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Stirling, Robert

Publications and source records attributed to Stirling, Robert.

Membrane Carbonation for 100% Efficient Delivery of Industrial CO 2 Gases

Industrial processes generate about one quarter of all greenhouse gases emissions in the US, about 80% of which is carbon dioxide (CO 2 ). Biological processes are one of the largest natural sinks for atmospheric CO 2 , but the rate of capture is limited by the low concentration in air (~0.04%). Industrial emissions have significantly higher CO 2 concentrations, ranging from 5–80% CO 2 , which can significantly increase the rate of biological CO 2 capture, including many-fold improvements for cultivating microalgae to produce food, fertilizer, and renewable fuel. However, traditional methods for delivering CO 2 to microalgae using bubbling is < 40% efficient, leading to significant residual CO 2 emissions and increased cost. This project developed the Membrane Carbonation (MC) technology to significantly improve the CO 2 delivery efficiency to microalgae from power plant flue gas, wastewater treatment plant anaerobic digesters biogas (Figure 1), and other CO 2 -containing industrial sources.

09 BIOMASS FUELS↗

Mining Air for Fuels and Fine Chemicals

The Intergovernmental Panel on Climate Change’s 2021 report underscores that Direct Air Capture (DAC) is an essential component to limiting global warming to 2 °C, yet separating CO 2 from air and its subsequent concentration for conversion into carbon neutral fuels/chemicals or permanent storage remains energy intensive and costly. Further, most DAC technologies rely on repetitive capture and release cycles that reduces the amount of time the DAC materials are able to collect CO 2 and increases wear and tear. Moisture swing (MS) sorption within anion exchange materials utilizes differences in relative humidity to capture and concentrate CO 2 up to 500-fold with negligible energy inputs and low-cost sorbents. Molecular modeling predicts that membranes with a dry and wet side would actively transport CO 2 from its dry side to its wet side against a counter flow of H 2 O evaporating on the dry side, however, existing MS materials are too brittle to be processed into membranes to test this hypothesis. This project brought together experts in DAC materials and design, techno-economic analysis and project management at Arizona State University (ASU), polymer processing at University of Texas at Austin (UTA) and modeling gas transport and exchange at Norther Arizona University (NAU) to develop hollow fiber membranes that use energy from water evaporation to continuously pump CO 2 from air against a concentration gradient to the membranes interior and requiring significantly less energy than current DAC technologies. While this project did not meet its ultimate objectives of demonstrating an active CO 2 pumping membrane, a number of key accomplishments were made in developing low-cost, flexible anion exchange membranes (AEM) at 3.5 m 2 scale, characterizing the ionic and molecular transport within MS materials, and developing several analytical and mathematical models of the MS and pumping process leading to new fundamental knowledge about key rate limiting steps of CO 2 flux in anion exchange membranes at low water activity. Technoeconomic models show that if CO 2 fluxes ≥ 25 µmol CO 2 m -2 s -1 (membrane surface area) are achieved that cost ≤ $\$$100/tonne CO 2 captured, purified and compressed to pipeline quality is possible. The knowledge gained in this research will guide future research in developing new materials toward overcoming these rate limiting steps that in turn could enable transformative and disruptive DAC technologies needed for capturing gigatons of CO 2 per year needed to limiting global warming to 2 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atmospheric CO 2 Capture and Membrane Delivery (Final Report)

Motivation: A major bottleneck for growing microalgae as a sustainable alternative to fossil carbon in economically producing fuels and chemical products is the cost of delivering CO 2 in sufficient concentrations for it not to limit growth. This project sought to develop and integrate two innovative technologies for capturing and concentrating CO 2 from air and delivering it to microalgae with high efficiency into an Atmospheric CO 2 Enrichment and Delivery (ACED) system. The CO 2 capture technology is based on moisture swing sorption (MSS), where specialized resin materials selectively capture CO 2 when dry and release it when wet into a confined space where the concentration can be increased up to 500-fold. The CO 2 -delivery technology is based on membrane carbonation (MC), which uses hollow fiber membranes that allow CO 2 to diffuse into the algae-containing liquid without forming bubbles, achieving nearly 100% delivery efficiency. Work completed: 1. Subsystem design, construction, and characterization [Months 1-6]. ACED integration requirements were defined; prototype MSS and MC sub-systems were constructed to conform to these requirements and characterized independently. 2. Subsystem optimization and evaluation [Months 7-12]. An iterative process of operating and upgrading each subsystem at lab scale, leading to compatibility at full integration. 3. System Integration with open raceway, testing, and modeling [Months 13-24]. Operation and testing of the integrated ACED system in an open raceway pond and modeling. Broader impacts: The ACED research program added to our understanding of 1) MC technology’s (i.e., hollow fiber membranes) utility for transferring pure CO 2 and CO 2 gas mixtures into microlagal cultures in laboratory and outdoor environments, 2) the first-of-a-kind MSS technology to capture CO 2 from ambient outdoor air, and 3) methods for storing captured CO 2 in carbonate/bicarbonate brines from which the CO 2 can be retrieved at high concentration (> 90%). Near-term commercial opportunities were outlined for the MC technology for small scale algae cultivation with high CO 2 costs (> $100/ton) and larger scale operators with continued development. This will help reduce costs for producing sustainable fuels and products and reduce cost for microalgal research for developing new applications. Research areas were identified for MSS technology to achieve cost competitive CO 2 produced from ambient air ($100/ton) as a means for closing the carbon cycle to make products from atmospheric CO 2 instead of fossil fuels and remove CO 2 from air to mitigate climate change.

09 BIOMASS FUELS↗