Production of Chemicals and Materials in Future Pulp Mill Biorefineries Karin Lindgren, Innventia INNVENTIA AB Staff 270 Swedish R&D company Serving customers globally Pulp, paper, packaging, printing, new materials and biorefining Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 2 Chemical pulping process Source: Aker Kvaerner Lindgren Italic 4 Biorefinery – Simultaneous production of fibres, energy and chemicals Increasing costs – Energy and wood Decreasing trend prices on pulp Biorefinery is the solution – – – – Handling of large volumes of biomass New pulp mill products New efficient separation processes Add “side” processes Innventia approach – Kraft/soda pulp mill platform – Focus on the major components – Efficient separation process and mill integration Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 4 Lignin carbon fibres Cellulose Wood/plants- a mine for valuable polymers Cellulose Softwoods Cellulose % Hardwoods Agro/annual Spruce Pine Birch Euca. glob. Euca. urogr. Bagasse 44 44 45 51 50 44 Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 6 Cellulose Products NanoCellulose Kraft Pulp Fibres Fibre PLA Composite Transparent Films Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 7 Lignin from black liquor - LignoBoost 50% of the wood ends up in cooking liquor Cellulose products Wood to kraft pulp mill Pulp Carbohydrates Black liquor Extractives Lignin 55-60 % of energy goes into the black liquor Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 9 Wood/plants – a mine for valuable polymers - lignin Softwoods Spruce Pine Lignin, % 27 28 Hardwoods Euca. glob. 24 Agro/annual Euca. Hemp Bagasse urogr. 29 25 22 Physical/chemical properties vary with species and process Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 10 The LignoBoost process Lignin IN Lignin OUT Evaporation Recovery Boiler Replacement of fossil fuel in lime kilns 50 L fuel oil ptp can be saved Lime Kiln Digester Wood Wood Chips Bleaching Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 11 Pulp/Paper The LignoBoost process Precipitation Filtration Filtration & Displacement washing Re-suspending H2SO4 Wash liquor Black liquor Lignin CO2 Back to the evaporation plant Back to the evaporation plant Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 12 LignoBoost lignin – a new material Typical composition, % C Na Ash S N 64 - 66 0.05 - 0.4 0.3 - 1 1-3 0.1 Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 13 OCH 3 OH OH HO HO lignin OCH 3 O lignin OH OCH 3 HO O O HO OH HO O OCH 3 O HO O HO HO OCH 3 Alkali Water O HO OH 1% 25% Sugar content 2% 10% H 3 CO S O OH O O O OCH 3 HO OH H 3 CO OH Ash content H 3 CO OCH 3 OH OH O O OCH 3 HO Solubility HO O O O HO OH OCH 3 OCH 3 OCH 3 O OH 3% 5% OH O HO Lignosulphonate H 3 CO OH HO OCH 3 HO Kraft lignin HO OCH 3 HO O HO OCH 3 OH O OCH 3 HO HO OCH 3 OCH 3 OCH 3 O HO O CHO O HO OH O OH HO O OCH 3 OH OCH 3 OH Metso filter in Innventias lignin demo plant VPA 1040 24 chambers 1-1.2 t lignin/h Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 15 Fossil fuel in pulp mill lime kilns In Sweden ca 300.000 tonne oil/year Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 16 Carbon fibres - High value application of lignin Construction material in composites Light Weight High Strength and Modulus High Resistans to Heat and Corrosion Expensive Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 17 Oil or renewable Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 18 Manufacturing process of carbon fibres Raw material Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 19 Carbon fibres from lignin Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 20 Lignin can make difference 650 000 ton pulp/year 10% lignin extracted … 16 000 ton carbon fibres = 33 000 ton …can replace 40 % steel in 160.000 cars Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 21 Activated carbon from lignin Water and gas cleaning Main industrial source coal Physical and chemical activation Surface area up to 3000 m3/g Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 22 Phenols from lignin OH R Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 23 Hemicellulose from black liquor, chips, saw dust and forestry residues Wood/plants – a mine for valuable polymers - Hemicelluloses Softwoods Hardwoods Agro/annual Spruce Pine Birch Euca. glob. Euca. urogr. Hemp Bagasse Xylan, % 9 8 26 21 16 29 28 Glucomannan, % 19 18 3 4 3 2 2 • Glucomannan degrades in alkali • Xylan is relatively stable in alkali Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 25 Chip leaching* for salt and hemicellulose removal Developed for pre-treatment prior to kraft pulping Leaching liquor (acid or alkaline) Wood chips Chip kidney To processing • pulping • pelletizing • gasification Polymeric hemicellulose and inorganic ions *Protected by patents: WO2004/050983, US2005/0034823, WO03/046276 Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 26 Xylan from black liquor Industrial ultrafiltration trials with in-line ceramic membrane 2007 Laboratory membrane filtration unit at Innventia since 2003 White liquor Principal outline of mill trial: Wood chips UF-membrane Feed To evaporation Retentate Unbleached pulp White liquor Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 27 Polymeric Xylan from black liquor Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 28 Potential hemicellulose applications Fiber additives Gas barriers O O HO O OH O HO O HO OH HO O OH O OH O SW fibre O OH O HO O OH OH OH O O O HO HO O HO HO O O HO OH O OH (Z ) OH OH HOOC O HO O O O OH O Hydrogels HO O O OH OH O OH O 4-5 times higher surface charge HO HO O OH O OH HO O OH O HO O Other applications Polymers (PLA) Xylitol, furfural Sugar acids Emulsifiers Carboxymethylation HO Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 29 Wood xylan feedstock for lactic acid and PLA Hemicelluloses (glucomannan and/or xylan) Acidic or enzyme hydrolysis Pentoses and hexoses Fermentation or alkaline oxidation Polymerization Polylactide (PLA) Lactic acid Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 30 2G Ethanol from forestry residues 2G Ethanol Acid/enzymatic pretreatment OR Alkaline preteatment – can handle all wood/forestry residues/annual plants – good separation of cellulose and lignin – established technology Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 32 Alkaline route from wood to ethanol Forestry Residues Ethanol Hydrolysis, Fermentation & Distillation Alkaline fractionation CO2 Lignin Separation Chemicals Recovery Energy Recovery Sulphur-Free Lignin Electric Power Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 33 2G Ethanol- Alkaline Process Will it work in practice? Yes! Tested in mill and pilot scale trials 70 t soda pulp produced 40 m3 pulp suspension used 700 litres of ethanol produced S-free lignin produced Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 34 The Future Wood/Agri Pulp Mill Biorefinery - many options available Pulpwood Fibre processing Black liquor Pulp & Cellulose Integrated Energy Heat & Power System Forestry/agri residues Primary treatment Conversion Conversion Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 35 Chemicals and materials Biofuels Possible time frame for commercialization 2- 5 years > Lignin Fuel oil replacement Pellet additive Dispersant Activated carbon Xylan Gas barrier Fibre surface additive Forestry residues 2G EtOH and S-free lignin High quality pellets Benzene Phenol Carbon fibres Lactic acid, PLA Polyesters Syngas FT-diesel/DME Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 36 5 years The pulp mill biorefinery Energy DME Ethanol FT-diesel Biooil Heat Electricity Solid fuel Lignin Chemicals/Materials Lignin Lignin Cellulose Phenols Carbon fiber Binders Dispersants Activated carbon Fiber additives Barriers Hydrogels Bark Hemicellulose Forestry residues Cellulose Fibers Derivatives Nanocellulose Extractives Functional polymers Bioactive compounds Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 37 Thank you for the attention Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries 38