TMP-Bio for Converting Cellulosic Biomass to 2nd Generation Sugar and Near-native Lignin

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TMP-Bio for Converting Cellulosic Biomass to 2nd Generation Sugar and Near-native Lignin Changbin Mao, Zhirun Yuan, Luis Fernando Del Rio, Waleed Wafa Al Dajani, David Wong, Thomas Browne FPInnovations, 570 Boul. Saint-Jean, Pointe-Claire, QC, H9R 3J9 Canada International Forest Biorefining Conference (IFBC) May 9-11, 2017, Thunder Bay, Ontario, Canada

Outline Introduction TMP-Bio Technology Unique Biomass Treatment Technology Robust Enzymatic Hydrolysis Technology TMP-Bio Scaling-up Products from sugar and H-lignin Summary 2

FPInnovations / Upstream New Technologies Improved Forestry Inventory Genome, Fibre attribute, Phytosanitary Bio-Products Integrated Forest Land-Use Management Forest Harvesting Sourcing

Creating Opportunities Beyond Traditional Markets Creating Value Added Wood Products Pulp & Paper Chemicals Develop New Processes and New Materials CNC CF Lignin Sugars Energy (NCC)

Current Commercial Cellulosic Biorefineries M&G and Guozhen 2014 JV Anhui province, CN Agriculture residue ~ 80 MGY 5 Steam explosion (SE) is the predominant pretreatment technology for cellulosic biomass treatment Develop a robust pretreatment technology is critical for * Ref. Novozymes 2014 cellulosic based biorefineries

To Overcome The Challenges 1. Extensive intra-chain hydrogen bonding 2. Cellulose is embedded in HCs and Lignin matrix Glucose Beta-glucosidase Endoglucanase (EGI-V) Cellobiose Reducing end Non-reducing end Exoglucanase CBH-I Exoglucanase CBH-II 6

TMP-Bio Process I Chemical treatment II Hydrolysis Digestible biomass 1000 kg Biomass treatment New products - E-lignin - A-lignin - Activated carbon - Resin - Additives - H-Lignin Bio products - Succinic acid - Lactic acid - Butanol - Ethanol - 400 kg 500 kg sugars 7

TMP-Bio is a CTMP/TMP-based Process Further process development allows us to easily incorporate TMP- Bio technology in both CTMP and TMP mills 8

Pre-treatment and Post-treatment Pilot Trials 100 Glucan conversion, % 80 60 40 20 0 BR42A Post-treatment (Pilot post-treatment) BR17 Pre-treatment (pilot pre-treatment) 0 5 10 15 20 Enzyme loading, FPU/g glucan Hydrolysis conditions: 2% solids, 72 hours. 9

Unique Biomass Treatment Technology Produce highly digestible biomass at large scale Low chemical, low energy, medium temperature Biomass treatment can be conducted prior or post refiner No need to extract HCs and lignin (Cel/HC/L, ~50/15/23) High sugar conversion yield (90%+ at high solid) Could use existing facilities at a large scale (+1000 ton/d) 10

Robust Enzymatic Hydrolysis Technology Cellulase (CL) at 20 FPU Formulation F3 at 20FPU 120 Sugar Conversion Yield, % 100 80 60 40 20 0 Xylose Glucose 0 24 48 72 96 120 144 E- Hydrolysis Time, Hrs Sugar Conversion Yield, % 100 80 60 40 20 0 Glucose Xylose 0 24 48 72 96 120 144 E-hydrolysis Time, Hrs With the F3 at 20 FPU, E-Hydrolysis bottleneck disappeared with glucan and xylan being simultaneously hydrolyzed 11

Enzyme Formula Optimization (F3) glucan yield 100 80 60 Estimated Response Surface BG=10.0 40 20 100 0 0 10 20 30 40 0 20406080 Ctec Htec Predicted conversion yield, % 100 80 60 40 20 0 fitted lower 95% upper 95% val-p % 0 20 40 60 80 100 Observed conversion yield, % 12

Robust Additives Glucose yield, % 100 80 60 40 20 +50% F3 with add. (6d) F3 with add. (3d) Model without add. (3d) R 2 =98% 0 0.038 0.076 0.114(ml enzyme/g cellulose) 0 5 10 15 20 25 Enzyme dosage, (Ctec1, FPU/g glucan) The additives work extremely well at low enzyme dosage (+50% at 5 FPU) At 5 FPU, sugar conversion yield is +75% (6 days) 13

Towards High Solids Enzymatic Hydrolysis (2% vs. 20%) Overall sugar yield Total sugar concentration Overall Sugar yield, % 100 80 60 40 20 0 Sugar yield-2% Sugar yield -20% 0 2 4 6 Hydrolysis time, days Sugar concentration, g/l 150 120 90 60 30 0 TSCon-2% TSCon-20% 0 2 4 6 Hydrolysis time, days Similar hydrolysis efficiency for both low and high solid loadings Much high sugar concentration at 20% solid loading 14

High solid (20%) Enzymatic Hydrolysis (50L) 15

High solid (20%) enzymatic hydrolysis (1,000L) 2 0 0 L 200 OD kg Biomass at 30% D1 12:08 4 barrels D1 14:25 4 barrels D1 14:41 6 barrels D2 10:17 8 barrels Total sugar: 113.3g/L 16

Sugar Lignin Separation 17

TMP-Bio Scale-up Biomass Screw press Centrifuge Grinder Press Impregnator I Refiner II Paddle Reactor LC Reactor Lignin for drying Latency Sugar Tank Totes for shipping Digester FPInnovations small TMP-Bio pilot plant (PC) 18

Major Equipment of The Pilot Plant Existing pilot equipment (A) A1 A2 A3 A4 Installed new pilot equipment (B) B1 B2 B3 B4 19

TMP-Bio pilot plant 20

Sugar Properties from Pilot Plant Operation 21

Sugar Quality from Pilot Plant Operation 22 Fresh sugar Concentrated sugar Average ph 5,1 5,3 Average density (kg/l) 1,065 1,213 Glucose concentration (g/l) 102 320 Xylose concentration (g/l) 32 97 Furfural (g/l) Not detected 0,031 5-(Hydroxymethyl) furfural (g/l) Not detected 0,023 5-Methyl furfural (g/l) Not detected Not detected 2-Methyl furan Not detected Not detected Acetic acid (g/l) 4,4 12,2 Hg, As, Pb, Cd (ppm) - <0.5 Fe, Mn, Cu (ppm) - <3.3 Ca (ppm) - 747 P (ppm) - 150 S (ppm) - 192

Lactic Acid Fermentation LA Lab result 23 Direct fermentation without detoxification Independent pilot trials confirmed sugar-free fermentation can be achieved Lactic acid yield: 80-93% (w/w)

H-lignin Powder Product Kraft lignin H-lignin Light color, no-sulfur, properties close to native lignin Particle size: 10-300 µm 24

Towards Commercialization Biomass Treatment 500 ton/d 100 ton/d Highly digestible biomass (Cel/HC/L: 50/15/23) Engineering Study on 1 ton/batch Enzymatic hydrolysis Yd, +90% HE-lignin HA-lignin Resin Additives Hydrolysis lignin (contains ~60% lignin) New products Succinic acid Lactic acid Butanol Ethanol Mixed sugar (con.>10%) 25

Summary FPInnovations has developed a proprietary TMP-Bio technology for cellulosic biomass conversion (Patented in US, CA, NZ, AU, CN) The unique biomass treatment technology can produce highly digestible biomass at industrial scale (1000ton/day) Robust enzymatic hydrolysis technology can simultaneously convert both glucan and xylan at 90% at 20% solid loading High quality sugar and near native H-lignin are produced in our pilot plant Various valued-added products can be developed from TMP-Bio sugar and H-lignin 26

Acknowledgment o The financial support from NRCAN, MRNF, partners and our member companies o Novozymes for providing us Cellic series enzymes o The ARS National Center for Agricultural Utilization Research, USDA, for providing us the strain for lactic acid o Our technicians and other staff in FPInnovations,... o IFBC committee 27

Thank you Changbin Mao Scientist - Biorefinery 514-782-4649 Changbin.Mao@fpinnovations.ca Zhirun Yuan Research manager - Biorefinery 514-782-4661 Zhirun.yuan@fpinnovations.ca Follow us on www.fpinnovations.ca