Cooperative Agreement DEEE0011096

HIGH EFFICIENCY LIQUID HYDROGEN (H2) CARRIERS ARE AN ESSENTIAL LINK IN H2 STORAGE, BECAUSE THEY ENABLE STORAGE DENSITIES SUPERIOR TO THE PARENT COMPRESSED GAS AND ARE EASY TO TRANSPORT. TRADITIONALLY, THE SPENT FUEL THAT RESULTS FROM H2 RELEASE FROM A 2-WAY CARRIER IS THEN TRANSPORTED TO A SOURCE OF LOW-COST HYDROGEN FOR RE-CHARGE. THE COST OF THIS TRANSPORTATION AND THE EFFICIENCY OF THE RE-HYDROGENATION REACTION IMPACT THE ENERGY AND COST EFFICIENCY OF THE OVERALL PROCESS. DESPITE COMMERCIALIZATION OF SYSTEMS BASED ON SUBSTITUTED TOLUENES THAT EXPLOIT THIS 2-WAY CARRIER MODEL, THESE OPERATE ONLY WITH SUBSIDY, AND THE ECONOMICS BECOME EVEN LESS FAVORABLE AS THE PRICE OF H2 APPROACHES $1/KG. OUR PROJECT CONTEMPLATES A STRATEGY IN WHICH A BIO-SOURCED, 1-WAY H2 CARRIER, ETHANOL OR GLYCEROL, IS DELIVERED TO THE LOCATION OF H2 NEED AND THEN DEHYDROGENATED BOTH TO PRODUCE GREEN H2 AND A HIGH-VALUE AGROCHEMICAL, THE LATTER GENERATING SUFFICIENT VALUE TO OFFSET THE COST OF H2 PRODUCTION FROM A C1 CARRIER AND DRIVE THE BALANCE OF PLANT H2 COST BELOW $1/KG. THE CENTRAL HYPOTHESIS OF THIS PROJECT IS THAT THE PRESSURE AND CONTINUOUS FLOW CAPABILITIES THAT WE DEVELOPED IN OUR FORMIC ACID REACTOR CAN ENABLE BOTH REVERSIBILITY OF OUR FORMIC SYSTEM AND DEHYDROGENATION OF ETHANOL AND OTHER ALCOHOLS, WITH THE LATTER INTRODUCING NEW A REVENUE-POSITIVE, 1-WAY LIQUID H2 CARRIERS. WE PROPOSE THAT ADDING THIS 1-WAY CARRIER TO AN H2 PRODUCTION PLANT CAN MAKE THE TOTAL COST OF OPERATION AND CARBON IMPACT FAVORABLE, BECAUSE OF VALUE IN THE CARBOXYLATE CO-PRODUCT. WE WILL THUS INTRODUCE VALUE INTO OUR PROPOSED GREEN H2 PLANT BY SHOWING PLAUSIBILITY FOR PRESSURIZATION OF HIGHER ALCOHOL CARRIERS AND DETERMINE HOW THE VALUE OF AGROCHEMICAL COPRODUCTS LOWERS THE COST FOR H2 DELIVERY. WE WILL ACCOMPLISH THIS THROUGH FOUR CONCURRENT WORK PACKAGES: 1. DEVELOP CONDITIONS FOR ETHANOL DEHYDROGENATION. WE WILL DEVELOP THIS REACTION TO BE A CONTINUOUS OPERATION PROCESS IN WHICH WE CAN ASSESS EFFICIENCY, CATALYST LONGEVITY, PRODUCT PURITY, PRESSURIZATION CAPABILITY, AND ENERGY EFFICIENCY. WE WILL ALSO ASSESS THE IMPACT OF ADDING GLYCEROL AS A FURTHER VALUE-ADDED CARRIER INTO THE BALANCE OF PLANT OPERATIONS. 2. DESIGN AND IMPLEMENT A CONTINUOUS OPERATION REACTOR FOR FORMATION AND SEPARATION OF AGRICHEMICAL CO-PRODUCTS. WE WILL DEVISE A BUILD A DEMONSTRATION REACTOR THAT WILL ENABLE THE SCALABLE, CONTINUOUS OPERATION OF THE REACTIONS ABOVE AND QUALIFY ITS ABILITY TO PRODUCE HIGH-PURITY, PRESSURIZED H2. 3. ILLUSTRATE EFFICIENCY AND PRODUCT DISTRIBUTION FOR CO2 RE-REDUCTION. WE EVALUATE FLOWING CO2 CAPTURED FROM FORMIC ACID DEHYDROGENATION BACK INTO OUR REACTOR TO CONVERT IT TO FUELS USING H2 THAT COULD BE GENERATED ON-SITE BY ELECTROLYSIS IN TIMES OF PLENTIFUL ELECTRICITY. THIS REACTION IS KEY TO PRESENTING A MEANINGFUL BALANCE-OF-PLANT MODEL FROM WHICH TO ASSESS TOTAL COST OF OWNERSHIP AND TOTAL CARBON BALANCE. DATA FROM THIS TASK WILL BE USED TO DEVELOP MEANINGFUL TEA AND LCA MODELS IN COLLABORATION WITH HYMARC. THE WORK IN THIS TASK WILL BE USED TO EVALUATE THE POTENTIAL FOR STRATEGIES THAT PAIR MULTIPLE CARRIERS TO ACHIEVE COST, EMISSIONS, AND SUPPLY/DEMAND BALANCE FOR MARKET ADOPTION OF THE CO-PRODUCT AGRICHEMICAL SYSTEM. 4. COMPUTATIONAL MODELING. WE WILL USE COMPUTATIONAL ASSETS AT BROOKHAVEN TO RESOLVE QUESTIONS OF CHEMICAL MECHANISM, SUCH AS PRESSURIZATION EFFECTS AND CHEMICAL SELECTIVITY, THAT MIGHT LIMIT OUR ABILITY TO ACHIEVE HIGH PRESSURE IN PACKAGES 1 AND 2. WE WILL ALSO LEVERAGE OUR MODELING TEAM BETTER TO UNDERSTAND OUR NASCENT CO2 HYDROGENATION REACTION. AS THE INVENTORS OF OUR STARTING POINT SYSTEMS FOR FORMIC ACID DEHYDROGENATION, THE USC INVESTIGATORS ARE UNIQUELY WELL-POSITIONED TO LEAD THEIR DEVELOPMENT AND DEPLOYMENT. BECAUSE OF THE ENGINEERING WORK REQUISITE TO BRING THESE TECHNOLOGIES TO DEPLOYMENT, WE ARE EXCITED TO WORK WITH THE ENGINEERING AND CATALYSIS PARTNERS AT LANL TO REALIZE THESE GOALS. WE WILL FURTHER LEVERAGE EXPERIENCE AND COMPUTATIONAL RESOURCES AT BNL TO AID IN CHEMICAL PROCESS OPTIMIZATION AND SCALING AND INCORPORATE TRAINEES FROM CALSTATE LA TO EXECUTE COMPUTATIONAL WORK AND REACTOR CONSTRUCTION THAT WILL BE LED OUT OF THE OTHER PARTNER INSTITUTIONS.