Revisiting Chlor-Alkali Electrolyzers: from Materials to Devices

Abstract

As an energy-intensive industry, the chlor-alkali process has caused numerous environmental issues due to heavy electricity consumption and pollution. Chlor-alkali industry has been upgraded from mercury, diaphragm electrolytic cell, to ion exchange membrane (IEM) electrolytic cells. However, several challenges, such as the selectivity of the anodic reaction, sluggish kinetics of alkaline hydrogen evolution, degradation of membranes, the reasonable design of electrolytic cell structure, remain to be addressed. For these reasons, this paper mainly reviews the research progress of the chlor-alkali industry from materials to devices, including hydrogen evolution anode, chlorine evolution cathode, IEM, and electrolytic cell system. Finally, the research directions and prospects in the chlor-alkali industry are proposed for its further improvement.

Keywords

Chlor-alkali / Process / Hydrogen energy / Ion exchange / Membrane / Hydrogen evolution / Chlorine evolution

References

[1] Crook J, Mousavi A The chlor-alkali process: a review of history and pollution. Environ Forensics, 2016, 17(3): 211-217.

[2] Fauvarque J The chlorine industry. Pure Appl Chem, 1996, 68(9): 1713-1720.

[3] Lakshmanan S, Murugesan T The chlor-alkali process: work in progress. Clean Technol Environ Policy, 2014, 16(2): 225-234.

[4] Chen YQ, Manzhos S Voltage and capacity control of polyaniline based organic cathodes: an ab initio study. J Power Sources, 2016, 336: 126-131.

[5] Cao YL, Yang HX, Ai XP, et al. The mechanism of oxygen reduction on MnO₂-catalyzed air cathode in alkaline solution. J Electroanal Chem, 2003, 557: 127-134.

[6] Cao YL, Xiao LF, Wang W, et al. Reversible sodium ion insertion in single crystalline manganese oxide nanowires with long cycle life. Adv Mater, 2011, 23(28): 3155-3160.

[7] Tan C Development and application of modified diaphragm. Chlor-Alkali Ind, 2005, 11: 21-24 in Chinese

[8] Bazinet L, Araya-Farias M Effect of calcium and carbonate concentrations on cationic membrane fouling during electrodialysis. J Colloid Interface Sci, 2005, 281(1): 188-196.

[9] Casademont C, Pourcelly G, Bazinet L Effect of magnesium/calcium ratio in solutions subjected to electrodialysis: characterization of cation-exchange membrane fouling. J Colloid Interface Sci, 2007, 315(2): 544-554.

[10] Dötzel O, Schneider L Non-asbestos diaphragms in chlor-alkali electrolysis. Chem Eng Technol, 2002, 25(2): 167.

[11] Stiegel GJ, Ramezan M Hydrogen from coal gasification: an economical pathway to a sustainable energy future. Int J Coal Geol, 2006, 65(3–4): 173-190.

[12] Xu JG, Froment GF Methane steam reforming, methanation and water-gas shift: I. Intrinsic kinetics. Aiche J, 1989, 35(1): 88-96.

[13] de Wild PJ, Verhaak MJFM Catalytic production of hydrogen from methanol. Catal Today, 2000, 60(1–2): 3-10.

[14] Rossmeisl J, Logadottir A, Nørskov JK Electrolysis of water on (oxidized) metal surfaces. Chem Phys, 2005, 319(1–3): 178-184.

[15] Kayfeci M, Keçebaş A, Bayat M (2019) Chapter 3-hydrogen production. Solar hydrogen production: processes, systems and technologies (1st Edition):45–83

[16] Kong FD, Zhang S, Yin GP, et al. IrO₂-graphene hybrid as an active oxygen evolution catalyst for water electrolysis. Int J Hydrog Energy, 2013, 38(22): 9217-9222.

[17] Levene JI, Mann MK, Margolis RM, et al. An analysis of hydrogen production from renewable electricity sources. Sol Energy, 2007, 81(6): 773-780.

[18] Lee DY, Elgowainy AA, Dai Q Life cycle greenhouse gas emissions of by-product hydrogen from chlor-alkali plants, 2017 USA Office of Scientific and Technical Information (OSTI)

[19] Elgowainy A Resourcing byproduct hydrogen from industrial operations, 2017 Houston H2@Scale Workshop

[20] Lee DY, Elgowainy A, Dai Q Life cycle greenhouse gas emissions of hydrogen fuel production from chlor-alkali processes in the United States. Appl Energy, 2018, 217: 467-479.

[21] Yu H (2018) Hydrogen energy production from chlor-alkali electrolyzers. Chlor-Alkali Ind (in Chinese)

[22] Ozturk M, Dincer I An integrated system for ammonia production from renewable hydrogen: a case study. Int J Hydrog Energy, 2021, 46(8): 5918-5925.

[23] Félix G, Quitian A, Rodríguez E, et al. Methods to calculate hydrogen consumption during hydrocracking experiments in batch reactors. Energy Fuels, 2017, 31(11): 11690-11697.

[24] Sharaf OZ, Orhan MF An overview of fuel cell technology: fundamentals and applications. Renew Sustain Energy Rev, 2014, 32: 810-853.

[25] Brinkmann T, Giner-Santonja G, Schorcht F, et al. Best available techniques (BAT) reference document for the production of chlor-alkali, 2014 Denmark Publications Office of the European Union

[26] Guandalini G, Foresti S, Campanari S, et al. Simulation of a 2 MW PEM fuel cell plant for hydrogen recovery from chlor-alkali industry. Energy Procedia, 2017, 105: 1839-1846.

[27] Cheng T, Wang L, Merinov BV, et al. Explanation of dramatic pH-dependence of hydrogen binding on noble metal electrode: greatly weakened water adsorption at high pH. J Am Chem Soc, 2018, 140(25): 7787-7790.

[28] Wang YH, Chen L, Yu XM, et al. Superb alkaline hydrogen evolution and simultaneous electricity generation by Pt-decorated Ni₃N nanosheets. Adv Energy Mater, 2017, 7(2): 1601390.

[29] Wang PT, Jiang KZ, Wang GM, et al. Phase and interface engineering of platinum-nickel nanowires for efficient electrochemical hydrogen evolution. Angewandte Chemie Int Ed, 2016, 55(41): 12859-12863.

[30] Mahmood N, Yao Y, Zhang JW, et al. Electrocatalysts for hydrogen evolution in alkaline electrolytes: mechanisms, challenges, and prospective solutions. Adv Sci, 2018, 5(2): 1700464.

[31] Zheng Y, Jiao Y, Vasileff A, et al. The hydrogen evolution reaction in alkaline solution: from theory, single crystal models, to practical electrocatalysts. Angew Chem Int Ed Engl, 2018, 57(26): 7568-7579.

[32] Safizadeh F, Ghali E, Houlachi G Electrocatalysis developments for hydrogen evolution reaction in alkaline solutions-a review. Int J Hydrog Energy, 2015, 40(1): 256-274.

[33] Lei CJ, Wang Y, Hou Y, et al. Efficient alkaline hydrogen evolution on atomically dispersed Ni–N _x species anchored porous carbon with embedded Ni nanoparticles by accelerating water dissociation kinetics. Energy Environ Sci, 2019, 12(1): 149-156.

[34] Sun QZ, Zhang B, Diao LC, et al. Engineering the electronic structure of 1T'-ReS₂ through nitrogen implantation for enhanced alkaline hydrogen evolution. J Mater Chem A, 2020, 8(23): 11607-11616.

[35] Zhao DJ, Zhang S, Yin GP, et al. Effect of Se in Co-based selenides towards oxygen reduction electrocatalytic activity. J Power Sources, 2012, 206: 103-107.

[36] Kintrup J, Millaruelo M, Trieu V, et al. Gas diffusion electrodes for efficient manufacturing of chlorine and other chemicals. Electrochem Soc Interface, 2017, 26(2): 73-76.

[37] Ding JS, Hua WQ, Hu BB, et al. Closed loop recycling of chlorine for sustainable development of polyurethane industry. Trans Tianjin Univ, 2011, 17(4): 298-304.

[38] Liu JJ, Yang C, Liu CG, et al. Design of pore structure in gas diffusion layers for oxygen depolarized cathode and their effect on activity for oxygen reduction reaction. Ind Eng Chem Res, 2014, 53(14): 5866-5872.

[39] Erikson H, Sarapuu A, Tammeveski K Oxygen reduction reaction on silver catalysts in alkaline media: a minireview. ChemElectroChem, 2019, 6(1): 73-86.

[40] Lipp L, Gottesfeld S, Chlistunoff J Peroxide formation in a zero-gap chlor-alkali cell with an oxygen-depolarized cathode. J Appl Electrochem, 2005, 35(10): 1015-1024.

[41] Kuwertz R, Gonzalez Martinez I, Vidaković-Koch T, et al. Energy-efficient chlorine production by gas-phase HCl electrolysis with oxygen depolarized cathode. Electrochem Commun, 2013, 34: 320-322.

[42] Zhang CZ, Fan FRF, Bard AJ Electrochemistry of oxygen in concentrated NaOH solutions: solubility, diffusion coefficients, and superoxide formation. J Am Chem Soc, 2009, 131(1): 177-181.

[43] Zhao DJ, Zhang S, Yin GP, et al. Tungsten doped Co-Se nanocomposites as an efficient non precious metal catalyst for oxygen reduction. Electrochim Acta, 2013, 91: 179-184.

[44] Röhe M, Kubannek F, Krewer U Processes and their limitations in oxygen depolarized cathodes: a dynamic model-based analysis. Chemsuschem, 2019, 12(11): 2373-2384.

[45] Röhe M, Botz A, Franzen D, et al. The key role of water activity for the operating behavior and dynamics of oxygen depolarized cathodes. ChemElectroChem, 2019, 6(22): 5671-5681.

[46] Chavan N, Pinnow S, Polcyn GD, et al. Non-isothermal model for an industrial chlor-alkali cell with oxygen-depolarized cathode. J Appl Electrochem, 2015, 45(8): 899-912.

[47] Clausmeyer J, Botz A, Öhl D, et al. The oxygen reduction reaction at the three-phase boundary: nanoelectrodes modified with Ag nanoclusters. Faraday Discuss, 2016, 193: 241-250.

[48] Franzen D, Ellendorff B, Paulisch MC, et al. Influence of binder content in silver-based gas diffusion electrodes on pore system and electrochemical performance. J Appl Electrochem, 2019, 49(7): 705-713.

[49] Morimoto T, Suzuki K, Matsubara T, et al. Oxygen reduction electrode in brine electrolysis. Electrochim Acta, 2000, 45(25–26): 4257-4262.

[50] Tseng CJ, Lo SK Effects of microstructure characteristics of gas diffusion layer and microporous layer on the performance of PEMFC. Energy Convers Manag, 2010, 51(4): 677-684.

[51] Passalacqua E, Squadrito G, Lufrano F, et al. Effects of the diffusion layer characteristics on the performance of polymer electrolyte fuel cell electrodes. J Appl Electrochem, 2001, 31(4): 449-454.

[52] Nara H, Momma T, Osaka T Impedance analysis of the effect of flooding in the cathode catalyst layer of the polymer electrolyte fuel cell. Electrochim Acta, 2013, 113: 720-729.

[53] Park S, Popov BN Effect of cathode GDL characteristics on mass transport in PEM fuel cells. Fuel, 2009, 88(11): 2068-2073.

[54] Kiros Y, Pirjamali M, Bursell M Oxygen reduction electrodes for electrolysis in chlor-alkali cells. Electrochim Acta, 2006, 51(16): 3346-3350.

[55] Marković NM, Schmidt TJ, Stamenković V, et al. Oxygen reduction reaction on Pt and Pt bimetallic surfaces: a selective review. Fuel Cells, 2001, 1(2): 105-116.

[56] Shao YY, Zhang S, Engelhard MH, et al. Nitrogen-doped graphene and its electrochemical applications. J Mater Chem, 2010, 20(35): 7491.

[57] Masa J, Xia W, Muhler M, et al. On the role of metals in nitrogen-doped carbon electrocatalysts for oxygen reduction. Angewandte Chemie Int Ed, 2015, 54(35): 10102-10120.

[58] Li JK, Jia QY, Ghoshal S, et al. Highly active and stable Fe–N–C catalyst for oxygen depolarized cathode applications. Langmuir, 2017, 33(37): 9246-9253.

[59] Mamtani K, Jain D, Co AC, et al. Investigation of chloride poisoning resistance for nitrogen-doped carbon nanostructures as oxygen depolarized cathode catalysts in acidic media. Catal Lett, 2017, 147(12): 2903-2909.

[60] Singh V, Nagaiah TC In situ incorporation of cobalt nanoclusters and nitrogen into the carbon matrix: a bifunctional catalyst for the oxygen depolarized cathode and chlorine evolution in HCl electrolysis. J Mater Chem A, 2019, 7(16): 10019-10029.

[61] Moussallem I, Pinnow S, Wagner N, et al. Development of high-performance silver-based gas-diffusion electrodes for chlor-alkali electrolysis with oxygen depolarized cathodes. Chem Eng Process Process Intensif, 2012, 52: 125-131.

[62] Burdyny T, Smith WA CO₂ reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions. Energy Environ Sci, 2019, 12(5): 1442-1453.

[63] Zhang LH, Fan Q, Li K, et al. First-row transition metal oxide oxygen evolution electrocatalysts: regulation strategies and mechanistic understandings. Sustain Energ Fuels, 2020, 4(11): 5417-5432.

[64] Petrykin V, Macounová K, Okube M, et al. Local structure of Co doped RuO₂ nanocrystalline electrocatalytic materials for chlorine and oxygen evolution. Catal Today, 2013, 202: 63-69.

[65] Halck NB, Petrykin V, Krtil P, et al. Beyond the volcano limitations in electrocatalysis—oxygen evolution reaction. Phys Chem Chem Phys, 2014, 16(27): 13682-13688.

[66] Macounová KM, Simic N, Ahlberg E, et al. Electrochemical water-splitting based on hypochlorite oxidation. J Am Chem Soc, 2015, 137(23): 7262-7265.

[67] Koper MTM Thermodynamic theory of multi-electron transfer reactions: implications for electrocatalysis. J Electroanal Chem, 2011, 660(2): 254-260.

[68] Karlsson RK, Cornell A Selectivity between oxygen and chlorine evolution in the chlor-alkali and chlorate processes. Chem Rev, 2016, 116(5): 2982-3028.

[69] Hansen HA, Man IC, Studt F, et al. Electrochemical chlorine evolution at rutile oxide (110) surfaces. Phys Chem Chem Phys, 2010, 12(1): 283-290.

[70] Exner KS Controlling stability and selectivity in the competing chlorine and oxygen evolution reaction over transition metal oxide electrodes. ChemElectroChem, 2019, 6(13): 3401-3409.

[71] Over H Surface chemistry of ruthenium dioxide in heterogeneous catalysis and electrocatalysis: from fundamental to applied research. Chem Rev, 2012, 112(6): 3356-3426.

[72] Trasatti S Electrocatalysis: understanding the success of DSA (R). Electrochim Acta, 2000, 45(15–16): 2377-2385.

[73] Nanni LC, Polizzi S, Benedetti A, et al. Morphology, microstructure, and electrocatalytic properties of RuO₂-SnO₂ thin films. J Electrochem Soc, 1999, 146(1): 220-225.

[74] Xiong K, Deng ZH, Li L, et al. Sn and Sb co-doped RuTi oxides supported on TiO₂ nanotubes anode for selectivity toward electrocatalytic chlorine evolution. J Appl Electrochem, 2013, 43(8): 847-854.

[75] Trasatti S Electrocatalysis in the anodic evolution of oxygen and chlorine. Electrochim Acta, 1984, 29(11): 1503-1512.

[76] Exner KS Beyond dimensionally stable anodes: single-atom catalysts with superior chlorine selectivity. ChemElectroChem, 2020, 7(7): 1528-1530.

[77] Exner KS, Anton J, Jacob T, et al. Chlorine evolution reaction on RuO₂(110): ab initio atomistic thermodynamics study—Pourbaix diagrams. Electrochim Acta, 2014, 120: 460-466.

[78] Kuo DY, Paik H, Nelson JN, et al. Chlorine evolution reaction electrocatalysis on RuO₂(110) and IrO₂(110) grown using molecular-beam epitaxy. J Chem Phys, 2019, 150(4): 041726.

[79] Exner KS, Anton J, Jacob T, et al. Full kinetics from first principles of the chlorine evolution reaction over a RuO₂(110) model electrode. Angew Chem Int Ed, 2016, 55(26): 7501-7504.

[80] Exner KS, Sohrabnejad-Eskan I, Anton J, et al. Full free energy diagram of an electrocatalytic reaction over a single-crystalline model electrode. ChemElectroChem, 2017, 4(11): 2902-2908.

[81] Spöri C, Kwan JTH, Bonakdarpour A, et al. The stability challenges of oxygen evolving catalysts: towards a common fundamental understanding and mitigation of catalyst degradation. Angewandte Chemie Int Ed, 2017, 56(22): 5994-6021.

[82] Vos J, Liu ZC, Speck FD, et al. Selectivity trends between oxygen evolution and chlorine evolution on iridium-based double perovskites in acidic media. ACS Catal, 2019, 9(9): 8561-8574.

[83] Moreno-Hernandez IA, MacFarland CA, Read CG, et al. Crystalline nickel manganese antimonate as a stable water-oxidation catalyst in aqueous 1.0 M H₂SO₄. Energy Environ Sci, 2017, 10(10): 2103-2108.

[84] Moreno-Hernandez IA, Brunschwig BS, Lewis NS Crystalline nickel, cobalt, and manganese antimonates as electrocatalysts for the chlorine evolution reaction. Energy Environ Sci, 2019, 12(4): 1241-1248.

[85] Ha H, Jin K, Park S, et al. Highly selective active chlorine generation electrocatalyzed by Co₃O₄ nanoparticles: mechanistic investigation through in situ electrokinetic and spectroscopic analyses. J Phys Chem Lett, 2019, 10(6): 1226-1233.

[86] Mogg L, Zhang S, Hao GP, et al. Perfect proton selectivity in ion transport through two-dimensional crystals. Nat Commun, 2019, 10: 4243.

[87] Mogg L, Hao GP, Zhang S, et al. Atomically thin micas as proton-conducting membranes. Nat Nanotechnol, 2019, 14(10): 962-966.

[88] Liang X, Wu L, Xu TW Role of ionomer in membrane electrode assembly for proton exchange membrane fuel cells. Sci Sin-Chim, 2018, 48(9): 1040-1057.

[89] Zeynali ME, Mohammadi F, Rabiee A Structural analysis and defect evaluation of ion exchange composite membranes used in electrolysis of sodium chloride in chlor-alkali process. Iran Polym J, 2015, 24(2): 85-93.

[90] Le Faucheur S, Vasiliu D, Catianis I, et al. Environmental quality assessment of reservoirs impacted by Hg from chlor-alkali technologies: case study of a recovery. Environ Sci Pollut Res, 2016, 23(22): 22542-22553.

[91] Moshtarikhah S, Oppers NAW, Groot MT, et al. Multicomponent ion transport in a mono- and bilayer cation-exchange membrane at high current density. J Appl Electrochem, 2017, 47(2): 213-221.

[92] Wang J, Wang XJ, Dou P, et al. Morphology and properties of perfluorosulfonic acid polymer/perfluorocarboxylic acid polymer blend membranes. Polym Eng Sci, 2015, 55(1): 180-189.

[93] Hou M, Chen L, Guo Z, et al. A clean and membrane-free chlor-alkali process with decoupled Cl₂ and H₂/NaOH production. Nat Commun, 2018, 9(1): 438.

[94] Brée LC, Bulan A, Herding R, et al. Techno-economic comparison of flexibility options in chlorine production. Ind Eng Chem Res, 2020, 59(26): 12186-12196.

[95] Kuang SY, Li ML, Xia R, et al. Stable surface-anchored Cu nanocubes for CO₂ electroreduction to ethylene. ACS Appl Nano Mater, 2020, 3(8): 8328-8334.

[96] Guo JH, Sun WY Integrating nickel-nitrogen doped carbon catalyzed CO₂ electroreduction with chlor-alkali process for CO, Cl₂ and KHCO₃ production with enhanced techno-economics. Appl Catal B Environ, 2020, 275: 119154.

[97] Zhang S, Fan Q, Xia R, et al. CO₂ reduction: from homogeneous to heterogeneous electrocatalysis. Acc Chem Res, 2020, 53(1): 255-264.

[98] Gao DF, Zhang Y, Zhou ZW, et al. Enhancing CO₂ electroreduction with the metal–oxide interface. J Am Chem Soc, 2017, 139(16): 5652-5655.

[99] Zhang S, Kang P, Meyer TJ Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate. J Am Chem Soc, 2014, 136(5): 1734-1737.

[100] Xia R, Zhang S, Ma XB, et al. Surface-functionalized palladium catalysts for electrochemical CO₂ reduction. J Mater Chem A, 2020, 8(31): 15884-15890.

[101] Liu S, Yang HB, Hung SF, et al. Elucidating the electrocatalytic CO₂ reduction reaction over a model single-atom nickel catalyst. Angew Chem Int Ed Engl, 2020, 59(2): 798-803.

[102] Liu H, Su YQ, Kuang SY, et al. High efficient CO₂ electrolysis within a wide operation window using octahedral tin oxide single crystals. J Mater Chem A, 2021, 9: 7848-7856.