Effect of magnesium/calcium ratios in solutions treated by electrodialysis: morphological characterization and identification of anion-exchange membrane fouling

The present study aimed the characterization of the fouling formed on anion-exchange membrane during electrodialysis treatment of model salt solutions at different Mg/Ca ratio (0, 1/20, 1/10, 1/5 and 2/5). The membrane fouling was characterized by membrane parameters (membrane thickness and electrical conductivity) and identified by membrane surface analysis (elemental analysis and X-ray diffraction). The mineral deposit was identified as Ca(OH)2 when no magnesium was present in the model salt. As soon as magnesium was present in the model salt solution for neutral pH((concentrate)) conditions a mix between CaCO3 and Ca(OH)2 was formed. This study is the first one to report the influence of magnesium in solution on the formation of CaCO3 fouling at the interface of anion-exchange membrane during electrodialysis.     

Electrodialysis with Bipolar Membranes: Principles,Optimization, and Applications

This paper is an overview of the bipolar membrane technology. The process of electrodialysis with bipolar membrane (EDBM) along with the different EDBM process configurations are presented. Some ways of optimization of both the bipolar membranes and the EDBM technology are envisaged. Most of the applications relate to the production or recovery of organic acids while the first plant has been commissioned by 1986 at Washington Steel (USA) for the recovery of HF/HNO₃ from waste pickling liquors. In the last few years, there has been increasing interest in using bipolar electrodialysis stacks in chemical and agro industrial processes to directly acidify or basify process streams without the addition of chemicals. This attractive feature of this technology has contributed to the implementation of several plants in fermentation process for the production of organic and amino acids.     

Study of pH correction process of chloride-bicarbonate dilute solutions by electrodialysis with bipolar membranes

The pH of a dilute chloride-hydrocarbonate solution and the concentrations of chloride ions and carbonic acid anions at the outlet of the alkaline and acid chambers of the electrodialysis cell formed by bipolar and anion-exchange membranes were determined. The decrease in the concentration of hydrocarbonate ions in the alkaline chamber with growth of current density was not equal to its increase in the acid chamber. This disbalance was caused by two concurrent processes: the electromigration ion transport through the anion-exchange membrane and the chemical reactions of hydrocarbonate ions with the water dissociation products formed on the bipolar and anion-exchange membranes. A mathematical model was suggested to describe the electrodialysis correction of the pH of a dilute chloride-hydrocarbonate solution. The experimental data on the correction of pH of the chloride-hydrocarbonate solution were well approximated by both the model that takes into account water dissociation on the anion-exchange membrane and the simplified model that neglects water dissociation. The experimental data agreed well with the results of calculations by the model in which the effective anion transport numbers were calculated only from ion concentrations and diffusion coefficients in solution. This reflects the outer diffusion character of the kinetics of ion transport through the anion-exchange membrane, with pH of dilute solutions corrected by electrodialysis.     

Ion and water transport during lithium chloride concentration from aqueous organic solutions by electrodialysis

The concentration of lithium chloride from aqueous organic solutions with different volume concentrations of N,N-dimethylacetamide (DMAA) was studied experimentally. An extended model of the limiting electrodialysis concentration of electrolytes from mixed media was developed. The model takes into account the osmotic and electroosmotic mechanisms of the transfer of water and organic solvent, as well as the electromigration and diffusion mechanisms of the salt transfer. Using the experimental data and the extended model, we evaluated the transport parameters of the MK-40/MA-40 membrane pair in aprotic solutions of variable compositions and studied how they changed with an increase in the volume fraction of DMAA in a mixed solution. The contribution of each of these mechanisms of ion and water transport to the electrodialysis concentration of electrolyte from aqueous and organic aqueous solutions was determined. Electroosmotic transfer was found to be the main mechanism of the solvent transfer that limits the stage of the electrodialysis concentration of the electrolyte from aqueous and organic aqueous solutions.     

Optimal current and voltage trajectories for minimum energy consumption in batch electrodialysis

Cost-effective operations of a batch electrodialyzer for removal of salt from a single salt solution are investigated. It is desired to minimize the operating cost for a particular batch. The operating cost for an electrodialysis (ED) stack is comprised of cost related to energy consumption and cost of maintenance of the ED stack. In effective operations of an ED stack, the maintenance cost is a small fraction of the total operating cost. The bulk of the operating cost is therefore proportional to total energy consumption, which is the sum of the electrical energy needed for salt removal and the energy required to pump various solutions through the ED stack. For fixed feed composition and the desired percent salt recovery, the total energy required is influenced by trajectories of current flowing through and the voltage applied across the ED stack and the operating time. In this regard, the following operations are studied: (I) constant current operation, (II) constant voltage operation, (III) constant current operation followed by constant voltage operation, (IV) constant voltage operation followed by constant current operation, and (V) operation with time-variant current and voltage. For arbitrary relations among salt concentration, current utilization, and stack resistance, optimal current and voltage trajectories that lead to minimum energy requirement are identified for each of the five operations. It is established analytically that operation V is superior to operations III and IV, which in turn are superior to operations I and II. Numerical illustrations reveal that the performance differences in these operations are enhanced as the percent salt recovery is increased.     

Ionic Transport in Electrodialysis of Ammonium Nitrate

During the electrodialysis of ammonium nitrate solution, the fluxes of salt ions pass through the maximum, which is observed near the limiting current, with increasing current density. A decrease in the flux of ammonium ions at the overlimiting current densities is caused by the effect of competitive transport of solution ions and by the formation of weak NH₃ ? H₂O electrolyte due to the alkalization of solution layer adjacent to the cation-exchange membrane in the desalination channel. A decrease in the flux of nitrate ions in the overlimiting current modes is caused by a change in the composition and catalytic activity of the functional groups of anion-exchange membrane towards the dissociation of water molecules due to the effect of ammonium ions.     

Development of thermoplastic polyurethane/polyaniline-doped membranes for the separation of glycine through electrodialysis

Recently, membrane-based separation processes, particularly electrodialysis, have attracted attention for the separation and purification of organic and amino acids from animal feedstock waste. In this study, cation exchange membranes were synthesized by making a composite of thermoplastic polyurethane and polyaniline (PANI) via the doping of various aromatic sulfonic acids, such as β -naphthol sulfonic acid and phenol sulfonic acid. The PANI was prepared using a standard method, which was further used in the composite blending at varying concentrations of 10%–20%. The impact of the concentration of PANI and the nature of the dopant on the membrane characteristics were comparatively studied. The membranes were analyzed by electric conductivity, water swelling, morphological studies (SEM), and thermogravimetric analysis. The membranes were used for the separation of glycine hydrochloride via electrodialysis.     

Formic acid regeneration by electromembrane processes

Waters containing low amounts of sodium formate and sodium hydroxide were processed in order to regenerate formic acid. The treatment was performed in three steps: wastewaters neutralization, sodium formate concentration by conventional electrodialysis (ED), and sodium formate splitting into formic acid and sodium hydroxide by bipolar membrane electrodialysis (BMED). A coupling of these processes was performed. ED was carried out with a current efficiency of 90% and sodium formate concentration up to 2 mol dm⁻³. BMED was performed in a three-compartment cell configuration. Formic acid solution up to 30% was obtained with current efficiency of 80% under a current density of 500 A m⁻². Diffusion of molecular formic acid explains the current efficiency loss. The current efficiency varies with acid concentration and current density. Diffusion is more important through the anion-exchange membrane than through the bipolar membrane (2.5-fold).

Depleted salt produced in BMED was recycled to the neutralisation step.     

Electrodialytic separation of cobalt(II) and nickel(II) using liquid membranes based on tri-n-octylamine and trialkylbenzylammonium chloride

Electrodialytic separation of Co(II) and Ni(II) in the course of their transfer from 3–4 M HCl solutions into dilute solutions of various acids using liquid membranes that contain anion-exchange carriers was studied. The influence exerted on the metal transport rate and separation efficiency by the compositions of the feed and receiving aqueous solutions and of liquid membranes and by the electrodialysis current density was examined. Under optimal conditions, in metal recovery from a solution containing an equimolar mixture of 0.01 M CoCl₂ and NiCl₂, the separation factor β_Co/Ni is 147; when nickel in the feed solution is in excess, it reaches 330, and when cobalt(II) is in excess, it exceeds 400.     

Short communications

The transport of carbonic acid anions through an anion-exchange membrane (AEM) during electrodialysis is studied. At current densities above limiting diffusion values, fluxes of hydrocarbonates and carbonates are lower than those of strong-electrolyte anions. The reason for the decreased fluxes is the recombination of carbonic acid ions with hydrogen ions that form during irreversible dissociation of water molecules at the solution/AEM interface     

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.     

Analysis of Preparation Conditions of H<Subscript>2</Subscript>SO<Subscript>4</Subscript> and NaOH from Sodium Sulfate Solutions by Electrodialysis

Preparation of sulfuric acid and sodium hydroxide from solutions containing sodium sulfate was studied by the electrodialysis method in a three-chamber (?three-compartment) electrodialyzer equipped with two membranes, an anion-exchange membrane AESD-2a and a cation-exchange membrane Nafion 427.     

双极膜技术在环境工程中的应用与展望

简述了双极膜的水解离电渗析及双重电荷排斥性能。介绍了双极膜在含氟废液的处理、有价氟的回收应用、垃圾发酵连续制备有机酸、脱除烟气中的SO2气体、水处理以及双极膜蓄电池等方面的应用现状及前景。双极膜作为一种新型膜,以其水解离电渗析的独特优点,为解决环境工程中存在已久的一些技术难题提供了许多新的思路和解决办法。巧妙地利用双极膜与单极膜的组合,可以设计出许多工艺。双极膜在环境工程中的应用研究值得引起重视。     

Three-compartment bipolar membrane electrodialysis for splitting of sodium formate into formic acid and sodium hydroxide: Role of diffusion of molecular acid

Bipolar membrane electrodialysis is used in a three-compartment configuration to regenerate formic acid and sodium hydroxide from sodium formate. A previous study showed that the diffusion of molecular formic acid induces the loss of acid current efficiency. The present study shows the following results: the diffusion of molecular formic acid through the bipolar membrane explains quantitatively the presence of sodium formate in the sodium hydroxide solution. The loss of acid current efficiency is only due to diffusion of molecular acid through both anion-exchange and bipolar membranes. The sodium hydroxide current efficiency is determined by acid diffusion through the bipolar membrane and OH⁻ leakage through the cation-exchange membrane. The flux of acid diffusion through the membranes is proportional to acid concentration and depends on sodium hydroxide concentration for bipolar membrane and on sodium formate concentration for anion-exchange membrane. The flux rates vary with temperature.     

Recovery of organic acids from fermentation broths

Rising concerns over the use of fossil resources have generated renewed interest in the production of commodity chemicals via fermentation. Organic acids are a particularly attractive target because their functionality enables downstream catalytic upgrading to a variety of compounds. In this article, we survey how common technical issues are addressed in the recovery schemes for several organic acids. We present results for the recovery of acetate using a new method based on amine complexation. Our reactive separation scheme produces a high-purity product, is energy efficient, and avoids the coproduction of a waste salt coproduct, all prerequisites for a large-scale production process.     

Competitive anion transport in desalting of mixtures of organic acids by batch electrodialysis

Desalting and separation of binary and quaternary acid mixtures via batch electrodialysis are investigated in this article. A monoselective cation exchange membrane and either a non-selective or a monoselective anion exchange membrane are employed in the electrodialysis stack. The effects of current density and composition of the initial feed of the electrodialysis stack (employing a non-selective anion exchange membrane) on its performance are studied in experiments involving mixtures of acetic and succinic acids. The effect of the type of the anion exchange membrane on the process performance is examined in desalting experiments involving a mixture of acetic, formic, lactic, and succinic acids. The trends observed in the experiments are interpreted in terms of species-specific parameters (such as molar concentration, charge on ionic species, molecular weight, degree of ionization, and ionic equivalent conductivity) and characteristics of anion exchange membrane used.     

Membrane electrodialysis process for recovery of sulfur dioxide from power plant stack gases

A new regenerative process for recovery of sulfur dioxide from stack gases by sodiumbased solution scrubbing is described. The spent solution from the scrubber, consisting mostly of bisulfite, is converted through the use of a novel low-energy membrane electrodialysis technique to a basic solution of sulfite/hydroxide suitable for reuse in the SO₂ absorbers, and a solution of sulfurous acid from which concentrated SO₂ is easily regenerated. p]This electrodialysis process, based on bipolar membrane technology, requires only a fraction of the energy required in conventional electrolysis. Engineering estimates indicate that this membrane/SO₂ process has a significant economical advantage over other gas desulfurization processes. In addition, this process has internal flexibility to operate under various conditions without the requirement of significant equipment modification.     

双极膜电渗析法处理工业高盐香料废水

采用双极膜电渗析法处理某企业的工业高盐香料废水,旨在将无机盐氯化钠从香料废水中脱除并转化为附加值更高、较高浓度的盐酸和氢氧化钠. 当一次性处理3 L废水时,保证了足够的处理时间,生成盐酸和氢氧化钠的浓度分别能达到1.93 mol·L^-1和1.70 mol·L^-1,脱盐率为99.4%,生成盐酸和氢氧化钠的电流效率分别为30.7%和36.0%,电耗为2.58 kW·h·kg^-1. 分别通过向盐室中补加废水原料和氯化钠固体的方式,均可抑制盐室中氯化钠浓度的减小,将生成的氢氧化钠浓度显著地提高,且后者提高的程度更为明显. 为提高酸、碱产品的纯度,分别考察了阳离子交换膜和阴离子交换膜对Cl^-和Na⁺的阻隔效果,阳离子交换膜对Cl-的阻隔效果有着JAM-II>N2030>TRJCM的顺序,阴离子交换膜JAM-II对Na⁺的阻隔效果高于TRJAM. JCM-II相比于N2030膜有着更低的膜电阻. 综合考虑使用JAM-II/BPM-I/JCM-II组合时效果最好,电耗最低.     

Influence of cations on the proton leakage through anion-exchange membranes

In the recovery of acids from wastewaters or the regeneration of acids and bases from salts by electromembrane processes, the most important phenomenon which limits the current efficiency is the transport of protons through the anion-exchange membrane (AEM). In this work, the proton leakage through an AEM is studied with a system containing hydrochloric acid or sulfuric acid on the cathodic side and the mixture of acid with one homoanionic salt (Li⁺, Na⁺, K⁺, Cr³⁺, NH₄⁺, (CH₃)₄N⁺ and (C₂H₅)₄N⁺) on the anodic side. The proton leakage is quantified from the value of the proton transport number. The results are analyzed assuming that the rate determining step of proton leakage is the interfacial transfer reaction of protons from the aqueous anodic solution to the membrane. The proton leakage is enhanced by the polarizing power of the cation. The transfer of protons into the membrane seems to be catalyzed by the presence of a layer of adsorbed cations on the surface of the membrane. The presence of salt decreases the proton leakage but it is always greater with H₂SO₄ solutions compared to HCl solutions.     

Electrodialysis Extraction and Electrodeposition of Lead(II) in Systems with Liquid Membranes

The extraction of lead(II) ions from nitric acid solutions through liquid membranes under galvanostatic electrodialysis with metal electrodeposition from the receiving solution of perchloric, nitric, or acetic acids is studied. The solitons of di(2-ethylhexyl)phosphoric acid with additives of tri-n-octylamine in 1,2-dichloroethane are used as liquid membranes. The effect of the current density of the electrodialysis and the composition of the initial aqueous solution and receiving solution (catholyte), as well as the composition of liquid membranes on the rate of membrane transport and electrodeposition of the lead(II) ions, is investigated. The optimal conditions of the process are determined. Fine-grained and highly adherent lead deposits are obtained on a platinum cathode during the deposition from perchloric acid solutions. It is shown that the degree of extraction of lead(II) ions from the initial aqueous solution is higher than 90% in the process, while the degree of electrodeposition amounts to 60% within 5 h of electrodialysis.