The document discusses 2nd generation biomass conversion and biorefining. It describes converting non-food biomass like lignocellulosic biomass into transportation fuels, fuel additives and chemicals. Key processes involved include thermal and catalytic upgrading of biomass-derived bio-oil and syngas, as well as chemical hydrolysis of biomass into platform chemicals like levulinic acid. The University of Limerick conducts research on these biomass conversion technologies, aiming to develop sustainable fuels and chemicals from biomass.

1. 2 nd Generation biomass conversion - biorefining J J Leahy –University of Limerick

4. Biomass Sugar/starch crops Lignocellulosic Biomass Oil plants extraction Vegetable oil hydrolysis sugar fermentation Bio-ethanol pyrolysis gasification Anaerobic digestion hydrolysis refining Catalytic upgrading syngas Catalytic reforming Bio-oil Motor fuels & Chemicals biogas methane sugar fermentation esterify biodiesel Bioalcohol

9. Need to select “good” varieties of plants? Novel varieties of Ryegrass, Miscanthus and Sweet Sorghum easier to bioprocess Smarter biofuels - Butanol: major advantages– production? Biogas methane: flexible fuel but production efficiency low? Processes based on novel enzyme technologies or chemical routes (catalysis) Demonstration-scale production New Irish businesses: 2nd and 3rd G biogas and butanol technologies

12. University of Limerick

15. Thermochemical-pyrolysis NONFOOD BIOMASS (grasses or residue from fermentation, etc) lignin (15-30%), cellulose (35-50%), hemicellulose (15-25%) Pyrolysis Gases, Char, Bio-oil T=450-550 o C, Residence time <2s, Heating rates 10 3 -10 4 K/s 70-80% yield

18. Hydrodeoxygenation of Bio-oil Bio-oil Hydrocarbons (naphtha equivalent) Diesel Refining, catalysts Hydrodeoxygenation, Mesoporous silica supported catalysts Bio-oil + H 2  Hydrocarbons + H 2 O 350-400 o C

19. Bio-oil + R-OH  Upgraded Bio-oil + H 2 O Esterification R 1 COOH + R-OH <-> R 1 COOR + H 2 O Acetalization Acid catalysts Acid catalysts, 50-80 o C Acid catalysts Esterification R 1 CHO + 2 R-OH <-> R 1 CH(OR) 2 + H 2 O

20. Gasification pyrolysis Feedstock analysis Feedstock selection & optimisation Biosyn gas Alcohol synthesis Bioethanol higher alcohols Catalytic upgrading Liquid hydrocarbon fuels Char Bio oil Biochar Activated carbon Catalytic Upgrading Diesel Miscible Biofuels Platform Chemicals Gas cleaning & conditioning Chemical Hydrolysis (Solid Acid Catalysts) Pretreatment (Ionic Liquids) Platform Chemicals & optimisation Lignin Residue Sugars Liquid Transport Fuels Alternatives to Petrol-Derived Products Fermentation Catalysis

21. Gasification Temperature Fluidising velocity Inert material Characteristics Residence time Particle size Moisture Mineral content Fixed carbon volatiles Feedstock parameters Process variables Gas quality

23. Gasification of Bio-oil Bio-oil Steam and autothermal reforming, >700 o C Supported metals Fischer-Tropsch Process (FT), supported Co or Fe catalysts Methanol Methanol to gaso- line process (MTG) Diesel CO + H 2 Gasoline Cu/Zn/Al 2 O 3 catalysts, high pressure Bio-oil + H 2 O (+ O 2 )  CO + H 2  Hydrocarbons + H 2 O Dimethyl ether (diesel substitute) zeolites synthesis gas

25. Hydrogen from Bio-oil Water soluble Bio-oil Steam and autothermal reforming, supported metals, >600 o C H 2 + CO 2 + some CO Preferential oxidation process (PROX), supported metals H 2 + CO 2 Energy Low temperature fuel cell Bio-oil + H 2 O (+ O 2 )  CO 2 + H 2 YIELDS – up to 90% Bio-oil H 2 O extraction Hydrogen production from bio-oil looks attractive

26. Hydrogen from Chemicals Derived from Biomass Steam reforming over supported metals and oxides as catalysts H 2 + CO 2 Formic acid, HCOOH Ethanol, C 2 H 5 OH Glycerol

27. Levulinic acid –platform chemical & primary goal of DIBANET (UL led FP7) CROPS ARGICULTURAL RESIDUES CELLULOSIC SLUDGES WOOD STARCH WASTE PAPER MOLASSES THE BIOFINE PROCESS LEVULINIC ACID FORMIC ACID FURFURAL LIGNEOUS CHAR DOWNSTREAM CONVERSION SPECIALTY CHEMICALS COMMODITY CHEMICALS HERBICIDES PESTICIDES ENERGY FUELS AUTOMOTIVE FUELS FEEDSTOCKS “ BIOMASS” PRODUCTS

28. Chemical hydrolysis of cellulose to LA Cellulose Sugars Intermediates I HMF Intermediates II Levulinic Acid (50wt %) First Stage Plug Flow Reactor Second Stage Back Mixed Reactor Fast Reaction (Seconds) Slow Reaction (Minutes) Tars (30 wt%) Formic Acid (20 wt %)

29. BIOREFINERY YIELDS 50% Cellulose 30% Hemicellulose 20% Lignin TYPICAL MOLAR YIELDS (OF THEORETICAL) TYPICAL MASS YIELDS (PER TONNE OF FEED) LEVULINIC ACID FORMIC ACID FURFURAL LIGNEOUS CHAR 70% 70% 70% 100% (MASS) 0.25 0.10 0.15 (VARIES) 0.45