1. Continuous deoxygenation of cellulose pyrolysis vapors in a staged autothermal reactor Nils Persson, Samuel Blass, Corey Rosenthal, Aditya Bhan, and Lanny Schmidt Department of Chemical Engineering and Materials Science University of Minnesota Twin Cities

2. Stage 1: Catalytic Partial Oxidation (CPO) of solid cellulose Stage 2: bifunctional ZSM-5/Pt catalyzed deoxygenation High throughput, autothermal, small scale Process Summary Integrated Partial Oxidation and Upgrading Fuel + O2 + Co-feed Pt Catalyst Oxidation + Pyrolysis Products Bifunctional zeolite Deoxygenated hydrocarbons 3. Reactive flash volatilization (video) 4. 4 Reactor HeatChemistry Fuel + O2 + Co-feed Catalyst Endothermic Exothermic Endothermic Conduction Convection impact melting volatilizationno char residue Oxidation + Pyrolysis Products Reactive flash volatilization of solid feedstocks J.L. Colby, P.J. Dauenhauer, Green Chem., 2008,10, 773-783 5. Cellulose Feed Grain hopper Auger N2 H2 Mounted electrical connection Relief valve O2 Pt/-Al2O31.3mm spheres CPO Stage700 C Atmospheric pressure Hydrogen co-feed for temperature control ~ 3.5 Standard Liters per Minute total gas flow rate GHSV = 75,000 h-1 9.5 g/h solid cellulose flow rate WHSV = 4.75 h-1 Effluent gases to gas chromatograph (GC) Apparatus Solid feedstock introduces challenges 6. Pt/-Al2O31.3 mmspheres H2 O2 2 SLPM N2 9.5 g/hr cellulose 0% 20% 40% 60% 80% 100% CO CO2 C1 C2 C3 Oxygenates FirstStage Carbon Yield First stage product distribution: predominantly oxygenates 7. Pt/-Al2O31.3 mmspheres H2 O2 2 SLPM N2 9.5 g/hr cellulose 0% 20% 40% 60% 80% 100% CO CO2 C1 C2 C3 Oxygenates Aldehydes Furans Acids Ketones Carbon Yield First stage product distribution: predominantly oxygenates FirstStage Levoglucosan 8. Cellulose Feed Grain hopper Auger N2 H2 Mounted electrical connection Relief valve O2 Pt/-Al2O31.3mm spheres CPO Stage700 C Apparatus Addition of second zeolite stage Use latent process heat to drive downstream reactions skip bio-oil Zeolite upgrading: HZSM-5, USY, HFER Bifunctional zeolite/Pt 9. Cellulose Feed Auger N2 H2 Relief valve Pt/-Al2O3HZSM-5 Zeolite stageHeating tape O2 Pt/-Al2O31.3mm spheres CPO Stage700 C 500 C Grain hopper Mounted electrical connection Use latent process heat to drive downstream reactions skip bio-oil Zeolite upgrading: HZSM-5, USY, HFER Bifunctional zeolite/Pt Apparatus Addition of second zeolite stage 10. Pt/-Al2O31.3 mmspheres H2 O2 2 SLPM N2 9.5 g/hr cellulose 0% 20% 40% 60% 80% 100% CO CO2 C1 C2 C3 Oxygenates Carbon Yield Second stage deoxygenates incoming pyrolysis vapors FirstStage 11. Pt/-Al2O31.3 mmspheres H2 Pt/-Al2O3HZSM-5O2 2 SLPM N2 9.5 g/hr cellulose 0% 20% 40% 60% 80% 100% CO CO2 0% 20% 40% 60% 80% 100% CO CO2 C1 C2 C3 Oxygenates C1 C2 C3 C4 Aromatics Mass balance closes SecondStage Carbon Yield FirstStage Second stage deoxygenates incoming pyrolysis vapors 12. Pt/-Al2O3 1.3 mm spheres H2 O2 N2, cellulose 0% 20% 40% 60% 80% 100% FirstStage Overall Carbon Yield SecondStage 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% HZSM- 5/Pt HZSM-5 Pt/- Al2O3 -Al2O3 Pyrolysis Vapor Carbon Yield CO CO2 CH4 C2 - C4 Aromatics Oxygenates Bifunctional HZSM-5/Pt combines individual functionalities 13. H2 O2 N2, cellulose SecondStage Methane is hydrogenolysis or methanation (Pt-catalyzed) product Aromatics are zeolite product Bi-functional catalyst exhibits compromise in behavior 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% HZSM- 5/Pt HZSM-5 Pt/- Al2O3 -Al2O3 Pyrolysis Vapor Carbon Yield CO CO2 CH4 C2 - C4 Aromatics Oxygenates Bifunctional HZSM-5/Pt combines individual functionalities 14. Bifunctional catalysts resist deactivation and coke formation HZSM-5/Pt: ~ 3% carbon yield to coke after 60 min. on stream (quantified by burn-off and by weight) No reactor plugging with solid coke formation 0 10 20 30 40 50 60 CarbonYieldtoOxygenates(%) 5 30Minutes on stream: 15. Decarbonylation appears to be predominant pathway for deoxygenation Short bed: C2-C4 are olefins Long bed: C2-C4 are paraffins Possible hydrogenation of coke precursors 50% oxygenates HZSM-5 / Pt bed length study decarbonylation predominates 16. Flash volatilization of solid feedstock Heat integration of millisecond pyrolysis with downstream zeolite upgrading High throughput, autothermal, small scale Process Summary Fuel + O2 + Co-feed CPO Catalyst Oxidation + Decomposition Products Bifunctional zeolite Deoxygenated hydrocarbons 17. National Science Foundation EFRI: Hydrocarbons from Biomass Bill Gruhlke Acknowledgements