Donnan Dialysis for Recovering Ammonium from Fermentation Solutions Rich in Volatile Fatty Acids.

For the production of polyhydroxyalkanoates (PHA) using nitrogen-rich feedstocks (e.g., protein-rich resources), the typical strategy of restricting cell growth as a means to enhance overall PHA productivity by nitrogen limitation is not applicable. In this case, a possible alternative to remove the nitrogen excess (NH4+/NH3) is by applying membrane separation processes. In the present study, the use of Donnan dialysis to separate ammonium ions from volatile fatty acids present in the media for the production of PHA was evaluated. Synthetic and real feed solutions were used, applying NaCl and HCl receiver solutions separated by commercial cation-exchange membranes. For this specific purpose, Fumasep and Ralex membranes showed better performance than Ionsep. Sorption of ammonium ions occurred in the Ralex membrane, thus intensifying the ammonium extraction. The separation performances with NaCl and HCl as receiver solutions were similar, despite sorption occurring in the Ralex membrane more intensely in the presence of NaCl. Higher volumetric flow rates, NaCl receiver concentrations, and volume ratios of feed:receiver solutions enhanced the degree of ammonium recovery. The application of an external electric potential difference to the two-compartment system did not significantly enhance the rate of ammonium appearance in the receiver solution. The results obtained using a real ammonium-containing solution after fermentation of cheese whey showed that Donnan dialysis can be successfully applied for ammonium recovery from such solutions.

Interplay between Forced Convection and Electroconvection during the Overlimiting Ion Transport through Anion-Exchange Membranes: A Fourier Transform Analysis of Membrane Voltage Drops.

Electrodialysis (ED) applications have expanded in recent years and new modes of operation are being investigated. Operation at overlimiting currents involves the phenomenon of electroconvection, which is associated with the generation of vortices. These vortices accelerate the process of solution mixing, making it possible to increase the transport of ions across the membranes. In this work, frequency analysis is applied to investigate the interaction between different parameters on the development of electroconvection near anion-exchange membranes, which would provide a basis for the development of ED systems with favored electroconvection. Chronopotentiometric curves are registered and Fast Fourier Transform analysis is carried out to study the amplitude of the transmembrane voltage oscillations. Diverse behaviors are detected as a function of the level of forced convection and current density. The synergistic combination of forced convection and overlimiting currents leads to an increase in the signal amplitude, which is especially noticeable at frequencies around 0.1 Hz. Fast Fourier Transform analysis allows identifying, for a given system, the conditions that lead to a transition between stable and chaotic electroconvection modes.

Investigation of ion-exchange membranes by means of chronopotentiometry: A comprehensive review on this highly informative and multipurpose technique.

Electrodialysis is mostly used for drinking water production but it has gained applicability in different new fields in recent decades. Membrane characteristics and ion transport properties strongly influence the efficiency of electrodialysis and must be evaluated to avoid an intense energy consumption and ensure long membrane times of usage. To this aim, conducting studies on ion transport across membranes is essential. Several dynamic characterization methods can be employed, among which, chronopotentiometry has shown special relevance because it allows a direct access to the contribution of the potential in different states of the membrane/solution system. The present paper provides a critical review on the use of chronopotentiometry to determine the main membrane transport properties and to evaluate mass transfer phenomena. Properties, such as limiting current density, electrical resistances, plateau length, transport number of counter-ions in the membrane, transition times, and apparent fraction of membrane conductive area have been intensively discussed in the literature and are presented in this review. Some of the phenomena evaluated using this technique are concentration polarization, gravitational convection, electroconvection, water dissociation, and fouling/scaling, all of them also shown herein. Mathematical and experimental studies were considered. New trends in chronopotentiometric studies should include ion-exchange membranes that have been recently developed (presenting anti-fouling, anti-microbial, and monovalent-selective properties) and a deeper discussion on the behaviour of complex solutions that have been often treated by electrodialysis, such as municipal wastewaters. New mathematical models, especially 3D ones, are also expected to be developed in the coming years.

Trade-Off between Operating Time and Energy Consumption in Pulsed Electric Field Electrodialysis: A Comprehensive Simulation Study.

Electrodialysis (ED) has been recently introduced in a variety of processes where the recovery of valuable resources is needed; thus, enabling sustainable production routes for a circular economy. However, new applications of ED require optimized operating modes ensuring low energy consumptions. The application of pulsed electric field (PEF) electrodialysis has been demonstrated to be an effective option to modulate concentration polarization and reduce energy consumption in ED systems, but the savings in energy are usually attained by extending the operating time. In the present work, we conduct a comprehensive simulation study about the effects of PEF signal parameters on the time and energy consumption associated with ED processes. Ion transport of NaCl solutions through homogeneous cation-exchange membranes is simulated using a 1-D model solved by a finite-difference method. Increasing the pulse frequency up to a threshold value is effective in reducing the specific energy consumption, with threshold frequencies increasing with the applied current density. Varying the duty cycle causes opposed effects in the time and energy usage needed for a given ED operation. More interestingly, a new mode of PEF functions with the application of low values of current during the relaxation phases has been investigated. This novel PEF strategy has been demonstrated to simultaneously improve the time and the specific energy consumption of ED processes.

Treatment of Cyanide-Free Wastewater from Brass Electrodeposition with EDTA by Electrodialysis: Evaluation of Underlimiting and Overlimiting Operations.

Growing environmental concerns have led to the development of cleaner processes, such as the substitution of cyanide in electroplating industries and changes in the treatment of wastewaters. Hence, we evaluated the treatment of cyanide­free wastewater from the brass electroplating industry with EDTA as a complexing agent by electrodialysis, aimed at recovering water and concentrated solutions for reuse. The electrodialysis tests were performed in underlimiting and overlimiting conditions. The results suggested that intense water dissociation occurred at the cathodic side of the commercial anion­exchange membrane (HDX) during the overlimiting test. Consequently, the pH reduction at this membrane may have led to the reaction of protons with complexes of EDTA-metals and insoluble species. This allowed the migration of free Cu2+ and Zn2+ to the cation-exchange membrane as a result of the intense electric field and electroconvection. These overlimiting phenomena accounted for the improvement of the percent extraction and percent concentration, since in the electrodialysis stack employed herein, the concentrate compartments of cationic and anionic species were connected to the same reservoir. Chronopotentiometric studies showed that electroconvective vortices minimized fouling/scaling at both membranes. The electrodialysis in the overlimiting condition seemed to be more advantageous due to water dissociation and electroconvection.

Electrochemical Degradation of Reactive Black 5 using two-different reactor configuration.

Novel Sb-doped SnO2 ceramic electrodes sintered at different temperatures, are applied to the degradation of Reactive Black 5 in both divided and undivided electrochemical reactors. In the undivided reactor the discoloration of the solution took place via the oxidation of RB5 dye, without the corresponding reduction in the chemical oxygen demand for the ceramic electrodes. However, in the divided one, it was possible to achieve the discoloration of the solution while at the same time decreasing the chemical oxygen demand through the ·OH-mediated oxidation, although the chemical oxygen demand degradation took place at a slower rate.

Study of the atenolol degradation using a Nb/BDD electrode in a filter-press reactor.

The present paper deals with the atenolol (ATL) degradation by advanced anodic oxidation using a boron-doped diamond anode supported on niobium (Nb/BDD). Cyclic voltammetry performed on this electrode revealed that it presents a high quality (diamond-sp3/sp2-carbon ratio), high potential for OER and that ATL can be oxidized directly and/or indirectly by the electrogenerated oxidants, such as hydroxyl radicals, persulfate ions and sulfate radicals. Electrolysis experiments demonstrated that ATL degradation and mineralization follow a mixed (first and zero) order kinetics depending on the applied current density. At high applied current densities, the amount of OH radicals is very high and the overall reaction is limited by the transport of ATL (pseudo first-order kinetics) whereas for low applied current densities, the rate of OH radicals generation at the anode is slower than the rate of arrival of ATL molecules (pseudo-zero order kinetics). Estimated values of kzero and kfirst based on the assumption of pseudo-zero or pseudo-first order kinetics were carried oud as a function of the supporting electrolyte concentration, indicating that both parameters increased with its concentration due the higher production of sulfate reactive species that play an important role in degradation. Finally, MCE increased with the decrease of current density, due to the lower amount of OH present in solution, since this species could be rapidly wasted in parasitic reactions; and the increase of sulfate concentration due to the more efficient production of persulfate.

Antibiotics mineralization by electrochemical and UV-based hybrid processes: evaluation of the synergistic effect.

Antibiotics are not efficiently removed in conventional wastewater treatments. In fact, different advanced oxidation process (AOPs), including ozone, peroxide, UV radiation, among others, are being investigated in the elimination of microcontaminants. Most of AOPs proved to be efficient on the degradation of antibiotics, but the mineralization is on the one hand not evaluated or on the other hand not high. At this work, the UV-based hybrid process, namely Photo-assisted electrochemical oxidation (PEO), was applied, aiming the mineralization of microcontaminants such as the antibiotics Amoxicillin (AMX), Norfloxacin (NOR) and Azithromycin (AZI). The influence of the individual contributions of electrochemical oxidation (EO) and the UV-base processes on the hybrid process (PEO) was analysed. Results showed that AMX and NOR presented higher mineralization rate under direct photolysis than AZI due to the high absorption of UV radiation. For the EO processes, a low mineralization was found for all antibiotics, what was associated to a mass-transport limitation related to the low concentration of contaminants (200 µg/L). Besides that, an increase in mineralization was found, when heterogeneous photocatalysis and EO are compared, due to the influence of UV radiation, which overcomes the mass-transport limitations. Although the UV-based processes control the reaction pathway that leads to mineralization, the best results to mineralize the antibiotics were achieved by PEO hybrid process. This can be explained by the synergistic effect of the processes that constitute them. A higher mineralization was achieved, which is an important and useful finding to avoid the discharge of microcontaminants in the environment.

The role of the anode material and water matrix in the electrochemical oxidation of norfloxacin.

The roles of the anode material, boron-doped diamond (BDD), with different boron (B) and substrate Silicon (Si) or Niobium (Nb) content, and one dimensionally stable anode (DSA®), were evaluated in the oxidation of norfloxacin (NOR) by electrochemical advanced oxidation process (EAOP). The effect of other components in real wastewater on the performance of EAOP was also studied. The anode materials were characterized by cyclic voltammetry, regarding diamond quality, electro-generation of oxidants and NOR oxidation mechanism (direct and/or indirect). The results showed that the anode material influences on the NOR oxidation pathway, due to distinct characteristics of the substrate and the coating. Apparently, low difference in diamond-sp³/sp2-carbon ratio (Si/BDD100 × Si/BDD2500) does not leads to significant differences in the EAOP. On the other hand, the variation in the sp³/sp2 ratio seems to be higher when Si/BDD2500 and Nb/BDD2500 are compared, which would explain the best current efficiency result for Si substrate. However, the Nb substrate presented a similar current efficiency and a 60% lower energy consumption. Dissolved organic matter (DOM) present in the real wastewater affect the EAOP-Nb/BDD due to HO and persulfate ions scavenged. However, when supporting electrolyte was added to a real wastewater spiked with NOR, the NOR decay reaches similar values found to the synthetic one. Due to the energy saving and mechanical properties, Nb substrate presents some technological advantages in relation to Si, which can facilitate the application to industrial levels.

Determination of the potential gold electrowinning from an ammoniacal thiosulphate solution applied to recycling of printed circuit board scraps.

The use of electrochemical techniques in the selective recovery of gold from a solution containing thiosulphate, ammonia, and copper, obtained from the leaching of printed circuit boards from mobile phones using ammoniacal thiosulphate, are shown in this work. First, cyclic voltammetry tests were performed to determine the potential of electrodeposition of gold and copper, and then, electrowinning tests at different potentials for checking the rates of recovery of these metals were performed. The results of the cyclic voltammetry show that copper deposition occurs at potentials more negative than -600 mV (Ag/AgCl), whereas the gold deposition can be performed at potentials more positives than -600 mV (Ag/AgCl). The results of electrowinning show that 99% of the gold present in solutions containing thiosulphate and copper can be selectively recovered in a potential range between -400 mV (vs Ag/AgCl) and -500 mV (vs Ag/AgCl). Furthermore, 99% of copper can be recovered in potentials more negative than -700 mV (vs Ag/AgCl).