Chromate Removal from Water Using Surfactant-Enhanced Crossflow Filtration

Abstract

Removal of chromate from water was investigated using the surfactant enhanced crossflow filtration technique in which the cationic surfactant, cetyl trimethylammonium bromide (CTAB), was the carrier for the metal ions. The variation of chromate and surfactant rejections, and permeate flux with time were measured as a function of CTAB/chromate concentration ratio, while maintaining a constant transmembrane pressure drop, membrane pore size, and pH of the feed solution. The method was found to be effective in removing chromate from water. It was observed that the efficiency of chromate removal increased with increasing CTAB/ chromate ratio. It was also found that the chromate concentration had a significant effect on the CTAB concentration in the permeate and on the time taken to establish the secondary membrane which consists of a highly viscous surfactant phase in the hexagonal state in the absence of chromate. In the presence of chromate, permeate flux increased at the same CTAB concentration although the surfactant and chromate rejections decreased, indicating lowering of the secondary membrane resistance to permeate flow. These conclusions were confirmed by deadend filtration experiments which showed that the fouling index decreased by the addition of chromate while the opposite was valid when sodium chloride was present in the surfactant/water/electrolyte ternary system.     

Arsenic removal from drinking water by a “loose” nanofiltration membrane

The removal of arsenic from water by a “loose” nanofiltration (NF) membrane was investigated. Prior to the arsenic removal studies, the loose NF membrane was characterized for molecular weight cut-off and pore size by saccharide retention measurements, and electrokinetic charge by streaming potential measurements. In addition, separation of both single salt and mixed salt electrolyte solutions was studied to investigate the ion transport properties of the membrane. Arsenic rejection experiments included variation of pH, arsenic feed concentration, and presence of background electrolyte. In general, arsenic rejection increased with increasing pH and arsenic feed concentration, and was enhanced in the presence of 0.01 M NaCl. Arsenic was removed 60–90% from synthetic feed waters containing 10, 32, 100, and 316 μg/L As(V), resulting in permeate arsenic concentrations of 4, 6, 10, and 25μg/L, respectively. The behavior of the membrane is consistent with the extended Nernst-Planck equation model predictions for an uncharged membrane where size exclusion controls ion retention. However, separation of Arsenic species was a due to a combination of size exclusion, preferential passage of more mobile ions, and charge exclusion.     

Dynamic Analysis and Optimization of Surfactant Dosage in Micellar Enhanced Ultrafiltration of Nickel from Aqueous Streams

Abstract

The micellar enhanced ultrafiltration of Ni(II) ions from the aqueous solution was studied for the dead end system using 20KD Polysulfone membrane. Dynamic behavior of the system was studied with respect to the rejection, yield, and normalized flux. The effect of feed metal ion concentration, surfactant concentration, pH, transmembrane pressure, and S/M ratio was investigated and the optimization of S/M ratio was done. The optimum S/M ratio was 10 while the critical S/M ratio was 5. The effect of monovalent salts was studied on the rejection of metal ions for the salt concentration between 10 mM to 500 mM.     

Affinity Dialysis–A Method of Continuous,Rapid Metal Ion Separation Using Dialysis Membranes and Selective,Water-Soluble Polymers as Extractants

Abstract

A membrane process utilizing dialysis and selective complexation by water-soluble polymers has been developed. This process, termed affinity dialysis, has been shown to selectively extract and concentrate both cations and anions in a manner similar to ion exchange or solvent extraction. The selective removal of calcium from sodium with selectivity of about 30, removal of chromate ion from dilute streams, and separation of transition metal ions such as Cu/Fe and Cu/Zn have all been successfully demonstrated. Effects of different polymers, polymer concentration, temperature, and flow rates have been studied. The effect of increased polymer concentration is to increase product concentration if appropriate changes in feed, polymer solution, and strip flow rates are made. A continuous polymer solution recycle and regeneration system has been constructed and operated with Cu/Zn and chromate/chloride feed streams. Removal of over 95% of the desired ion in one pass and concentration factors of product over effluent in excess of 100 have been achieved at feed flow rates of 24 gal/d. Product concentrations of greater than 3% from as little as 400 ppm feed have been demonstrated in a continuous process. In addition, the degree of polymer loss to the effluent stream has been shown to be less than 0.01%/d for a typical system. Metal removal from typical feeds is about 0.9 g/m² per 1000 ppm metal in the feed. It is expected that this technique may be useful in the separation of organic and biological materials, as well as for ionic species     

Novel polyethyleneimine/TMC-based nanofiltration membrane prepared on a polydopamine coated substrate

Most commercial NF membranes are negatively charged at the pH range of a typical feed solution. In order to enhance the removal of cations (such as Mg²⁺ or Ca²⁺), we utilized polyethyleneimine (PEI) and trimesoyl chloride (TMC) to perform interfacial polymerization reaction on a polydopamine coated hydrolyzed polyacrylonitrile substrate to obtain a positively charged nanofiltration membrane. Effects of polydopamine coating time, PEI concentration, TMC reaction time and concentration on the membrane physicochemical properties and separation performance were systematically investigated using scanning electron microscopy, streaming potential and water contact angle measurements. The optimal NF membrane showed high rejection for divalent ions (93.6±2.6% for MgSO₄, 92.4±1.3% for MgCl₂, and 90.4±2.1% for Na₂SO₄), accompanied with NaCl rejection of 27.8±2.5% with a permeation flux of 17.2±2.8 L·m⁻²·h⁻¹ at an applied pressure of 8 bar (salt concentrations were all 1000 mg·L⁻¹). The synthesized membranes showed promising potentials for the applications of water softening.     

Separation of Zinc Ions from an Acidic Mine Drainage using a Stirred Transfer Cell–Type Emulsion Liquid Membrane Contactor

Abstract

This is a report on the separation and recovery of zinc ions from an acidic mine drainage using a stirred transfer cell‐type emulsion liquid membrane contactor. Di(2‐ethylhexyl) phosphoric acid was used as a highly selective carrier for the transport of zinc ions through the emulsified liquid membrane. A study was made of the effect on the extraction extent and initial extraction rate of the following variables: pH and initial metal concentration of the feed phase, carrier content in the organic solution, a stripping agent concentration in the receiving phase, and stirring speed in the transfer cell. The content of sulfuric acid as a stripping agent did not show in the studied range any significant influence on metal permeation through the SLM, although a minimum hydrogen ion concentration of 100 g/L is suggested in the internal aqueous solution to ensure an acidity gradient between both aqueous phases to promote the permeation of metal ions toward the strip liquor. Results show that using a pH of 4.0 in the feed acid solution, a concentration of 3% w/w_o of phosphoric carrier in the organic phase and a H₂SO₄ content of 100 g/L in the strip liquor, the extent and rate of extraction through the liquid membrane can be highly favored, pointing to the potential of this method for extracting heavy metals from many kinds of dilute aqueous solutions.     

Transport and hydrolysis of urea in a reactor–separator combining an anion-exchange membrane and immobilized urease

A membrane reactor–separator, in which an anion-exchange membrane and a urease-immobilized poly(vinyl alcohol) (PVA) membrane were clamped together to separate the feed solution and the stripping solution of a dialysis cell, was constructed. The urea in the feed solution passed through the anion-exchange membrane, water film, and then was hydrolyzed to ammonium carbamate in the urease-immobilized PVA membrane. The experimental results showed that no ammonium ion was found in the feed solution under either phosphate or citrate buffer systems at 0·05–0·2 mol dm^?3 and pH 6–9, and various initial concentrations of urea in the feed solution (20–200 mmol dm^?3). This indicates that the water film between two membranes allows the carbamate ions to decompose into ammonium and carbonate ions completely before entering the anion-exchange membrane. The device therefore can be used for the removal of urea from feed solution, while preventing the backflow of ammonium ions from the stripping solution or water film into feed solution. It has significant potential in the development of a wearable or portable artificial kidney. The properties of the urease-immobilized PVA membrane were examined. A kinetic model describing the transport-reaction behavior of urea in the membrane reactor–separator was developed, and the optimum values of the reactor parameters were obtained.     

Removal of Ag(I) and Cr(VI) by Complexation-Ultrafiltration and Characterization of the Membrane by CFSK Model

Removal of Ag(I) and Cr(VI) by complexation-ultrafiltration, anionic polyacrylamide being the complexation agent, has been reported. Effects of operating variables such as initial metal ions concentration in feed, feed pH, polymer-to-metal ions ratio, and applied pressure on the removal of metal ions were studied at a constant feed flow rate of 15 L/min. Maximum rejection obtained were close to 100% for Ag(I) and 94% for Cr(VI) ions in single ion system; and for binary ions system it is 87% for Ag(I) and 76% for Cr(VI) ions. The membrane was characterized using the combined-film theory-Spiegler-Kedem (CFSK) model.     

Ultrafiltration of Humic Acid Solution: Effects of Self‐dispersible Carbon Black and Cations

Abstract

Effects of carbon black (CB) addition on membrane fouling and rejection of macromolecular humic acids (HA) were evaluated by a stirred‐cell ultrafiltration unit. Stable CB dispersions increased filtration resistances, but enhanced HA rejection by the membranes. Monovalent and divalent ions affected the filtration resistance of CB solution differently; namely, NaCl solution showed a very high resistance due to the concentration of CB in the diffusion boundary layer near the membrane surface, whereas CaCl₂ and MgCl₂ solutions showed only cake resistance. The cake layer containing both CB and HA was more easily removed from the membranes than HA‐cake layer.     

ELECTRO-DEIONIZATION OF Cr (VI)-CONTAINING SOLUTION. PART II: CHROMIUM TRANSPORT THROUGH INORGANIC ION-EXCHANGER AND COMPOSITE CERAMIC MEMBRANE

Cr (VI) transport through a composite ceramic membrane containing an ion-exchange component, namely xerogel of hydrated zirconium dioxide, was investigated. The diffusion coefficient of Cr (VI) species through the membrane, which has been determined under open circuit conditions, is 1.80 × 10^?10 m² s^?1. The transport number of Cr (VI) species through the ceramic membrane was found to rise with increasing voltage and reached 0.17 under “over-limiting current” conditions. On the other hand, the transport of chromate ions through hydrogel of hydrated zirconium dioxide becomes more intensive with a decrease in potential drop through the system involving ion-exchanger bed and ceramic membrane due to decrease in the membrane resistance. The diffusion coefficient of Cr (VI) ions in hydrogel of the inorganic ion exchanger was estimated as 4.36 × 10^?12 m² s^?1. A possibility of Cr (VI) removal from a weakly acidic diluted solution using an electro-deionization method was shown: the degree of solution purification was found to reach 50%. The transport of species is realized through both the solution and the ion exchanger.     

Chemically modified polybenzimidazole nanofiltration membrane for the separation of electrolytes and cephalexin

A novel chemical modification process has been proposed to prepare polybenzimidazole (PBI) nanofiltration membrane with desirable pore sizes and pore-size distribution. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis have verified the proposed chemical modification reaction between the PBI membrane and p-xylylene dichloride. Depending on the post-treatment process in the p-xylylene dichloride/heptane solution, one can finely control the pure water permeability of the modified membrane. The modified PBI membranes have a decreased effective mean pore size, a narrowed pore size distribution, and demonstrate superior ion rejection performance for liquid separation, especially for the fractionation of multivalent cations and anions from monovalent ions. It is also found that the charge characteristics of PBI membrane may vary with the solution pH, which is reflected by the rejection of NaCl under different pH. Particularly, this modified PBI NF membrane can be employed for the separation and concentration of cephalexin with impressive high rejection rates under a wide range of pH.     

Adsorption of some heavy metal ions from aqueous solutions on Nafion 117 membrane

Nafion 117 membrane was investigated for the removal of Ni(II), Co(II), Pb(II), Cu(II) and Ag(I) metal ions from their synthesized aqueous solutions. The different variables affecting the adsorption capacity of the membrane such as contact time, initial metal ion concentration in the feed solution, pH of the sorption medium and temperature of the solution were investigated on a batch sorption basis. The affinity of Nafion 117 membrane towards heavy metal ions was found to increase in the sequence of Cu(II), Ni(II), Co(II), Pb(II), and Ag(I) with adsorption equilibrium achieved after 30 min for all metal ions. Among all parameters, pH has the most significant effect on the adsorption capacity, particularly in the range of 3.1-5.9. The variation of temperature in the range of 25-65 °C was found to have no significant effect on the adsorption capacity. Nafion 117 membrane was found to have high stability combined with repeated regeneration ability and can be suggested for effective removal of heavy metal ions such as Cu(II), Ni(II) and Co(II) from aqueous solutions.     

Boron removal by ion exchange membranes

Boron removal from aqueous solution was studied through Neosepta-AHA membrane by Donnan dialysis (DD) method as a function of concentration, pH, conduct time, membrane structure and effect of accompanying ions. The feasibility of the system was examined and the highest boron removal was obtained when the pH of the feed phase was 9.5. On the other hand, it was determined that reverse flow transition was accelerated by counter ions and HCO₃⁻ ion was found to be more effective than Cl⁻ and SO₄⁻² ions. It was determined that obtained results of AHA membrane was compared with Neosepta AFN and AMH membranes and the flow rate of boron through Neosepta AHA, AFN and AMH anion exchange membranes were found to be between 3.10⁻⁸−3232.10⁻⁸ mmol cm⁻² s⁻¹ depending on concentration of feed and receiver phases, pH as well as counter ion properties. The order for recovery of boron for membranes was found to be as AFN>AMH>AHA. It could be concluded that the DD method is an appropriate method for boron removal from aqueous solution when an appropriate counter anion was chosen at suitable pH value.     

Application of reverse osmosis to reduce pollutants present in industrial wastewater

Reverse osmosis (RO) is increasingly used as a separation technique in chemical and environmental engineering; desalination, selective separation and wastewater treatment are well established examples. Treatment by RO reduces high levels of dissolved salts but has certain limitations in the removal of organics from chemical industry effluents. We describe a comparative study of four different polyamide membranes that were tested for their ability to reduce the concentrations of pollutants in a synthetic effluent stream containing acrylnitrile and three inorganic species (sulphate, ammonium and cyanide). The pH value of the solution plays an important role in the ionization of the different species and, subsequently, in their rejection. The membranes were checked using a 3×10⁻³ m² flat cell where the permeated and concentrated currents were recirculated to the feed reservoir. In a preliminary set of experiments the pH of the feeding solution was 9.0. The rejection percentage of sulphate ion was high in all the membranes tested (96% to 99.4%) regardless of the working pressure. Ammonium rejection values were between 72.3% and 83.9%, while acrylnitrile rejection was low (10.5% to 28.8%) compared with the results obtained for the other pollutants. Cyanide rejection was negative for all membranes tested except for HR95PP, which produced a rejection percentage of 16.5%. The same membrane also produced higher rejection percentages for cyanide and acrylnitrile than the other membranes. Finally, this membrane was selected to study the influence of the feed stream pH on the rejection of ammonium and cyanide ions. The study concluded that cyanide and ammonium could not be acceptably eliminated in a single step operation when they are simultaneously present in industrial wastewater. The results pointed to the need to carry out several steps at different pH values to reduce the level of both pollutants in the studied wastewater.     

Effect of pH on the rejection of inorganic salts and organic compound using nanofiltration membrane

Nanofiltration (NF) has recently received increased attention as a possible tertiary treatment process providing high rejection of solutes and high water flux rate. In this research, solute separation experiments using NF membranes were made with inorganic salts including heavy metal and organic compounds in different pH levels. The rejection of inorganics from feed solution was found to be dependent on the electric charge of membrane as well as the ionic radius and valence of ion. The divalent cation appeared to reduce the potential of negatively charged membrane to lower the rejection of ion. The results of organic compounds showed that the rejection could be estimated from the pKa value and molecular weight of organics, and the pH of the feed solution.     

Relation between salt rejection and electrokinetic properties on Shirasu porous glass (SPG) membranes with nano-order uniform pores

The salt rejection by Shirasu porous glass (SPG) membranes having nano-order uniform pores was investigated for understanding the electrokinetic mechanism resulting from the surface charge developed on the membrane when in contact with salt solutions. Due to the dissociation of the hydroxyl groups such as silanol groups on the membrane surface, the membrane was negatively charged over a pH range of 3–10 from electrophoretic measurements. Cross-flow filtration experiments showed that up to 63% of NaCl was rejected by an SPG membrane having a mean pore diameters of 33 nm in a 1 mol m⁻³ NaCl solution at pH 7 under a transmembrane pressure of 74 kPa, even though the pore diameter is much larger than the ion diameter. This is a consequence of the electrostatic repulsive interaction between the co-ions (Cl⁻ ions) and the membrane surface. At the same pH, the rejection factor of NaCl decreased with increasing salt concentration due to an increase in the ionic strength. More negative charge on the membrane surface at higher pH resulted in higher rejection factors of NaCl for a fixed salt concentration. Higher rejection factors of NaCl by SPG membranes with smaller pore sizes for a fixed concentration are due to the higher ratio of the thickness of the electric double layer (Debye length) to the pore radius. The SPG membrane showed a salt rejection sequence: Na₂SO₄, NaCl and CaCl₂ at the same pH. This is because divalent anions (SO₄²⁻) are more strongly repelled by the negatively charged membrane, while divalent cations (Ca²⁺) adsorb specifically onto the membrane surface than monovalent cations (Na⁺). The salt rejection factor increased with increasing permeate volume flux. Due to the stronger acidity of the membrane materials, SPG membranes had a higher rejection factor and a lower isoelectric point (IEP < 3) than ceramic membranes.     

Use of Foam Flotation to Remove tert-Butylphenol from Water

Abstract

The surfactants cetyl pyridinium chloride (CPC) and sodium dodecyl sulfate (SDS) were used in a study of an adsorptive bubble flotation process in batch mode to remove tert-butylphenol (TBP) from water. The TBP removal is maximized when the surfactant concentration is around the critical micelle concentration (CMC). Since micelles form above the CMC, this indicate that the higher the surfactant monomer concentration, the better the removal, but the micelles compete with the air/water interface for the TBP, resulting in micelles reducing removal efficiency. The addition of NaCl to the feed solution results in a significant reduction of the ability of CPC to remove TBP, while it improves the ability of SDS to remove TBP.     

纳米SiO2/SDBS复合强化超滤处理含镉废水的影响因素

以纳米SiO2同阴离子表面活性剂十二烷基苯磺酸钠（SDBS）复合的胶束强化超滤处理含镉废水。考察了粉体加入、pH值、粉体浓度对超滤的影响。结果表明,纳米SiO2加入后,膜通量提高了25%,Cd2+截留率有所提高,渗透液中SDBS的浓度在一定条件下有所降低。膜通量、SDBS及Cd2+的截留率随pH值的变化而变化,三者随纳米SiO2加入量的增大而降低。另外,膜阻力主要为膜面吸附和膜孔堵塞阻力。     

Modification of cellulose acetate: Its characterization and application as an ultrafiltration membrane

The development of cellulose acetate blend membranes using a commercial grade Mycell cellulose acetate and cellulose diacetate with suitable pore structure is discussed. These membranes were characterized in terms of resistance of the membrane, pure water flux, the molecular weight cutoff, water content, pore size, and porosity. The removal of copper metal ions by this blend membrane using polyethyleneimine as a chelating agent was studied. The effects of copper ion concentration and casting solution composition on separation are also discussed. A possible correlation between feed and permeate concentration of copper ion is evaluated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1939–1946, 1998     

Characteristics of thin-film nanofiltration membranes at various pH-values

Salt rejection and ion selectivity of NF-255 and NF-45 nanofiltration (NF) membranes were investigated. The rejection of two cations (Na⁺, Ca²⁺) and two anions (Cl⁻, SO_4²⁻) which are common in natural and in industrial wastewater, were studied as a function of pH at permanent pressure and temperature. The ion rejection of NF membranes were investigated in single salt solutions like NaCl, CaCl₂, Na₂SO₄, CaSO₄, and in multicomponent systems that contained all the previous ions. We found that, there is a minimum rejection of the Na⁺ and Cl⁻ ions between pH 4-5 in NF-255 and between pH 7-8 in NF-45. The rejection of calcium ions were increased in each case at lower pH in both membranes. However the pH value where the ion rejection behaviour of membranes changed, were different: pH 4 in NF-255 and pH 8 in NF-45. In NF-45 the chloride ion has negative rejection which depends on the quality of ions and the pH. We found that below pH values of 4 the selectivity of mono- and multivalent cations considerable increased in NF-255. This phenomena may be used for separation of calcium ions from sodium ions from weakly acidic (hydrochloric and sulfuric acid) solution, e.g. regeneration solution of sodium form softening ion exchangers.