New ion exchange membrane derived from sulfochlorated polyether sulfone for electrodialysis desalination of brackish water

The purpose of this work is to study the desalination of brackish water using a new ion exchange membrane, made from sulfochlorated polyethersulfone (Cl‐PES), and crosslinked using aminated polyethersulfone (NH2‐PES) as a crosslinking reagent. This membrane, named ClNH2 membrane, has been obtained by reaction between Cl‐PES with 1.3 SO₂Cl groups per monomer unit and 0.2 equivalent amount of NH2‐PES. ClNH2 membrane has been characterized in terms of contact angle, transport number, intrinsic conductivity, and water uptake (as a function of temperature). Electrodialysis performances of the newly synthetized membranes have been measured using an electrodialysis cell at a laboratory scale and compared to commercial membranes. All the experiments have been performed using synthetic brackish water solutions prepared from sodium chloride salts with different concentrations (varying from 0.5 to 5.0 g/L). The concentration of different water samples obtained has been found to be below the amount recommended by the World Health Organization (WHO) for drinking water.     

Recovery of organic acids from waste salt solutions derived from the manufacture of cyclohexanone by electrodialysis

The possibility of recovery of organic acids from waste salt solution, derived from the manufacture of cyclohexanone, by means of single anion-exchange membrane electrodialysis was studied in this paper. Some key parameters, such as voltage, current density, pH value, current efficiency and specific energy consumption are studied and analyzed in details on theoretical basis. Results indicate that single anion-exchange membrane electrodialysis is found to be a feasible method for recovery of organic acids. Several valuable acids, such as butyric and adipic acids are effectively separated from waste salt solution by only one-step electrodialysis. And it consumes less energy compared to the conventional processes.     

Separation of sodium ions from trivalent chromium by electrodialysis using monovalent cation selective membranes

Trivalent chromium Cr(III) in wastewaters produced by leather tanning processes must be treated before discharge in the environment. Electrodialysis was studied for this application. Cr(III) ion is separated from sodium ion by using modified cation-exchange membranes. The membrane modification consists of a polyethylenimine layer electrodeposited on the membrane surface. This layer is positively charged in acidic media and repels multivalent ions while monovalent ions cross the membrane. The modified membrane in this study was a Nafion^® 324 membrane. The transfer of chromium, sodium, calcium, magnesium, chloride and sulphate ions from a mixture was investigated. The pH must be regulated in order to avoid chromium hydroxide precipitation in the dilute chamber. The behaviour of sulphate chloride system is unusual for the AMX membrane. Adsorption of PEI on the membrane surface is assumed to explain this behaviour. The overall current efficiency was close to 96–98% for cations and anions.     

Innovative beneficial reuse of reverse osmosis concentrate using bipolar membrane electrodialysis and electrochlorination processes

Reverse osmosis (RO) is a widely used and rapidly growing desalination technology. A major disadvantage of this process is that the concentrate from the RO process, which could be as much as 25% of the feed stream, represents a polluting stream. This waste stream could pose a significant challenge to the implementation of this process, particularly for inland communities which do not have the option of ocean disposal. An excellent environmentally benign approach to disposal could be beneficial reuse of the waste stream. This study presents two innovative beneficial reuse strategies for RO concentrate produced by an integrated membrane system (IMS) from a wastewater reclamation facility. The technologies evaluated in this study included bipolar membrane electrodialysis (BMED) for conversion of RO concentrate into mixed acid and mixed base streams, and electrochlorination (EC) for onsite chlorine generation. Bench-scale studies conducted with BMED demonstrated that RO concentrate could be desalted while producing mixed acids and mixed bases with concentrations as high as 0.2N. Similarly, the EC process was capable of producing a 0.6% hypochlorite solution from RO concentrate. The acids and bases as well as the hypochlorite produced could be directly applied to the RO process as well as upstream pre-treatment processes. A preliminary economic evaluation of the viability of these two approaches was conducted by conducting rough order of magnitude cost estimates based on the bench-scale performance of these processes on RO concentrate. A comparison of the overall costs of an Integrated Membrane System utilizing these innovative reuse strategies with conventional disposal options and thermal zero liquid discharge treatment is presented. This comparison indicates that a reuse approach might be economically viable for inland wastewater reuse facilities that utilize RO membranes and have limited options for concentrate disposal.     

Analysis of fouling potential in the electrodialysis process in the presence of an anionic surfactant foulant

Fouling of ion exchange membranes in an electrodialysis process is highly sensitive to the concentration of a surfactant. To investigate the influence of the fouling on the process performance, an anion exchange membrane was characterized by electrochemical properties as well as physical and chemical properties. The fouling potential was then quantitatively analyzed using the membrane fouling index as a function of the surfactant concentration. It was observed that the fouling mechanism is initiated by the micelle formation. That is, most of SDBS molecules form a fouling layer on the membrane surface at a higher concentration than the critical micelle concentration. Also the SDBS fouling mechanisms caused by the fouling layer were examined by the electrochemical impedance spectroscopy. The equivalent circuits show that the fouling potential of the system was increased by an additional layer, simultaneously increasing the electrical resistance to permeation of ions through the membrane. However, the SDBS fouling on the membrane was a reversible process.     

Effect of concentrate solution pH and mineral composition of a whey protein diluate solution on membrane fouling formation during conventional electrodialysis

The aim of this work was to study the effect of the concentrate solution pH and the composition in calcium, carbonate and protein of the diluate solution to be treated by conventional electrodialysis on the fouling of ion-exchange membranes. Conductivity, system resistance, pH of the diluate and cation migration were monitored to follow the evolution of the demineralization. Total cation migration was similar for all conditions although different forms of fouling were identified after three consecutive 100 min electrodialysis treatments. The nature of fouling and the membrane surface fouled depended on the concentrate pH value, the diluate mineral composition and the intrinsic composition of the whey isolate. Once conditions leading to membrane fouling were identified, an alternative configuration for our electrodialysis stack is proposed to prevent fouling onset.     

Polymeric membranes based on cellulose acetate loaded with candle soot nanoparticles for water desalination

This study is concerned with modifying cellulose acetate (CA)/polyethylene glycol (PEG) membranes prepared via phase inversion technique in the presence of carbon nanoparticles; candle soot (CS) resulting from combusted candle. CS nanoparticles were analyzed via Fourier transform infrared spectroscopy and transmission electron microscopy. The developed membranes were characterized for their surface morphology, mechanical properties as well as thermal stability. CS nanoparticles contributed in improving the salt rejection % with a slight reduction in the water flux behavior. Employing the annealed cellulose acetate/polyethylene glycol membranes loaded with candle soot nanoparticles provides an adequate approach towards water desalination implementations.     

The desalination of a mixed solution of an amino acid and an inorganic salt by means of electrodialysis with charge-mosaic membranes

A new electrodialysis with charge-mosaic membranes was proposed to achieve efficient desalination of a mixed solution of an amino acid and an inorganic salt. For such a mixed solution, the conventional electrodialytic desalination with both cation-and anion-exchange membranes had resulted in a considerable loss of the amino acid through the membranes. In this method, however, the amino acid in the desalination channel of the electrodialyzer migrates away from the membranes so that the permeation loss of the amino acid through the membrane can be prevented.

Batchwise desalination experiments by this method were carried out with a glutamic acid or arginine solution including NaCl under the condition of constant electric current density. Similar experiments by the conventional method were also carried out. As a result of comparing both methods, the amino acid loss in this method became much smaller than that in the conventional one. It was confirmed that this method was very useful for the desalination of an amino acid solution. The effects of operating conditions on the desalination process are also discussed.     

Diffusion of water and ethanol in ion-exchange membranes: limits of the geometric approach

Diffusion coefficients of water as a solvent and ethanol as a tracer in sulphonated polyethylene (SPE) were measured by the pulsed-gradient spin-echo NMR method. Comparison with the data available for a number of ionic and non-ionic polymers and solvents shows that, except for Nafion, all the materials exhibit a fairly universal dependence of diffusivity on the volume fraction of the solvent. This result is explained on the basis of the geometric obstruction approach and general conditions are formulated for the observed universal dependence. Explanations are proposed for the peculiar behaviour of Nafion and for the low diffusivity of ethanol within the same framework.     

Influences of colloidal stability and electrokinetic property on electrodialysis performance in the presence of silica sol

Negatively charged silica sol is known to lead to fouling of anion exchange membranes during electrodialysis (ED) as a result of its deposition on the membrane surface. It is known that the fouling potential is related to the physical and electrochemical properties of the silica particles as well as those of the anion exchange membranes. In this study, the properties of the silica sol were characterized in terms of its particle size, turbidity, and zeta potential in order to predict their effects on the electrodialysis performance. In the stability of colloidal particles, the critical coagulation concentrations of silica sol were determined as functions of ionic strength, cation species, and solution pH. In the electrodialysis of NaCl solution containing silica sol with various concentrations of CaCl(2), the colloidal behavior related to deposition and transport was examined during and after electrodialysis. The electrodialysis experiments clearly showed that the deposition and transport of silica sol during electrodialysis were related to the colloidal stability of dispersion.     

Preparation and characterization of mono-valent ion selective polypyrrole composite ion-exchange membranes

Polypyrrole composite cation- and anion-exchange membranes (CEM and AEM), in which polypyrrole (PPY) coated on one surface of the membrane as a thin layer, were prepared by chemical polymerization of pyrrole in the presence of high oxidant concentration (Na₂S₂O₈). Existence of polypyrrole layer on the both types of ion-exchange membranes were confirmed by recording their coating density, SEM images and conductivity. These membranes were extensively characterized by recording their properties such as water uptake, ion-exchange capacity, contact angle, permselectivity and membrane conductivity as a function of polymerization time such as. It was observed that due to coating of PPY for 2 h, membrane permselectivity of CEM for NaCl (0.907) was reduced to 0.873, while it was increased from 0.747 to 0.889 in the case of AEM. Similar behaviors were also obtained for bi-valent electrolytes. Electrodialysis experiments were also conducted with polypyrrole composite ion-exchange membranes using mixed electrolytic systems. Relative dialytic rates for NaCl with respect to other bi-valent electrolyte were varied in between 5 and 8 (depending on bi-valent electrolyte), which suggested the feasible and efficient separation of mono-valent from bi-valent electrolyte. Slower electro-migration of bi-valent electrolyte (CaCl₂, MgCl₂ and CuCl₂) in comparison to NaCl was explained on the basis of synergetic effect of sieving of bulkier bi-valent cations by tight and rigid polypyrrole layer and the difference in electrostatic and hydrophobic–hydrophilic repulsion force between bi-valent cations and mono-valent cation. It was concluded that these composite membranes are suitable for the efficient separation of same type of charged ions by electro-driven separation techniques.     

Investigation of the mass transfer processes during the desalination of water containing phenol and sodium chloride by electrodialysis

Oxidation processes are used in wastewater treatment when conventional processes are not effective due to the presence of recalcitrant organic contaminants, like phenol. However, the presence of ionic compounds associated with organic pollutants may retard the oxidation. In this work the transport of species contained in an aqueous solution of phenol containing sodium chloride was evaluated in an electrodialysis (ED) system. An experimental study was carried out in which the influence of the process variables on the phenol loss and sodium chloride removal was investigated. Experiments were also performed without current, in order to determine the phenol transfer due to diffusion. The phenol and salt concentration variations in the ED compartments were measured over time, using dedicated procedures and an experimental design to determine the global characteristic parameters. A phenomenological approach was used to relate the phenol, salt and water fluxes with the driving forces (concentration and electric potential gradients). Under ED conditions, two contributions were pointed out for the phenol transport, i.e. diffusion and convection, this latter coming from the water flux due to electroosmosis related to the migration of salts. The fitting of the parameters of the transport equations resulted in good agreement with the experimental results over the range of conditions investigated.     

Application of relaxation periods during electrodialysis of a casein solution: Impact on anion-exchange membrane fouling

Electrodialysis (ED) is a membrane process used on a large scale. However, one of the common problems is fouling of ion-exchange membranes stacked in the cell. The use of pulsed power, consisting in applying a constant current density during a fixed time of application (T_on) followed by a pause duration (T_off), was demonstrated recently as an effective fouling mitigation method for electrodialysis. Up until now, no work has investigated the potential of electrodialysis using pulsed electric field on protein fouling. The aim of the present work was to study the influence of pulsed electric field (PEF) with a low frequency square shaped periodic signal (T_on = 10 s–T_off = 10 s, T_on = 10 s–T_off = 40 s) in comparison with dc current during electrodialysis of a casein solution at different current densities (10, 20 and 30 mA/cm²) on membrane fouling. It appeared from these results that PEF, under certain conditions of pulse, would avoid fouling on anion-exchange membranes. For 10 s–40 s pulsed electric field conditions, no fouling was observed with any density, while for 10 s–10 s PEF conditions, fouling appeared only at current density over 10 mA/cm². dc current, whatever the current density conditions, led to a fouling on the diluate side of the AEM. Furthermore, when fouling occurred, magnitude layer thickness and dry weight increased with the applied current density. The nature of the fouling was identified as 97% protein. The protein fouling would be due to the dissociation of water molecules and/or heat increase at the anion-exchange membrane interface. The relaxation time of the pulse would limit both phenomena on the membrane.     

Performance enhancement of thin‐film composite membranes in water desalination process by wood sawdust

In this study, polysulfone/wood sawdust (PSf/WSD) mixed matrix membrane (MMM) was prepared as a novel substrate layer of thin‐film composite (TFC) membrane in water desalination. The main aim was to evaluate how different amounts of WSD (0‐5 wt%) and PSf concentrations (12‐16 wt%) in the porous substrate affect the properties of the final TFC membranes in the separation of organic and inorganic compounds. Morphological and wettability studies demonstrated that the addition of small amount of WSD (less than or equal to 1 wt%) in the casting solution resulted in more porous but similar hydrophobic substrates, while high loading (greater than or equal to 2 wt%) of WSD not only changed the substrate wettability and morphology but also increased and decreased the swelling and mechanical properties of substrate layer. Therefore, PA layer formed thereon displayed extensively varying film morphology, interfacial properties, and separation performance. Based on approximately stable permeate flux (ASPF) and apparent salt rejection efficiency (ASRE), the best TFC membrane was prepared over the substrate with 12 to 14 wt% of PSf and around 0.5 to 1 wt% of WSD. Although notable improvements in permeate flux were obtained by adding a small amount of sawdust, the results clearly indicate that the salt rejection mechanism of TFC membrane was different from the glycerin rejection mechanism. Furthermore, durability results of TFC membranes showed that in continuous operation for 30 days, TFC‐14/0.5 and TFC‐14/01 have the maximum plateau levels of stable permeate flux and salt rejection among the all TFC membranes.     

Nature identification and morphology characterization of cation-exchange membrane fouling during conventional electrodialysis

The aim of this work was to study the effect of a concentrate solution pH value and of the composition in calcium, carbonate, and protein of a diluate solution to be treated by conventional electrodialysis on the fouling of cation-exchange membranes (CEM). It appeared that after demineralization of solutions containing CaCl(2) and CaCl(2)+Na(2)CO(3) using a concentrate solution maintained at a pH of 12, mineral fouling appeared on both sides of the CEM. The nature of the deposits was identified as calcium hydroxide and/or carbonate on both surfaces. The mineral fouling presented an aggregation-like crystal following a carnation-like pattern of aggregates of small rhombohedral crystals with CaCl(2) added alone, while CaCl(2)+Na(2)CO(3) yielded a smoother spherical crystal. Protein fouling was detected only on the CEM surface in contact with the diluate after demineralization of a solution containing CaCl(2)+Na(2)CO(3) using a concentrate pH value of 2.     

Heats of solution and the influence of solutes on the temperature of maximum density of water

The influence of N,N-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidinone, N-methyl-2-pyrrolidinone, and N-t-butyl-2-pyrrolidinone on the temperature of maximum density (TMD) of water has been investigated. Heats of solution for these compounds and for diethylsulfoxide, tetramethylene sulfoxide, tetramethylene sulfone, dimethyl sulfoxide, and tetrahydrofuran in water at 23°C are also reported. These data, together with published TMD and heat of solution data for other solutes, are used to examine the relationship between the enthalpy change on dissolution of a solute in water and the effect of the dissolved substance on the structure of water as reflected by changes in the temperature of maximum density of the system.     

Performance evaluation of the different nano-enhanced polysulfone membranes via membrane distillation for produced water desalination in Sert Basin-Libya

A Polysulfone-Polyethylene glycol (PS/PEG) flat sheet membrane was prepared by phase inversion technique. Dimethyl Formamide (DMF) was utilized as a solvent and deionized water was utilized as the coagulant. Polyethylene glycol (PEG) of a various dose of PEG 2000 was utilized as the polymeric improvers and as a pore-forming agent in the casting mixture. The single-walled carbon nanotube (SWCNTs), multi-walled carbon nanotube (MWCNTs), aluminum oxide (Al₂O₃) and copper oxide (CuO) nanoparticles (NPs) were utilized to improve the PS/PEG membrane performances. The characterizations of the neat PS, PS/PEG, PS/PEG/Al2O3 (M1) PS-PEG/CuO (M2), PS-PEG/SWCNTs (M3) and PS/PEG/MWCNTs (M14) nanocomposite (NC) modified membranes were acquired via Fourier-transform infrared analysis (FTIR), water contact angle estimation (WCA), scanning electron microscope (SEM), dynamic mechanical analyzer (DMA) and thermogravimetric analysis (TGA). Enhanced Direct contact membrane distillation (EDCMD) unit was used for estimating the efficiency of the performance of the synthesized NC membranes via 60 °C feed synthetic water and/or saline oil field produced water samples containing salinities 123,14 mg/L. Adjusting the operational procedures and water characteristics confirmed a high salt rejection of 99.99% by the synthesized NC membranes. The maximum permeate flux achieved in the order of SWCNTs (20.91) > Al₂O₃ (19.92) > CuO (18.92) > MWCNT (18.20) (L/m².h) with adjusted concentration of 0.5, 0.75, 0.75, 0.1 wt% compared with PS weight, i.e. 16%. The optimum operational circumstances comprised feed and permeate temperatures 60 °C and 20 °C, respectively. The achieved flux was 5.97 L/m².h, using brine oil field produced water, via PS/PEG/SWCNTs membrane with 0.5 wt% of SWCNTs. Moreover, the membrane indicated sustaining performance stability in the 480 min continuous desalination testing, showing that the synthesized PS/PEG/SWCNTs NC modified membrane may be of magnificent potential to be activated in EDCMD procedure for water desalination.     

Pilot plant studies of novel membranes and devices for direct contact membrane distillation-based desalination

A small pilot plant for direct contact membrane distillation (DCMD) based desalination was built and operated successfully on a daily basis for 3 months. The operation employed hot brine at 64–93 °C and distillate at 20–54 °C. The hot brine was either city water, city water containing salt at the level of 3.5, 6 or 10%, or sea water trucked in from Long Island Sound, CT. One to ten horizontal crossflow hollow fiber membrane modules each having either 2448 or 2652 hollow fibers and 0.61 or 0.66 m² surface area were combined in various configurations to study the plant performance. The highest water vapor flux of 55 kg/(m² h) was achieved with two modules in series; the flux varied between 15 and 33 kg/(m² h) for configurations employing 6–10 modules. The highest distillate production rate achieved was 0.62 gallons per minute (gpm). The membrane modules never showed any sign of distillate contamination by salt. The plant operated successfully with a very limited flux reduction at salt concentrations up to 19.5% from sea water. A mathematical model was successfully developed to describe the performance of the pilot plant with multiple crossflow modules in different test configurations.     

Catalyst-free efficient synthesis of 2-aminothiazoles in water at ambient temperature

A highly efficient and facile method has been described for the synthesis of substituted 2-aminothiazoles in water without any added catalyst or co-organic solvent. The reaction was carried out at ambient temperature and the products were obtained in excellent isolated yields. The developed protocol is successfully applied for the preparation of an anti-inflammatory drug, fanetizole.     

焙烧温度对Fe-Mn催化剂结构和F-T合成性能影响

研究了焙烧温度对Fischer-Tropsch(F-T)合成Fe-Mn催化剂的织构性质、还原行为以及在还原和反应过程中结构变化的影响；在H2/CO=2.0、260 ℃、2.5 MPa和1 000 h－1条件下在固定床反应器上考察了焙烧温度对Fe-Mn催化剂F-T合成反应活性、烃产物选择性和运行稳定性的影响。XRD和TPR结果表明，随着焙烧温度的升高，催化剂中α-Fe2O3晶粒增大，催化剂比表面积降低，促进Mn3+渗入α-Fe2O3晶格中，形成了铁锰固溶体物相，使得催化剂难于还原，当焙烧温度升高到700 ℃时，催化剂中的α-Mn2O3相完全消失。催化剂F-T合成反应评价表明，在不降低催化剂活性的同时，焙烧温度的升高可显著地提高催化剂的反应运行稳定性，并促使烃产物分布向高碳数方向偏移；600 ℃焙烧的Fe-Mn催化剂运行200 h，总体活性高，失活速率较低，对低碳烯烃和中间馏分油段产物选择性好。