Lignin valorization towards materials, chemicals and energy 2 nd Lund symposium on lignin and hemicellulose valorisation, November 3-4, 2015 Lund Dr. Richard Gosselink
Contents Lignin valorization Biorefineries Conversion technologies for lignin Take home messages 2
Lignin valorization Lignin = glue in woody type of biomass Abundantly available at relatively low costs Energy source Versatile raw material for many applications Additional revenues for Pulp&Paper industry (focus on cellulose) and 2 nd Generation Biorefinery industry (focus on fuels) 3
Chemicals and materials driven biorefineries - Developing biobased chemicals will increase the profitability of second generation biofuels production - Biobased chemicals and materials driven biorefineries can also be created alongside traditional vegetable oil, starch, sugar and paper producers - Agrifood industries are diversifying their product slate; increasingly engaging in non-food products - Traditional pulp and paper industry focus on side stream valorization (lignin initiatives of Domtar, Stora Enzo, West Fraser,...) 4
Lignin structure Lignin Lignocellulose architecture: Rubin 2008 Model softwood lignin: Brunow 2001 5
Composition of lignocellulosic (LC) feedstocks (wt% dm) Origin Species Carbohydrates Lignin C6 sugars C5 sugars Hardwoods Mixed (stem) 60-75 40-50 16-20 18-25 Softwoods Grasses Agricultural residues Mixed (stem) Sugar cane bagasse 60-67 40-50 15-18 27-33 60-70 33-36 20-25 19-24 Corn cobs 75 40 30-34 15 Wheat straw 55-60 30-35 20-23 16-21 Rice husks 50-55 30-35 20-22 20-22 6
Technical lignin availability (dry ton/y) Pulp & Paper industry 50 M ton lignin extracted, 2% commercial lignins 1 M ton lignosulfonates, 0.1 M ton kraft lignins, 5-10 kton sulfur-free lignins Efficient processing and extraction in 2020 2-4 M ton extra kraft lignin Biomass conversion (Biorefinery) Some commercially available, but no current lignin production Steam explosion (eg. Biochemtex, Abengoa) Organosolv lignins (eg. Lignol, CIMV, Dechema) Hydrolysis lignins (eg. POET-DSM, Inbicon/DONG, SEKAB) Large quantities expected in EU in 2020 (4-5 M ton) 1 ; in 2030 (12 M ton) 1 1 EU directive 10% biofuels in 2020, 25% in 2030 7
Lignin production versus utilisation
Aromatic chemicals & materials derived from lignin Polymerisation Depolymerisation Binders/resins Fractionation Oligomeric fragments Chemical/ Enzymatic upgrading (Bio-)catalysis Monomeric chemicals Composites Coatings Surfactants Bitumen (asphalt, roofing) Confidential 9 9
Final products Application sectors 2 nd generation fuels Ethanol Thermoplastics Energy PVC, polyolefins, polyurethanes, polyesters Materials Varied biomass Fractionation Intermediates Chemistry Biotechnology Packaging Cereal byproducts Hemicellulose Resins/Adhesives Forestry waste Cellulose Food additives Detergents Building SRC wood Lignin Wood panels Adhesives and 10 paints
INTERMEDIATE PRODUCTS Cellulose (glucose) Hemicelluloses (xylose and arabinose) Lignins 11 11
FURTHER VALUE CHAIN ASSESSMENT Lignin- PU elastomer coatings Rigid lignin-pu foams Bio-ethanol for fuel or PVC Biobased lignin-phenol-formaldehyde resins Itaconic acid for paint 12
Lignin application in asphalt (macromolecule) Bitumen = asphalt binder In future more scarcity and lower quality; increase of price level Lignin in combination with vegetable oil Substitution of 50% bitumen by lignin in low temperature asphalt testroad (Biobased Infra project Zeeland NL; July 2015) Monitoring of road quality / performance / durability coming years 13
Relevance of (bio)aromatics Aromatic chemicals used in a lot of consumer products: high performance polymers, resins, fuel additives, flavours, agrochemicals, fragrances, coatings, bottles etc. Production capacity is over 100 Mton annually and demand is growing Shale gas leads to less production of aromatics Alternative sources are needed Lignin, the largest aromatic biopolymer in nature, is a good option 14
Conversion technologies for lignin to chemicals combustion Heat electricity gasification CO, CO2, H2, CH4 chemicals B/A hydrolysis oxydation vanillin (C7) Lignin reduction phenylpropane (C9) hydrogenolysis oil Mixed aromatics pyrolysis BTX (C6,C8) solvolysis char Phenols (C6) supercritical Ionic liquids /DES fermentation 15
Sub- and supercritical water / hydrothermalin to Target defunctionalised aromatics (BTX, phenolics) Moderate temperature for hydrothermal (200-300 C) High temperature / pressure (300-400 C, > 220 bar) at sc conditions Green solvent Various catalysts showing higher selectivity Moderate yields of monomers (typically >20%) Added phenols yield complete conversion in dimers Demonstrated at R&D 16
Hydrothermal lignin depolymerization Biomass Focus: Biorefinery lignins Aromatics and phenolics O H Turn lignin into high value aromatics (BTX) and building blocks (phenol) Approach: Selective catalytic hydrothermal depolymerisation without external hydrogen; Prevent re-condensation Van Es, D.S., Van der Klis, F., Van Haveren, J., Gosselink, R.J.A., Method for the 17 depolymerization of lignin, WO2014/168473 17
Relative Abundance Hydrothermal lignin conversion RT: 4.00-23.00 100 95 90 85 80 75 70 65 10.84 NL: 7.59E6 TIC MS Lignin1603 11 60 55 50 45 40 35 30 25 20 12.02 20.42 14.68 15 10 5 13.04 15.29 8.54 8.62 16.09 20.37 14.03 11.17 8.84 12.59 16.27 19.10 22.32 4.04 4.38 5.81 7.22 9.90 13.29 17.80 7.08 7.27 19.19 20.47 21.00 0 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Time (min) Lignin depolymerization is 20% over Pd/C Limited product distribution; 1 compound (guaiacol) in 50% Monomers further converted into BTX, cyclohexanone for chemicals and fuel additives 18
Lignin/biomass conversion to aromatics Technology Company Type of development Feedstock Scale Product portfolio Pyrolysis ECN (NL) RTD lignin 1 kg/h Lignin oil, char, gas Catalytic pyrolysis Biobtx (NL) RTD biomass 1 kg/h Pyrolysis oil, BTX Catalytic fast pyrolysis Anellotech (US) Pilot biomass 1 kg BTX, hydrocarbons, gas BCD Borregaard (No) Commercial Lignosulfonate 1500 t/y Vanillin HDO UOP (US) RTD lignin 25 g Lignin oil 19
Take home messages LC biorefineries will generate large amounts of lignin Lignin valorization can lead to more profit Lignin conversion to valuable products (fuel additives, chemicals and materials) is expanding area Technologies for deriving aromatic base and specialty chemicals are leaving the initial stages of infancy Catalytic conversion of lignin is leading A number of viable concepts to get to biobased fuels, chemicals and materials have been demonstrated Lignin biorefinery leads to multiple outlets including chemicals, materials and energy 20
Wageningen UR Lignin Platform Focus on lignin to bioaromatics + materials NL knowledge institutes + industrial partners EU projects: NL projects: Ocobinders Industry sponsored projects: coatings, resins, life sciences,... Networks: LigniFAME More info: Wageningenur.nl/ligninplatform Richard.gosselink@wur.nl 21