Biorefinery concepts for non-wood raw materials Dr. Päivi Rousu Vice President, R&D, IPR

The future is BIOREFINING Biorefinery concepts for non-wood raw materials Dr. Päivi Rousu Vice President, R&D, IPR

Outline of presentation Chempolis corporation formico - 3 rd generation biorefining technologies Analysis of cellulosic ethanol costs and revenues Profitability of cellulosic sugar and lignin platforms Comparison of low-cost cellulosic ethanol feedstocks Chempolis biorefinery Summary and conclusions

Chempolis - the biorefining technology corporation Chempolis supplies sustainable, globally patented biorefining technologies: formicobio the cellulosic ethanol technology formicofib the non-wood fibre technology Chempolis is a privately owned company established in 1995. Chempolis has a biorefinery with HQ and R&D Centre in Oulu, Finland.

Chempolis Achievements International recognitions Proprietary biorefinery plant IPR IFC (a private sector arm of the World Bank), evaluated Chempolis s technology as the most economical and environmentally sustainable non-wood pulping technology In a study by the Department of Energy of the USA, Chempolis s technology was evaluated as the most energy-efficient among modern pulping technologies Nominated in top 3 list on the Global Cleantech Cluster Associations contest The superiority of Chempolis technologies has been proven in Chempolis own biorefinery and in various evaluations Chempolis has invested some MEUR 20+ in its own biorefinery, which also functions as a development and marketing centre for testing customer s raw materials and producing samples of cellulosic sugars, bioethanol, biochemicals, and papermaking fibres The plant is capable of processing of various lignocellulosic raw material The plant was designed and implemented by Chempolis itself in record time; 8 months IPR strategy has been professionally executed, in cooperation with patent office AB Kolster Oy Portfolio of patents includes more than granted 100 patents and several patents pending and new are continuously applied Process patents, unit process patents, product patents and hardware patents Chempolis products creates formico -family formicobio ; formicofib ; formicosystems

Chempolis partners with the Leaders in India Partnership agreement with NRL, subsidiary of Bharat Petroleum 2014 Teaming up with Oil and Natural Gas of India (ONGC) 2013 NRL is a Government of India Public Sector Undertaking which operates a 3.0 MMTPA Refinery at Numaligarh, Assam, India. NRL is a subsidiary of Bharat Petroleum Corporation Ltd (BPCL) ONGC (Oil and Natural Gas Corporation Limited) is India's leading oil & gas exploration company.

Evolution of biorefining technologies 3G 2G Lignocellulosics (e.g. straw) - selective fractionation by recyclable biosolvent - co-production of ethanol and other products 1G Lignocellulosics (e.g. straw) - non-selective chemical and mechanical pretreatments - (bio)chemical hydrolysis and fermentation to ethanol Food: sugar & starch - fermentation to ethanol

formico - the true 3G platform Cellulose products Paper fibres Paper, board, tissue High value fibres Viscose, CMC, Nano Non-Food and Non-Wood biomass Cellulose Hemicellulose Lignin, nutrients Glucose Ethanol, butanol, Lactic acid, succinic acid Hemicellulose products Pentose sugars Xylose, arabinose Platform chemicals Acetic acid, furfural Lignin products 3G formico biorefinery integrates biomass conversion process and equipment to produce multiple fuels, power, heat, platform biochemicals and fibres from biomass 3G formico biorefinery is analogous to petroleum refinery, which produces multiple fuels and products from petroleum Lignin Polymers, plastics Biocoal Steam, electricity Nutrients Fertilizer

First implementations of the 3G formicobio technology Cellulose products Non-Food biomass Glucose Ethanol, chemicals Cellulose Hemicellulose Lignin, nutrients Hemicellulose products Sugars Ethanol, chemicals Platform chemicals Acetic acid, furfural Lignin products Biocoal Steam, electricity

formicobio technology as a cellulosic sugar platform Non-food biomass formicodeli (biomass fractionation) Biosolvent Washing Water Cellulose Hydrolysis Glucose Processing of sugars Biofuels, biochemicals Evaporation formicopure (distillation) Water Acetic acid Separation of hemicell. sugars Furfural Xylose and other sugars Biocoal/ lignin Power plant / processing of lignin

formicofib technology Biosolvent Water Water Non-wood biomass formicodeli Washing TCF bleaching Pulp Evaporation formicopure Filtrate treatment Acetic acid Furfural Dry biofuel Power plant

Principles of techno-economic calculations of biorefining Ethanol Sales as fuel ethanol Biomass (e.g. straw, bagasse) Biorefinery Battery limit of calculations Lignin, stillages, steam condensate Furfural, acetic acid Sales to chemical industry or treated as effluent Biomass composition Cellulose C5 in hemicelluloses C6 in hemcelluloses Power plant Steam, electricity Lignin and other components Energy sales (power to the grid, steam, )

Key economic variables affected by fractionation or pretreatment Accessibility and ease of hydrolysis of cellulose Yield of glucose from cellulose Required enzyme dose Conversion of hydrolysis of hemicelluloses (i.e. share of hemicelluloses that react into soluble sugars) Reactions of hemicellulose sugars (solubilized sugars react further, especially into furfural) Recovery and sales of reaction products of hemicelluloses Acetic acid (all processes hydrolyze acetate esters present in hemicelluloses) Furfural

Lignin in lignocellulosic feedstocks Lignin is present both around and between cellulose fibrils Pictures taken from - Koch G (2008) Raw Material for Pulp. In: Sixta H (ed) Handbook of Pulp. Vol. 1. Wiley-VCH Verlag. - Gullichsen J (1999) Fiberline Operations. In: Gullichsen J & Paulapuro H (eds) Papermaking Science and Technology, Book 6A, Chemical Pulping. Fapet Oy

Lignin in lignocellulosic feedstocks Behaviour during fractionation or pretreatment Presence in hydrolysis Impact on the performance of hydrolysis formicobio Almost complete dissolution (e.g. 96%) is achieved during biomass fractionation. Minor concentration in cellulose (e.g. 2% of cellulose). Absence of lignin improves the access of enzymes reduces the required enzyme dose increases yield of hydrolysis improves overall economics Typical 2G Remains insoluble. Almost all of the original lignin is present in hydrolysis (e.g. 50% of cellulose) both around and between cellulose fibrils. Presence of lignin hinders the access of enzymes increases the required enzyme dose decreases the yield of hydrolysis impairs overall economics

Reactions of hemicelluloses 1. Hydrolysis of hemicelluloses into sugars: polysaccharides hydrolyze into sugars O O OH OH O OH OH OH OH O O OH O OH Polysaccharide chain Sugars 2. Reaction of hemicellulose sugars OH OH OH O OH C5 sugars Furfural 3. Generation of acetic acid by hydrolysis of acetate esters of hemicelluloses

Reactions of hemicelluloses Hydrolysis of hemicelluloses into sugars Reaction of hemicellulose sugars Hydrolysis of acetate esters of hemicelluloses formicobio Almost complete hydrolysis (98%) is achieved during biomass fractionation. Controlled conversion of C5 sugars into furfural from 10% upwards. Furfural is recovered as a co-product. Almost complete hydrolysis takes place during biomass fractionation. Acetic acid is recovered as a co-product. Typical 2G High conversion is targeted but it is limited by further reactions of sugars. 85% is a practical figure, a part of hemicelluloses hydrolyze during enzymatic hydrolysis. Around 10% of C5 sugars react further, mainly into furfural. Furfural is not recovered and it is treated as waste. Almost complete hydrolysis takes place during biomass pretreatment. Acetic acid is not recovered and it is treated as waste.

Product yields of biorefining formicobio Typical 2G Yield of glucose from cellulose (enzymatic hydrolysis) 90% 80% Yield of glucose from cellulose, kg/t biomass 340 300 Yield of ethanol from cellulosic glucose, kg/t biomass 160 140 Conversion of hydrolysis of hemicelluloses 98% 90% Yield of sugars from hemicelluloses, kg/t biomass 260 260 Yield of ethanol from hemicellulose sugars, kg/t biomass 95 95 Enzyme consumption (relative figure) 10 20 Generation of chemicals Acetic acid, kg/t biomass Furfural, kg/t biomass 35 25 35 (treated as waste) 10 (treated as waste) Overall product yield, kg/t biomass 315 235

Value per unit of biomass Overall economics of biorefining 120 100 3G formicobio 2G (pretreatment + enzymatic hydrolysis) 80 60 40 20 0 Revenues Operating cost Gross profit Chempolis 3G formicobio technology enables superior profitability

Glucose and lignin platforms Biomass fractionation enables production of pure glucose for value-added applications, e.g. chemicals, medicines Biomass fractionation enables production of pure lignin for down-stream processing e.g. into adhesives Cellulose products Non-Food biomass Glucose Ethanol, chemicals Cellulose Hemicellulose Lignin, nutrients Hemicellulose products Sugars Ethanol, chemicals Platform chemicals Acetic acid, furfural Lignin products Biocoal Steam, electricity

Products from fractions C6 sugars Ethanol, butanol, microbial oil, penicillin, succinic acid, levulinic acid, formic acid C5 sugars Furfural, ethanol, lactic acid Lignin Particle board adhesive Cellulose Paper and board products Viscose fibres Nano-cellulose

Value per unit of biomass Economics of glucose and lignin platforms 120 100 80 base case pharma-grade glucose lignin to refining 60 40 20 0 Revenues Operating cost Gross profit formicobio technology enables superior profitability in various biorefining applications

Raw materials Wood Agricultural residues Energy crops etc. Acacia Birch Chestnut Eucalyptus Oil palm trunk Pine Tropical hardwood mix Local forest residues Bagasse Castor stalk Cassava stem Corn stalk, cob, stover Cotton stem EFB Oat straw OPF Rye straw Pineapple Rice straw Sugar cane thrash Wheat straw Other industrial waste streams Arundo donax Bamboo Chinese alpine rush Common reed Flax Miscanthus sinensis Reed canary grass Sarganda Sisal Various local grasses

Lignocellulosic feedstocks Biomass Cereal straws Sugarcane bagasse Wood Price range (dry basis) 30 80 EUR/t 25 60 EUR/t 40 100 EUR/t Overall product yields vary typically +/- 10% Price of feedstock and its secure supply determines its feasibility, not the composition

Chempolis Biorefinery serving customers and visitors EU Commissioner Oettinger, 2011 NDRC, China, 2010 Indian Minister of New and Renewable Energy, 2011 Total investment > 20 MEUR Customer trials Dimensioning of machinery and formico systems Products of the biorefinery pulp for paper, board, textiles and nano glucose for fuels and chemicals xylose for fuels and chemicals acetic acid, furfural biocoal, lignin

Milestones of the Chempolis own biorefinery 2008 Biorefinery production line of papermaking fibres commenced 2009 Successful non-wood papermaking production test runs completed 2010 Licence to produce bioethanol in Oulu biorefinery 2010 Inauguration of 3 rd generation bioethanol production line (May) 2010 Several customer and in-house trial runs and high-level visitors Finland s Prime minister Vanhanen

Design principles of Chempolis biorefinery Continuous operations Industrially proven solutions straightforward scale up of commercial production Dimensioning of machinery Modern DCS (formicocont )

Key figures of Chempolis biorefinery 85 equipment 70 tanks and 80 pumps 28 heat exchangers 550 pipelines 390 instruments, incl. 95 control valves 120 motors 85 frequency converters 500 I/O

Main experiences gained at the biorefinery formico technologies work! Reliability and long-term durability of the equipment and materials Dimensioning data for full scale Enhanced control of selective biomass fractionation Tailored serving of customers with specific raw materials and needs

Summary and conclusions Selective fractionation of biomass using formicobio technology enables superior economics in biorefining: Higher product yields, higher revenues Lower operating costs, especially lower enzyme cost Option for value added products from glucose, xylose and lignin Good economics can be achieved with various biomasses as long as their prices are competitive The 3 rd generation formicobio technology has been demonstrated and it is ready for commercial take-off