Сoncentration Polarization in Membrane Systems

Мұқаба

Дәйексөз келтіру

Толық мәтін

Ашық рұқсат Ашық рұқсат
Рұқсат жабық Рұқсат берілді
Рұқсат жабық Рұқсат ақылы немесе тек жазылушылар үшін

Аннотация

Concentration polarization (CP) in membrane systems is understood as the phenomenon of the emergence of concentration gradients in a solution near the membrane surface, which is a result of the selective transfer of certain components of the solution through the membrane under the influence of transmembrane driving forces. CP accompanies all types of membrane processes. It affects transfer conditions and reduces the efficiency of separation processes: in most cases, there is a decrease in the overall transfer rate and an increase in energy consumption, as well as a loss of permselectivity. This review examines the general patterns and features of the CP phenomenon in the processes of electrodialysis, reverse osmosis, nanofiltration, ultrafiltration, pervaporation, as well as in membrane sensor systems and fuel cells. The fundamental principles of the CP phenomenon and experimental methods for its study are considered.

Толық мәтін

Рұқсат жабық

Авторлар туралы

P. Apel

Joint Institute for Nuclear Research

Email: v_nikonenko@mail.ru
Ресей, Dubna, Moscow region, 141980

P. Biesheuvel

Wetsus, European Centre of Excellence for Sustainable Water Technology

Email: v_nikonenko@mail.ru
Нидерланды

O. Bobreshova

Voronezh State University

Email: v_nikonenko@mail.ru
Ресей, Voronezh, 394018

I. Borisov

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences

Email: v_nikonenko@mail.ru
Ресей, Moscow, 119991

V. Vasil’eva

Voronezh State University

Email: v_nikonenko@mail.ru
Ресей, Voronezh, 394018

V. Volkov

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences

Email: v_nikonenko@mail.ru
Ресей, Moscow, 119991

E. Grushevenko

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences

Email: v_nikonenko@mail.ru
Ресей, Moscow, 119991

V. Nikonenko

Kuban State University

Хат алмасуға жауапты Автор.
Email: v_nikonenko@mail.ru
Ресей, Krasnodar, 350040

A. Parshina

Voronezh State University

Email: v_nikonenko@mail.ru
Ресей, Voronezh, 394018

N. Pismenskaya

Kuban State University

Email: v_nikonenko@mail.ru
Ресей, Krasnodar, 350040

I. Ryzhkov

Institute of Computational Modeling SB RAS; Siberian Federal University

Email: v_nikonenko@mail.ru
Ресей, 50-44 Akademgorodok, Krasnoyarsk, 660036; Krasnoyarsk, 660041

M. Sharafan

Kuban State University

Email: v_nikonenko@mail.ru
Ресей, Krasnodar, 350040

A. Yaroslavtsev

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: yaroslav@igic.ras.ru
Ресей, Moscow, 119991

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2. Fig. 1. Scheme of concentration polarization with constant (a) and variable (b) thickness of the boundary layer (under tangential filtration conditions).

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3. Fig. 2. Scheme of concentration profiles in the COM and in adjacent diffusion layers (DL) during the flow of sublimiting current (a) and superlimiting current (b). The space charge region (SCR) and electroconvective vortices, as well as the dissociation of water molecules, are shown. Jie and Jid are the electromigration and diffusion fluxes of ions i. δ is the thickness of the Nernstian diffusion boundary layer.

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4. Fig. 3. Scheme of the main processes initiated by the phenomenon of CP in super-limit current modes.

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5. Fig. 4. a) Dependence of the total current density and partial current densities of H+ and Na+ ions for MK-40 and MK-41 membranes in 0.001 M NaCl solution; b) Dependence of the diffusion layer thickness on the total current density. Markers – experimental data; lines – trend lines.

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6. Fig. 5. Schematic representation of the constituent flows of lithium ions through a track membrane during the separation of cations by the EBM method.

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7. Fig. 6. Interferograms displaying the concentration profiles and the structure of the diffusion layer in a sodium chloride solution at the boundary with the MK-40 cation-exchange membrane (a, b) and in the electrodialyzer chamber formed by the MK-40 and MA-40 membranes (c) at the sublimiting j = 0.5 jlim (a), superlimiting j = 2jlim (b) and j = 10jlim (c) current densities. δtot is the total thickness of the DPS; δ is the Nernstian thickness of the diffusion layer at j < jlim; δ’ and d are the thicknesses of the region with the dominant diffusion mechanism of ion transport and the region of convective instability, respectively, arising at j > jlim. Adapted from [133].

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8. Fig. 7. Dependence of the thicknesses of different structural regions of the complete diffusion layer on the current density normalized to its critical value jcr, corresponding to the occurrence of unstable electroconvection by the Rubinstein-Zalzmann mechanism [78]. The results correspond to a section at a distance of y = 2.7 cm from the entrance to the electrodialyzer channel. The dots are experimental data obtained by processing the concentration profiles measured by laser interferometry, the dashed lines are trend lines. The solid curves are calculated using the “basic” 2D model [70]. Adapted from [133].

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9. Fig. 8. Schemes of generation of protons and hydroxyl ions in the AOM/NaH2PO4 solution system by the mechanisms of “acid dissociation” (index 1) and catalytic dissociation of water with the participation of fixed membrane groups (index 2), as well as in the bipolar region formed by positively charged fixed groups and negatively charged “bound particles” (index 3). A is the acid residue of an oxyacid (phosphoric, tartaric, citric, etc.).

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10. Fig. 9. Volt-ampere characteristics of anion exchange membranes with strongly basic (ASE, Astom, Japan) and weakly basic (CJMA-2, ChemJoy LTD, China) fixed groups in 0.02 M NaxH(3-x)PO4 solutions with pH values of 4.4 and 7.2.

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11. Fig. 10. Calculated chronopotentiograms and time dependences of the effective transport numbers of H+ and H2PO4− ions calculated in the depleted boundary diffusion layer at a distance of 0.2 μm from the AOM. The simulation was performed at j = 2.2 jlimLev for the AMX membrane (Astom, Japan) in a 0.02 M KH2PO4 solution. The inset shows the initial sections of the presented dependences. The first (τ1) and second (τ2) transition times are marked with vertical dotted lines.

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12. Fig. 11. Visualization of electroconvective vortex structures in a depleted solution at the surface of the AMX membrane. The studies were carried out in 0.02 M NaCl solution, j/j = 3.0 (a) and NaH2PO4, j/j = 5.5.

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13. Fig. 12. Volt-ampere characteristic and power of the membrane-electrode unit based on Nafion/PEDOT at 65оС (a), constructed according to data from [180]. Contributions of ohmic polarization (b), activation polarization (c) and concentration polarization (d) for a membrane-electrode unit with similar characteristics at 40о and 80оС, constructed according to data from [181].

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14. Fig. 13. Concentration polarization modulus depending on the composition of the raw material at different values of the Peclet number, Cp = 1.

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15. Fig. 14. Volt-ampere characteristics of a track membrane with asymmetric nanopores [255] in KCl solutions of different concentrations (shown to the left of the curves, in mol/l).

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16. Fig. 15. Micrographs of cleavages of track membranes with asymmetric pores – conical in shape (A) and cylindrical with a bullet-shaped mouth (B). The scale bar is 5 µm in both images.

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17. Fig. 16. Internal concentration polarization in a track membrane with asymmetric pores [256]. Distribution of the concentration of K+ cations (A) and Cl– anions (B) along the longitudinal axis of the pore at a positive (1, 2) and negative (3, 4) potential of 0.5 V from the mouth side. Conical pore (1, 3) and pore with a bullet-shaped mouth (2, 4). The concentration of KCl in the bulk of the solution is 0.1 mol/l. The radius of the pore mouth is 2 nm. The pore mouth is located at the point x/d = 0, where d is the pore length.

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18. Fig. 17. Schematic representation of the sorption centers of the MF-4SK and MF-4SK/PANI membranes; SEM micrograph of the cross section of the MF-4SK/PANI membrane (obtained by treatment with 0.005 M C6H5NH3Cl and 0.00625 M (NH4)2S2O8) with elemental mapping by F, S, C, N; calibration dependences of the response of PD sensors based on MF-4SK and MF-4SK/PANI membranes obtained by treatment with a monomer/oxidizer (N1) or an oxidizer/monomer/oxidizer (N2), including subsequent hydrothermal treatment (HT) at 120°. The figure was compiled using the data presented in [286, 288].

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