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Figure 1. Air-to-Barrel Methanol Synthesis from Ambient Environmental Inputs A proposed scheme for methanol synthesis using ambient solar energy, CO2, and water. The order- of-magnitude area of a solar photovoltaic park and the frontal area of a CO2 capture unit, as well as the daily water volume inputs, are illustrated for a 10,000 ton/day methanol plant. The energy requirements for each primary component are presented in kJ mol1 CO2 converted and include the bipolar membrane electrodialysis (BPMED) step, CO2 electrolyzers, and H2O electrolyzers. The overall reaction for solar-to-MeOH synthesis is then described by the stoichio- metric reaction in Equation 1 and shown in the Supplemental Information: CO2 from air at 400 ppm + 2H2OðlÞ/CH3OHðlÞ + 1:5O2ðgÞ; GJ (Equation1) DG0 z23:1 ton MeOH In this equation, the entropic contribution of separating CO2 from an ideal mixture is also included as 20 kJ/mol CO2 (0.64 GJ/ton MeOH). With these boundaries in mind, an electrified MeOH synthesis route driven by solar en- ergy can then be envisaged by combining 5 individual, yet integrated sub-processes: (1) conversion of sunlight to electricity via photovoltaic modules, (2) an atmospheric CO2 capture system using aqueous KOH as a capture agent, (3) BPMED coupled with water splitting for regeneration of the capture solvent, (4) electrochemical conver- sion of CO2 and water to synthesis gas (CO + H2), and finally (5) a standard MeOH syn- thesis step. An overall proposed reaction scheme of the process is presented in Figure 1. With these envisioned sub-processes, we can now fully expand the overall reaction described in Equation 1 to include the capture and concentration step of CO2 using BPMED (Equation 2), the formation of CO via a CO2 electrolyzer (Equation 3), the for- mation of H2 via an H2O electrolyzer (Equation 4), and the synthesis of MeOH (Equation 5): CO2 400ppm /CO2 aq CO2 aq / COðgÞ + 0:5O2ðgÞ 2H2OðlÞ / 2H2ðgÞ + O2ðgÞ COðgÞ + 2H2ðgÞ/CH3OHðlÞ (Equation 2) (Equation 3) (Equation 4) (Equation 5) The proposed scheme in Figure 1 for MeOH synthesis was chosen as integration possibilities exist between the CO2 capture, regeneration, and conversion Joule 3, 1822–1834, August 21, 2019 1825PDF Image | Pathways to Industrial Scale Fuel from CO2 Electrolysis
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