1. L OUISIANA T ECH U NIVERSITY COLLEGE OF ENGINEERING & SCIENCE Large Scale Reactors to Reduce Cellulosic Ethanol Costs November 5, 2009 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

2. L OUISIANA T ECH U NIVERSITY 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

3. L OUISIANA T ECH U NIVERSITY COLLEGE OF ENGINEERING & SCIENCE OH H H C H OHH C C C O CC O H H O H Sugar (glucose) H H Ethanol Carbon Dioxide O H H C H OH H C C C O C C H O H H H H O H H C H H C C C O C C H O H H H H O H H C H H C C C O C C H O H H H H O H H C H H C C C O C C H O H H H H O H H C H H C C C O C C H O H H H H O O O O Cellulose

4. L OUISIANA T ECH U NIVERSITY 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

5. L OUISIANA T ECH U NIVERSITY COLLEGE OF ENGINEERING & SCIENCE Layer-by-Layer Nano Self-Assembly For Enzyme Immobilization LbL can be reapplied easily in manufacturing environment (large scale) LbL applicable to mixture of enzymes ------------- ++++++++++++ Polyelectrolytes Enzymes ------------- Polyelectrolytes ++++++++++++ Enzymes -------------

6. L OUISIANA T ECH U NIVERSITY COLLEGE OF ENGINEERING & SCIENCE Accomplishments QCM and Zeta potential confirm LbL 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!

7. L OUISIANA T ECH U NIVERSITY COLLEGE OF ENGINEERING & SCIENCE Immobilized enzyme is lower than “free” enzyme; this is expected, savings calculated assumed 10x less activity!

8. L OUISIANA T ECH U NIVERSITY COLLEGE OF ENGINEERING & SCIENCE Future Work Nanotechnology opportunities to improve activity Impact of pre-treatments Test cellulose from wood mills (other commercial sources)

9. L OUISIANA T ECH U NIVERSITY COLLEGE OF ENGINEERING & SCIENCE Questions? Comments?

10. L OUISIANA T ECH U NIVERSITY COLLEGE OF ENGINEERING & SCIENCE Polyelectrolytes Studied Polyvinylsulfate Polystyrenesulfonate Polyethylenimine Polyallylamine Polydiallyldimethylammonium Polycations Polyanions