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further applied directions. To perform this analysis, we first propose and describe a technical pathway from atmospheric CO2 to a final product and determine the approximate renewable energy input and efficiency of each step in the process, tak- ing note of integration opportunities between technologies. From these energy in- puts, we take practical operating conditions into account (e.g., wind speed, current densities, and location) to determine the minimum physical scales of CO2 capture units, renewable energy inputs, and CO2 electrolyzer catalyst areas required to replace today’s industrial-scale mega-plants with a renewable solar fuel alternative. From this analysis, we lastly provide perspectives on the practicalities of small versus large plants and a centralized versus decentralized approach for the production of energy-dense fuels using CO2 electrolyzers from comparatively dilute renewable energy resources. For simplicity, our analysis considers that electricity is generated by solar photovoltaic (PV) modules and CO2 for the system is provided via direct air capture (DAC). MeOH is chosen as a final product because of its high energy density (22.7 MJ/kg; 18 MJ/L HHV), its versatility to be converted into a variety of products (e.g., gasoline and kerosene), and its ability to be made from CO and H2, two small molecules that can be produced electrochemically from CO2 and H2O. A scale of 10,000 tons of MeOH/day, the size of a large industrial chemical plant (see Shell’s ~16,500 ton/day equivalent Pearl Gas-to-Liquid),28 is chosen to exemplify the scale of renewable electricity, air capture units, and electrochemical equipment, which will be required if future solar fuels are produced on the order of today’s existing mega- plants. While many chemical routes exist to produce fuels and intermediates from CO2 (e.g., reverse water-gas shift, direct CO2 to MeOH heterogeneous catalysis,27,29,30 and solid-oxide CO2 electrolysis31), we have chosen to highlight one specific combination of technologies as a tool for indicating the typical footprint, compatibility, and energy balance of an integrated capture and conversion system. Solar-Driven Synthesis Routes for MeOH Using CO2 Electrolyzers Commercial MeOH synthesis is a two-step process in which the energy and mole- cules in a fossil fuel (i.e., methane) are converted to MeOH.32,33 The first step of the process uses steam-methane reforming to convert CH4 into a mixture of H2, CO, and a few percent of CO2. This synthesis gas is subsequently converted to MeOH in the second step, which operates at elevated temperatures (z250C) and pressures (z50–100 bar). While MeOH synthesis cannot be directly created electrochemically from CO2 with high selectivities or current densities at this point in time,34–37 CO2 and water electrolyzers have the capacity to replace the steam- methane reforming step of current MeOH synthesis by producing CO and H2 from CO2 and H2O. In essence the energy, carbon, and hydrogen content of CH4 are re- placed by solar energy, CO2, and H2O. For a purely solar-driven MeOH synthesis process, which does not rely on industrial inputs (e.g., CO2 from cement, steel plants, etc.), these CO2 and H2O molecules will need to come from feedstocks initially in equilibrium with the environment. A suit- able feedstock is water (from the environment) and CO2 from air at 400 ppm. For the CO2 electrolyzer to operate, this dilute CO2 from the atmosphere first needs to be concentrated. For the DAC of CO2, we have used potassium hydroxide (KOH) as a capture solvent, where ambient CO2 is converted into carbonate upon contact. Here, the KOH and CO2 are then recovered using an electrically driven bipolar membrane electrodialysis (BPMED) step.38 The KOH is then recirculated to the capture unit while CO2 remains in an aqueous electrolyte and is pressurized to 50 bar in a KHCO3 electrolyte before being fed to the CO2 electrolyzer. 1824 Joule 3, 1822–1834, August 21, 2019PDF Image | Pathways to Industrial Scale Fuel from CO2 Electrolysis
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