Biogenic carbon capture at pulp mills via sodium spiking and oxy-fuel calcination

• Over 13 million metric tons of biogenic carbon dioxide (CO 2 ) are mineralized yearly in pulp mill recovery boilers in the US as molten sodium carbonate. • Sodium spiking enhances CO 2 mineralization in the recovery boiler of kraft processes, and combined with oxy-fuel calcination, represents an innovative method for biogenic CO 2 capture at existing kraft pulp mills. • The novel concept of sodium spiking in biomass pulp mills lowers the cost and increases the capacity of CO 2 capture from lime kilns. • Combining sodium spiking with oxy-fuel combustion in lime kilns reduces CO 2 capture costs by 31 % and increases capacity by 13 %. Over 13 million metric tons of biogenic carbon dioxide (CO 2 ) are mineralized yearly in United States (US) pulp mill recovery boilers as molten sodium carbonate. The mineralized CO 2 is released downstream in the rotary lime kiln where it can be captured at a relatively low cost for permanent sequestration. The use of biocarbon and bioenergy at pulp mills enables the possibility for atmospheric carbon removal when biogenic CO 2 is captured and sequestered. We demonstrate the feasibility of capturing biogenic CO 2 via sodium spiking coupled with oxy-fuel calcination in the rotary lime kiln at existing kraft pulp mills. Sodium (Na) spiking elevates the Na ion loading in the kraft chemical looping process by replacing chlorine-based bleaching with a highly alkaline bleaching sequence. Chemical pulping processes are modeled and simulated to understand the technical limits of implementing sodium spiking in existing pulp mills. Each 1 % of sodium added to the bleaching operations increases the rate of CO 2 mineralization by 4 %, and the maximum increase in sodium content in the kraft process is 9 %. Without sodium spiking, estimated CO 2 capture costs are $131 and $107/mt CO 2 for air and oxy-fuel combustion, respectively. With the implementation of sodium spiking, the cost of CO 2 captured decreases by 27 % and 31 %, showing costs of $96 and $74/mt CO 2 for air and oxy-fuel combustion, respectively. Oxy-fuel combustion reduces the costs of CO 2 capture compared to air combustion, but merged deployment with sodium spiking seems to be the most cost-effective pathway to integrate carbon capture.