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LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Large Scale Reactors to Reduce Cellulosic LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Large Scale Reactors to Reduce Cellulosic Ethanol Costs College of Engineering and Science Dr. James D. Palmer, Dr. Yuri Lvov, Dr. Hisham Hegab, Dr. Dale Snow Qi Xing, Dezhi Zhang, Joe Nealy, Bam Aryal November 5, 2009

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Ethanol for Fuel • Sugar (Current LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Ethanol for Fuel • Sugar (Current technology) – fermented from sugar (corn or sugar cane) • Cellulose – waste biomass, wood, switchgrass • Does not compete with food • Reduces Green-House Gas emissions by 86% • Cellulose must be converted to sugars – then fermented as normal

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Sugar (glucose) Carbon Dioxide H H LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Sugar (glucose) Carbon Dioxide H H C OH C HO O OH CH OH C H H C OH Cellulose H H OH C C H H O C H H H OH C O H Ethanol H C O C H H O C H O H C O H H C C O H C H H O C H O H C O H H H OH C C O H C H H O C H O H C O H H C O C H H O C H O H C H

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Cellulosic Ethanol • Priority by Department LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Cellulosic Ethanol • Priority by Department of Energy (2 billion gal. – 2013, 16 billion gal. – 2022) • Best Technology uses Expensive Enzymes – Iogen, Genencor, Novozymes • “Free Enzyme” can only be used one time or Immobilized onto surface to Reuse • Estimated savings by Reusing ~$32 million each ethanol plant, or $7. 5 billion in nation • June 2002 NREL technical report NREL/TP-510 -324388 “Lignocellulosic Biomass to Ethanol Process Design and Economics utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic Hydroylsis for Corn Stover

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Layer-by-Layer Nano Self-Assembly For Enzyme Immobilization LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Layer-by-Layer Nano Self-Assembly For Enzyme Immobilization • Lb. L can be reapplied easily in manufacturing environment (large scale) - - - Enzymes • Lb. L applicable to mixture of enzymes ++++ + + + + - - - ++++ + + + + Polyelectrolytes Enzymes - - - - Polyelectrolytes

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Accomplishments • • QCM and Zeta LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Accomplishments • • QCM and Zeta potential confirm Lb. L immobilization is effective Free enzyme batch reactor data for benchmark (one commercial enzyme MUCH more active than others tested) Immobilized enzyme batch reactor data Pre-treatment methods (base, acid, ultrasound) – very big impact on conversion!

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Conversion Immobilized enzyme is lower than LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Conversion Immobilized enzyme is lower than “free” enzyme; this is expected, savings calculated assumed 10 x less activity! 0. 12 0. 1 0. 08 0. 06 0. 04 0. 02 0 Immobilized Enzyme - 5 layers 0 1000 2000 3000 4000 5000 Time (min) 6000 7000 8000 9000

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Future Work 30 Ultrasound Pretreatment Average LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Future Work 30 Ultrasound Pretreatment Average particle size (microns) • Nanotechnology opportunities to improve activity • Impact of pre-treatments • Test cellulose from wood mills (other commercial sources) 25 20 15 10 5 0 0 20 40 60 Time (min) 80 100

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Questions? Comments? LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Questions? Comments?

LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Polyelectrolytes Studied Polycations Polyanions Polyvinylsulfate Polystyrenesulfonate LOUISIANA TECH UNIVERSITY COLLEGE OF ENGINEERING & SCIENCE Polyelectrolytes Studied Polycations Polyanions Polyvinylsulfate Polystyrenesulfonate Polyethylenimine Polyallylamine Polydiallyldimethylammonium