Electrodialysis with Bipolar Membranes for the Generation of NaOH and HCl Solutions from Brines: An Inter-Laboratory Evaluation of Thin and Ultrathin Non-Woven Cloth-Based Ion-Exchange Membranes
Abstract
:1. Introduction
2. Materials and Methods
2.1. Reagents and Membranes
2.2. Laboratory-Scale Experimental Set-Up
2.3. Analytical Methodologies and Chemical Analysis
2.4. Experimental Campaign
2.5. EDBM Performance Parameters
2.6. Reproducibility Analysis Procedure to Assess the Inter-Laboratory Results
3. Results
3.1. Reproducibility Analysis
3.2. Effect of Current Density in the Different Types of Membrane Configurations Used in the EDBM Set-Ups
3.3. Performance Parameters of the Two Types of Membranes
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
Nomenclature
Acronyms/Abbreviations | |
AEM | anion exchange membrane |
ANOVA | ANalysis of VAriance |
BMED | bipolar membrane electrodialysis |
BPM | bipolar membrane |
CEM | cation exchange membrane |
CRM | critical raw material |
EDBM | electrodialysis with bipolar membranes |
EI | economic importance |
EU | European Union |
IEM | ion-exchange membrane |
MLD | minimum liquid discharge |
SR | supply risk |
SWRO | sea water reverse osmosis |
UNIPA | UNIversità degli studi di PAlermo |
UPC | Universitat Politècnica de Catalunya |
ZLD | zero liquid discharge |
Symbols | |
α | significance level parameter |
concentration of NaOH at time 0, mol L−1 | |
concentration of NaOH at time t, mol L−1 | |
CE | current efficiency, % |
F | faraday constant, C mol−1 |
Fc | calculated F-value |
Fcr | critical F-value |
I | applied electric current, A |
NaOH mole mass, kg. mol−1 | |
N | number of triplets |
S | active membrane area, m2 |
SEC | specific energy consumption, kWh kg−1 |
SP | specific productivity, kg m−2 y−1 |
t | operation time, s |
U | EDBM voltage, V |
volume of the base solution at time 0, L | |
volume of the base solution at time t, L | |
volume of the salt solution at time 0, L |
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Manufacture | Membrane | Identification | Functional Groups | Ion-Exchange Capacity | Wet Thickness (μm) | Membrane Support | Permselectivity (%) | Areal Resistance (ohm cm2) | Ref. |
---|---|---|---|---|---|---|---|---|---|
1 SUEZ | AEM | AR103P | quaternary ammonium | 2.37 (meq/dry g resin) | 570 | Woven polypropylene | 92 | a 9.4 | [30] |
CEM | CR61P | sulfonic acid | 2.2 (meq/dry g resin) | 580 | 94 | a 10 | |||
AEM-treated | 4 AR103A tr. | quaternary ammonium | 2.37 (meq/dry g resin) | 300 | 92 | n.a. | |||
1 SUEZ | AEM | 2 AR103N | quaternary ammonium | 2.37 (meq/dry g resin) | 300 | Thin non-woven polypropylene | 92 | a 2.8 | [30] |
AEM | 3 AR118U | quaternary ammonium | 2.37 (meq/dry g resin) | 130 | Ultra-thin non-woven polyester cloth | 90 | a 11 | ||
CEM | 2,3 CR61N | sulfonic acid | 2.2 (meq/dry g resin) | 300 | Thin non-woven polyester cloth | 95 | a 3.6 | ||
AEM-treated | 2,3,4 AR103N tr. | quaternary ammonium | 2.37 (meq/dry g resin) | 300 | 92 | n.a. | |||
LLC Innovative Enterprise, Schekinozoat | AEM | MB-1 | quaternary ammonium | 4.0 (eq/L) | <900 | Polystyrene divinylbenzene with polyethylene binder | 98 | n.d. | [31] |
CEM | sulfonic acid | 1.4 (eq/L) | <900 | 98 | n.d. | ||||
Membranes International, Inc. | AEM | BMI-9000 | quaternary ammonium | 1.3 (meq/dry g resin) | 450 | Gel polystyrene crosslinked with divinylbenzene | 91 | b <40 | [28] |
CEM | sulfonic acid | 1.6 (meq/dry g resin) | 450 | 91 | b <30 |
UPC | UNIPA | |
---|---|---|
Pumping system | 4 centrifugal pumps (BED 1–4 from PCCell GmbH) | 4 peristaltic pumps (BT601S from Lead Fluid Technology, Co., Ltd., Baoding, China) |
Sampling | Samples are taken from tanks coupled with ball valve taps | Samples are taken from the tanks using syringes. |
Power Supply | HCS-3202 | BK precision 1902B |
Volume measurement | Graduated vessels allow for monitoring volume variations | The volume is calculated as a function of mass and density. The mass variation is monitored using an analytical scale. |
Current Density | Channel | Initial Concentration | Initial Volume | Flow-Rate |
---|---|---|---|---|
100–300 A m−2 | Acid | 0.05M HCl | 1.0 L | 50 L h−1 * |
Base | 0.05M NaOH | 1.0 L | 50 L h−1 * | |
Salt | 2M NaCl | 1.5 L | 50 L h−1 * | |
ERS | 0.25M Na2SO4 | 1.5 L | 50 L h−1 * |
Set-Up | Experimental Conditions | Concentrations (mol/L) | Performance Parameters | Ref. | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Membranes | Membrane Stack | Active Area (cm2) | Nº Triplets | Current Density (A·m−2) | Operation Time (min) | Operation Mode | Initial Salt Solution | Final HCl | Final NaOH | SEC (kWh/kg) | CE (%) | ||
SUEZ | AEM: AR118U & AR103N | HDWR (MK-1) Suez | 280 | 5 | 100–300 | 120 | Batch | 2 M NaCl | 1.77 | 1.25 | 3.29 | 48.5 | This work |
CEM: CR61N | |||||||||||||
BM: AR103N-treated layered with CR61N | |||||||||||||
P CCell | CEM: PC-SK | PCCell ED64-004 | 64 | 3 | 520 | 405 | Batch | 3.2 M NaCl | 2.01 | 1.87 | 2.71 (NaOH) | 88–55 | [20] |
AEM: PC Acid 60 | |||||||||||||
BM: PC BP | |||||||||||||
M EGA | CEM: M-PP RALEX | Elektrolyse Project | 100 | 1 | 1000 | 2400 | Semi-batch | 1 M NaCl | 3.17 | 3.63 | 41.0 (HCl) | n.d. | [21] |
AEM: M-PP RALEX | |||||||||||||
Fumatech | BM: Fumasep FBM | ||||||||||||
Qianqiu | CEM | Shandong Tianwei Membrane Technology Co., Ltd. | 88 | 3 | 570 | 140 | Batch | Pre-treated RO concentrate | 0.65 | n.d. | 9.0 (HCl) | n.d. | [19] |
AEM | |||||||||||||
Fumatech | BM | ||||||||||||
Neosepta | CEM: Neosepta CMX | PC-Cell EDQ380 | 385 | 8 | 121 | - | Single-pass | 0.19 M NaCl | 0.15 | 0.14 | 3.65 (HCl) | 80 | [22] |
AEM: Neosepta ACM | |||||||||||||
BM: Neosepta BP-1 |
Current Density (A m−2) | NaOH Target Concentration | |
---|---|---|
Scenario 1 | 100 | 0.4 M |
Scenario 2 | 100 | 0.8 M |
Scenario 3 | 300 | 0.4 M |
Scenario 4 | 300 | 0.8 M |
Critical Fvalue (Fcr) = 5.9874 | |
---|---|
Fcalculated (Fc) | |
SEC | 0.0849 |
CE | 0.7251 |
Yield | 0.0098 |
Process Time | 0.0604 |
SP | 0.0037 |
Efficiency | 0.0098 |
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León, T.; Abdullah Shah, S.; López, J.; Culcasi, A.; Jofre, L.; Cipollina, A.; Cortina, J.L.; Tamburini, A.; Micale, G. Electrodialysis with Bipolar Membranes for the Generation of NaOH and HCl Solutions from Brines: An Inter-Laboratory Evaluation of Thin and Ultrathin Non-Woven Cloth-Based Ion-Exchange Membranes. Membranes 2022, 12, 1204. https://doi.org/10.3390/membranes12121204
León T, Abdullah Shah S, López J, Culcasi A, Jofre L, Cipollina A, Cortina JL, Tamburini A, Micale G. Electrodialysis with Bipolar Membranes for the Generation of NaOH and HCl Solutions from Brines: An Inter-Laboratory Evaluation of Thin and Ultrathin Non-Woven Cloth-Based Ion-Exchange Membranes. Membranes. 2022; 12(12):1204. https://doi.org/10.3390/membranes12121204
Chicago/Turabian StyleLeón, Tamara, Syed Abdullah Shah, Julio López, Andrea Culcasi, Lluis Jofre, Andrea Cipollina, José Luis Cortina, Alessandro Tamburini, and Giorgio Micale. 2022. "Electrodialysis with Bipolar Membranes for the Generation of NaOH and HCl Solutions from Brines: An Inter-Laboratory Evaluation of Thin and Ultrathin Non-Woven Cloth-Based Ion-Exchange Membranes" Membranes 12, no. 12: 1204. https://doi.org/10.3390/membranes12121204