pressure, and electrolyte concentration. Results show that flux was dominated by the osmotic pressure created from the presence of NaCl, and that dye concentration did not significantly effect the flux or rejection. Working at low pressures of up to 500 kPa, relatively high fluxes were obtained, with an average dye rejection of 98% and NaCl rejections of less than 14%. Thus, a high quality of reuse water could be recovered. Even after a number of cycles, the membrane did not foul irreversibly, with an overall mean waterflux recovery of 99%.     

Influence of filtration conditions on the performance of nanofiltration and reverse osmosis membranes in dairy wastewater treatment

Filtration performance and fouling of nanofiltration (NF) and reverse osmosis (RO) membranes in the treatment of dairy industry wastewater were investigated. Two series of experiments were performed. The first one involved a NF membrane (TFC-S) for treating the chemical-biological treatment plant effluents. The second one used a RO membrane (TFC-HR) for treating the original effluents from the dairy industry. The permeate flux was higher at higher transmembrane pressures and higher feed flowrates. The curves of permeate flux exhibited a slower increase while the feed flowrate decreased and the pressure increased. Membrane fouling resulted in permeate flux decline with increasing the feed COD concentration. Furthermore, the flux decline due to the COD increase was found higher at higher pressures for both NF and RO membranes.     

Rejection of salt mixtures from high saline by nanofiltration membranes

Nanofiltration (NF) membranes have recently been employed as pretreatment unit operations in seawater desalination processes and as partial demineralization to seawater. The present paper investigates the performance of selected commercial NF membranes to reject salts of high concentrations at salinity levels representative of brackish and sea water. Two commercial nanofiltration membranes (NF90 and NF270) have been investigated in detail to study their performance in filtering aqueous solutions containing different salt mixtures in a cross-flow NF membrane process within the pressure range from 4 to 9 bar. Spiegler-Kedem model (SKM) was used to fit the experimental data of rejection with the permeate flux. The results showed that NF90 membrane was shown to have a distinct ability to reject both monovalent and divalent ions of all investigated mixtures with very reasonable values but with relatively low flux. This will make NF90 more suitable for the application in the pretreatment of desalination processes. On the other hand, NF270 can reject monovalent ions at relatively low values and divalent ions at reasonable values, but at very high permeate flux. The SKM model only fitted well the experimental data of divalent ions in salt mixture. Based on the evaluation of the overall performance of NF90 and NF270 membranes, their distinct ability to reject salts at high salinity from seawater is considered an advantage in the field of pretreatment of seawater feed to desalination units.     

Chemical cleaning of reverse osmosis and nanofiltration membranes fouled by licorice aqueous solutions

The aim of this work was finding optimum cleaning agents and conditions for cleaning reverse osmosis (RO) and nanofiltration (NF) membranes fouled by licorice aqueous solutions. The effect of various chemicals on flux recovery (FR) and resistance removal (RR) of the fouled membranes was investigated. For both membranes the results indicate that a combination of ethylene diamine tetra acetic acid (EDTA), sodium dodecyl sulphate (SDS) and sodium hydroxide may be used as cleaning agents to achieve an optimum cleaning efficiency. Zeta potential and contact angle measurements indicate the changes in charge and hydrophilicity of the surface of RO and NF membranes at various pH solutions, respectively. The effect of surface characteristics is evident in efforts to select the optimal operating conditions. The effect of cleaning condition such as concentration, temperature, pH and cleaning time was studied. The optimum temperature, cleaning time, pH and concentration were found as 35 ± 1 °C, 20 min, 12 and 0.1 wt.%, respectively. SEM pictures showed the surface morphology of RO and NF membrane.     

Bipolar nanofiltration membranes based on plasma modified microfilters

Track‐etched membranes were used as support for deposition of plasma polymerized layers and formation of bipolar nanofiltration membranes. The 75 KHz plasma reactor was applied for that purpose. Three kinds of monomers were plasma polymerized. They were as follows: n‐butylamine, allylamine, and acrylic acid. For each monomer, the best polymerization parameters were selected. It was determined that acrylic acid deposited at the highest rate, then deposited allyloamine and finally n‐butylamine. Among the electrodes, the grounded one offered more stable layer and can be used for plasma polymer deposition. The obtained membranes showed good rejection properties toward bivalent ions. It was shown that the sequence of deposited layers did not affect the separation properties. For some investigated membranes, rejection reached 50–80% value. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39790.