title: Electrochemical splitting of calcium carbonate to increase solution alkalinity: implications for mitigation of carbon dioxide and ocean acidity.
abstract: Electrochemical splitting of calcium carbonate (e.g., as contained in limestone or other minerals) is explored as a means of forming dissolve hydroxides for absorbing, neutralizing, and storing carbon dioxide, and for restoring, preserving, or enhancing ocean calcification. While essentially insoluble in water, CaCO3 can be dissolved in the presence of the highly acidic anolyte of a water electrolysis cell. The resulting charged constituents, Ca2+ and C03(2-), migrate to the cathode and anode, respectively, forming Ca(OH)2 on the one hand and H2CO3 (or H2O and CO2) on the other. By maintaining a pH between 6 and 9, subsequent hydroxide reactions with CO2 primarily produce dissolved calcium bicarbonate, Ca(HCO3)2aq. Thus, for each mole of CaCO3 split there can be a net capture of up to 1 mol of CO2. Ca(HCO3)2aq is thus the carbon sequestrant that can be diluted and stored in the ocean, in natural or artificial surface water reservoirs, or underground. The theoretical work requirement for the reaction is 266 kJe per net mole CO2 consumed. Even with inefficiencies, a realized net energy expenditure lower than the preceding quantity appears possible considering energy recovery via oxidation of the H2 produced. The net process cost is estimated to be <$100/tonne CO2 mitigated. An experimental demonstration of the concept is presented, and further implementation issues are discussed.
authors.affiliation: Institute of Marine Sciences, University of California, Santa Cruz, California 95064, USA. rau4@llnl.gov
authors.forename: Greg H
authors.initials: GH
authors.lastname: Rau
mesh_terms: D000143:Acids / Q000737:chemistry*; D000468:Alkalies / Q000737:chemistry*; D002119:Calcium Carbonate / Q000737:chemistry*; D002126:Calcium Hydroxide; D002245:Carbon Dioxide / Q000737:chemistry*; D055664:Electrochemical Techniques / Q000191:economics; D006863:Hydrogen-Ion Concentration; D009792:Oceans and Seas; D012623:Seawater / Q000737:chemistry; D012996:Solutions / Q000737:chemistry*; D013816:Thermodynamics; D013997:Time Factors
chemical_list: D000143:Acids; D000468:Alkalies; D012996:Solutions; D002245:Carbon Dioxide; D002119:Calcium Carbonate; D002126:Calcium Hydroxide