Catalyst Design and Reaction Strategies for the Optimization of
Transcription
Catalyst Design and Reaction Strategies for the Optimization of
DR. STEVEN CROSSLEY, Page 1 of 11 Catalyst Design and Reaction Strategies for the Optimization of Liquid Products from Biomass Pyrolysis Steven Crossley University of Oklahoma, School of Chemical, Biological and Material Engineering Norman, OK, USA OK EPSCoR RESEARCH: OBJECTIVE 3 CATALYTIC/THERMOCHEMICAL CONVERSION PROCESSES R. Jentoft (OU), Kumar (OSU): Biomass composition effects on pyrolysis and gasification Nicholas, Halterman (OU): Novel homogeneous catalysts for oxygenates conversion Mallinson (OU): Catalytic upgrading of bio-oil small oxygenates F. Jentoft (OU): Spectroscopic characterization of catalyst adsorbates Striolo (OU): Atomistic simulation of nanohybridstabilized emulsions ph HO ase mig rati on O CH3 oil phase decarbonylation 250°C HO Mallinson, Lobban (OU): Fast, staged pyrolysis to bio-oil Resasco, Crossley (OU): Emulsion conversion of complex mixtures Hydrogenation 100°C O CH 3 OH HO CH3 O CH 3 Hydrogenolysis 200°C HO O CH3 O HO CH3 O CH 3 igration phase m HO O CH 3 OH + CH3 Resasco,Crossley (OU): Catalytic upgrading of biooil phenolic compounds aqueous phase Pd nanoparticles DR. STEVEN CROSSLEY, Page 2 of 11 Ex‐Situ Catalytic Fast Pyrolysis OBJECTIVES BIOMASS Switch grass Sawdust, Pine Torrefied-biomass Drying Increase Liquid Yield Remove Oxygen Minimize Deactivation Pyrolysis Fluidizing Bed Short Residence Time Grinding Liquid Bio-oils CHAR Inert Gas What should we ask from the catalysts ? O CH3 • Small oxygenates ( aldehydes, alcohols, ketones, acids ) • Sugar-derived compounds ( levoglucosan, furfurals ) • Lignin-derived phenolics ( guaiacol, vanillin, anisole, etc. ) Challenges to catalysts: Biomass ‐ Cellulose ‐ Hemicellulose ‐ Lignin • • • • • Remove O Maximize C capture Minimize H2 consumption Minimize catalyst deactivation Tolerate hot liquid water Biomass Resasco, Journal of Physical chemistry Letters, 2, 2294‐2295, 2011 DR. STEVEN CROSSLEY, Page 3 of 11 BIOMASS Switch grass Sawdust, Pine Torrefied-biomass Drying OBJECTIVES Increase Liquid Yield Remove Oxygen Minimize Deactivation Grinding Pyrolysis Fluidizing Bed Short Residence Time Liquid Bio-oils Desirable Reactions O CH3 OH CHAR CH3 Inert Gas + CO2 2 OH CH3 CH3 UNIQUE COLLABORATIVE APPROACH Bio‐oils PILOT SCALE INDUSTRIAL RESEARCH GASOLINE $$$ LAB SCALE FUNDAMENTAL RESEARCH + THEORY DR. STEVEN CROSSLEY, Page 4 of 11 Approach O • • • • • CH3 Vapor phase Condensed phase Model compounds Real bio‐oil Bio oil vapors OH Model Compound Studies lignin‐derived phenolics undesirable pathway + CH4 + 2*H2O desirable pathway guaiacol +2*H2O Interface Surface defects Ru * Vapor phase T=400°C P=1atm H2/Guaiacol molar ratio=60 S. Boonyasuwat, T. Omotoso, D.E. Resasco, S. Crossley Catalysis Letters (submitted) H Surface OH groups DR. STEVEN CROSSLEY, Page 5 of 11 Influence of support on catalyst stability O CH3 OH 100 Guaiacol Conversion (wt%) Ru/C (0.22h) Guaiacol (feed) 90 Ru/SiO2 (1.15h) 80 Ru/Al2O3 (0.3h) 70 Ru/TiO2 (0.06h) Less catalyst needed 60 50 More stable! 40 30 20 10 0 0 50 100 150 200 250 Time on Stream (minutes) 300 350 S. Boonyasuwat, T. Omotoso, D.E. Resasco, S. Crossley Catalysis Letters (submitted) Metal Particle Size Metal particle diameter (nm) Catalyst dXRD dTEM Ru/C - 1.7 Ru/Al2O3 11.8 4.1 Ru/SiO2 5.7 2.5 Ru/TiO2 5.5 3.3 Metal particle size does not explain increase in activity and stability DR. STEVEN CROSSLEY, Page 6 of 11 Methyl Retention CH3 O OH (mol methyl‐aroma c ring C‐C bonds formed) (mol guaiacol fed) CH3 80 70% of methyl groups conserved on ring 70 60 50 RU/C 40 W/F (h) Conversion (mol %) 0.29 45 5 wt% Ru/Al2 O3 Al 2 O3 0.29 18 5 wt% Ru/TiO2 * 0.33 100 TiO2 0.33 7 *note: 100% conversion was achieved at W/F of 0.2h RU/SIO2 30 Ru/Al2O3 20 Ru/TiO2 10 0 0 0.2 0.4 0.6 0.8 1 1.2 W/F (h) Strong synergy between reducible oxide and metal S. Boonyasuwat, T. Omotoso, D.E. Resasco, S. Crossley Catalysis Letters (submitted) Ru / TiO2 / Carbon Catalyst ‐ XPS 5000 Intensity Ti4+ (a) 4000 3000 TiO2/C (calcined) 2000 1000 c b a 0 Intensity 8000 457 (b) 462 Binding Energy (eV) 467 Ti3+ Ru/TiO2/C (calcined); 6000 4000 2000 0 452 457 10000 (c) Intensity 8000 462 Binding Energy (eV) 467 472 Ru/TiO2/C (reduced at 500oC in H2) 6000 1 472 4000 2000 Normalized intensity 452 0.8 0.6 0.4 0.2 0 455 460 Binding Energy (eV) 0 452 457 462 Binding Energy (eV) 467 Resasco et al. (2012) Journal of Catalysis 472 Ru/TiO2 interaction promotes the formation of oxygen vacancies New active sites? DR. STEVEN CROSSLEY, Page 7 of 11 Ru/TiO2 conversion of real bio oil vapors Shaolong Wan, Trung Pham, Sarah Zhang, Lance Lobban, Daniel Resasco, and Richard Mallinson AIChE Journal (in press). Real pyrolysis oil vapors • 4g Ru/TiO2 – 400°C – 1Atm H2 • 30g oak/batch Less change in MW upon aging after Ru/TiO2 treatment Shaolong Wan, Trung Pham, Sarah Zhang, Lance Lobban, Daniel Resasco, and Richard Mallinson AIChE Journal (in press). DR. STEVEN CROSSLEY, Page 8 of 11 Real pyrolysis oil vapors Ru/TiO2 catalytic upgrading produces a stable intermediate product that has a high solubility in oil. Shaolong Wan, Trung Pham, Sarah Zhang, Lance Lobban, Daniel Resasco, and Richard Mallinson AIChE Journal (in press). Concept: catalytic cascade coupled with multi‐stage pyrolysis Acetone 250-275°C 300-350°C 550-600°C Light oxygenates: Acetic acid, Acetol, Acetaldehyde, Water Sugar derived compounds: Furfurals Lignin derived compounds: Phenolics Alkylation H2 Isopropanol Alkylation Aldol Condensation C6‐C8 Phenolics C10‐C13 Phenolics C8‐C13 Oxygenates Hydro‐ deoxygenation To Gasoline or Diesel pool DR. STEVEN CROSSLEY, Page 9 of 11 Alkylation of phenolics with light alcohols OH + CH3 L. Nei, D. Resasco, Applied Catalysis A: General 447– 448 (2012) 14– 21 Pyroprobe for rapid catalyst evaluation Auto sampler SEPARATE CATALYTIC REACTOR DR. STEVEN CROSSLEY, Page 10 of 11 Pyroprobe 5250 SEPARATE REACTOR VARY REACTOR CONDITIONS INDEPENDENTLY OF PYROLYSIS CONIDITONS MEASURE CATALYST DEACTIVATION WITH MULTIPLE PULSES Results: HZSM‐5 vs. HY Aromatics Conditions Catalyst Bed Temperature: • 400°C Pyrolysis Temperature: • 500°C Weight of Catalyst: • HY5mg • HZSM‐55mg Si/Al: • HY40 • HZSM‐545 DR. STEVEN CROSSLEY, Page 11 of 11 Thank You R. Jentoft (OU), Kumar (OSU): Biomass composition effects on pyrolysis and gasification Nicholas, Halterman (OU): Novel homogeneous catalysts for oxygenates conversion Mallinson (OU): Catalytic upgrading of bio-oil small oxygenates F. Jentoft (OU): Spectroscopic characterization of catalyst adsorbates Striolo (OU): Atomistic simulation of nanohybridstabilized emulsions ph HO ase mig rati on O CH3 oil phase decarbonylation 250°C HO Mallinson, Lobban (OU): Fast, staged pyrolysis to bio-oil Resasco, Crossley (OU): Emulsion conversion of complex mixtures Hydrogenation 100°C O CH 3 OH HO CH3 O CH 3 Hydrogenolysis 200°C HO O CH3 O HO CH3 O CH 3 igration phase m HO O CH 3 OH + CH3 Resasco,Crossley (OU): Catalytic upgrading of biooil phenolic compounds aqueous phase Pd nanoparticles