Lignocellulosic biorefinery pathways to biobased chemicals and materials

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1 Lignocellulosic biorefinery pathways to biobased chemicals and materials 1 st Int. Forest Biorefinery Conference, Thunder Bay, Canada May 9-11, 2017 Richard Gosselink, Carmen Boeriu, Paulien Harmsen, Jeroen Hugenholtz

2 Contents Wageningen Food & Biobased Research Biorefinery value chains Lignin valorization to materials and chemicals Microbial production of biochemicals

3 2 Partners Wageningen Research 2,410 FTE of faculty and staff 11,000 students Revenue in 2015: 635 million

4 Wageningen Food & Biobased Research In-depth knowledge of the entire agri-food chain Connecting agri-food with chemistry, materials and energy production Market oriented R&D approach Multi-disciplinary applied R&D project teams Up-scaling: from lab to pilot > 200 employees with a yearly turnover of 30M Sustainable Food Chains Biobased Products Healthy & Delicious Foods

5 Research Topics BU Biobased Products Biorefinery & Sustainable value chains Biomass sourcing & logistics Biomass resources & characterization Biomass pretreatment (mechanical/chemical) Composite materials Sustainable building materials Sustainable Chemistry Bioplastics, coatings and packaging Fine chemicals (plasticizers, polymer building blocks) Polymeric foams Fire retardants Bioconversion Fermentation (H 2, ethanol, lactate, ABE, fatty acids) Bio-catalysis

Chemicals and materials driven biorefineries Developing biobased chemicals will increase the profitability of second generation biofuels production Biobased chemicals and materials driven

6 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 Agri-food industries are diversifying their product slate; increasingly engaging in non-food products

7 Composition of lignocellulosic feedstocks (wt% dm) Origin Species Carbohydrates Lignin C6 sugars C5 sugars Hardwoods Mixed (stem) Softwoods Grasses Agricultural residues Mixed (stem) Sugar cane bagasse Corn cobs Wheat straw Rice husks

Pretreatment of lignocellulose Fibres: pulp, paper, building materials Dissolving cellulose: textile Sugars: molecules for conversion Make the polysaccharides accessible to catalysts Using low/high

8 Pretreatment of lignocellulose Fibres: pulp, paper, building materials Dissolving cellulose: textile Sugars: molecules for conversion Make the polysaccharides accessible to catalysts Using low/high ph, high temperatures, oxidative agents, mechanical forces (explosion) Catalysts for polysaccharide hydrolysis: enzymes or acid Micro-organisms can use the monosaccharides in fermentation processes

9 Pretreatment technologies Chemi-mechanical Green biorefineries Alkaline hydrolysis Autohydrolysis (only water) Organosolv pretreatment using acetic acid Thermal pretreatment Mild pretreatment (assisted by enzymes)

11 Enzymatic pretreatment (see poster)

$CIMV organosolv fractionation process Acetic/formic acid RAW MATERIAL (wood, straw, bagasse ) Since 2006$ recycling RAW PULP Delignification / Peracids Lignin / sugars separation Washing / Neutralisation

recycling RAW PULP Delignification / Peracids Lignin / sugars separation Washing / Neutralisation

12 CIMV organosolv fractionation process Acetic/formic acid RAW MATERIAL (wood, straw, bagasse ) Since 150 kg/h Mechanical conditioning Organic refining SUGARS & LIGNINS Organic acid solutions Organic Acid recycling RAW PULP Delignification / Peracids Lignin / sugars separation Washing / Neutralisation Bleaching / Washing LIGNINS C 5 SUGARS Cellulose C 6 PULP M. Delmas, Chem. Eng. Technol. 2008,31,No.5,

13 Intermediate products Cellulose (glucose) Hemicelluloses (xylose and arabinose) Lignins 13

14 Further value chain assessment PU elastomer coatings Rigid PU foams Bio-ethanol for fuel or PVC plasticizer Biobased phenol-formaldehyde resins Itaconic acid for paint

15 Drivers for lignin valorization Additional revenues beyond energy value Development of sustainable processes and products Biobased and circular economy Unique functionality Aromatic structure Polymer properties Crosslinking ability (softwood lignin) UV stability Flame retardance Anti-microbial Hydrophobicity Bulk versus niche markets

Enzymatic upgrading (Bio-)catalysis Monomeric chemicals Composites Coatings

16 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) Marine fuels Polymer building blocks Confidential 16

17 Examples for lignin applications Application Scale of operation TRL Main challenges Bio-asphalt Demonstration 6-7 Costs reduction, industrial handling Thermoset resins Pilot / demo 5-6 Reactivity Polyurethanes Pilot 5-6 Viscosity, reactivity Carbon fibres Pilot 5-7 Strength performance Marine fuels Pilot 5-6 Sulphur-free, viscosity Aromatic chemicals R&D Commercial for vanillin Desulphurisation, coke formation

$074 Lignin fractionation Aim: produce$ $homogeneous and purified lignin fractions with$ $fractionation Solvents with increasing Hansen$ COOH Aliphatic OH Syringyl-OH p-hydroxyl-oh

COOH Aliphatic OH Syringyl-OH p-hydroxyl-oh

$134 ppm Lignin fractions ranges from Mw 1000 to$ in purity and functionality Gosselink, R.J.A.

18 Lignin fractionation Aim: produce homogeneous and purified lignin fractions with tailored molar mass and properties Solvent fractionation Solvents with increasing Hansen solubility parameters Internal std Guaiacyl-OH COOH Aliphatic OH Syringyl-OH p-hydroxyl-oh Condensed OH ppm Lignin fractions ranges from Mw 1000 to 7000 g/mol Lower molar mass fractions increases in purity and functionality Gosselink, R.J.A., J.C. van der Putten, D.S. van Es, Fractionation of technical lignin, WO2015/

$oxidative polymerisation Lignin substrates: LMW fractions of 5 technical lignins Laccase$

19 Laccase-mediated oxidation of lignin Explore the effect of lignin composition on enzymatic oxidative polymerisation Lignin substrates: LMW fractions of 5 technical lignins Laccase Acetone/water 50:50

20 Laccase-mediated oxidation of lignin Enzymatic modification of lignins in water/acetone Lignin oxidative polymerization Kinetics Products DP = f(s, G, H) Fitigau et al, 2013, ABP

Bio-asphalt Bulk / low value application Substitution

lower temperature (lower CO 2 ) Infra project Zeeland

demonstration 2 public demonstration roads in The

21 Bio-asphalt Bulk / low value application Substitution of fossil bitumen ( / ton) Manufacturing at lower temperature (lower CO 2 ) Infra project Zeeland (NL): 50% substitution of bitumen by lignin from lab to demonstration 2 public demonstration roads in The Netherlands Challenges: costs lignin raw material, industrial handling

Hydrothermal lignin depolymerization Biomass Focus:

Turn lignin into high value aromatics (BTX) and

catalytic hydrothermal depolymerisation without

22 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 22 depolymerization of lignin, WO2014/168473

23 Relative Abundance Hydrothermal lignin conversion RT: NL: 7.59E6 TIC MS Lignin Time (min) Lignin depolymerization to monomers is 20% over Pd/C in water Oligomeric lignin fragments 60-80% Char formation <10% Limited product distribution 1 compound in 50% (Guaiacol) Monomers further converted into BTX, cyclohexanone

24 Fermentation challenges Maximize gas transfer & cooling capacity Prevent substrate and product inhibition Minimize costs for product recovery Minimize substrate costs Maximize performance of micro-organism

25 Microbial production of MC-Fatty Acids Cheap waste streams as substrate for MCFA production Various microbial platforms for MCFA production Cryptococcus curvatus Yarrowia lipolytica Pseudomonas putida (hydroxy-fa s/pha) Various Microalgae Metabolic Engineering Tailor-made chain length Tailor-made saturation level

26 X Fatty acid degradation through the β-oxidation pathway. X Unsaturated fatty acids 26

27 Pseudomonas for hydroxy-fa production Oleic acid C18:1 Linoleic acid C18:2 Linolenic acid C18:3 Palmitic acid C16:0 Tetradecanoic acid C14:0 Partial degradation Pseudomonas putida KT 2442 X PHA X TesB 3OH-C6 3OH-C8 3OH-C10 3OH-C14 27

28 Anaerobic fermentation to alcohols ABE (acetone/butanol/ethanol) and IBE (isopropanol/butanol/ethanol) production by Clostridia CRISPR/CAS introduction in C. beijerinckii Conversion of cellulose and hemicellulose Chemical and enzymatic conversion of alcohols to highvalue alcohols/aldehydes/esters/etc. (Anaerobic) Production of flavours, surfactants, fatty acids Conversion of C1-gasses/syngas to various alcohols by mixed anaerobic cultures

29 Waste streams to ABE

30 C1 (CO/CO 2 ) to alcohols

31 Production of organic acids at low ph Approach: Select potential host based on required process condition, High product and substrate tolerance Ability to grow on envisaged substrate Suitable metabolism Rapid growth/substrate conversion rate Simple medium requirements Genetic accessibility Engineer production pathway in selected host

tolerance to lactic acid and sugar (glucose + xylose) at low ph on mineral medium Best

32 Example: Lactic acid production Lactic acid: food & feed conservation, monomer for PLA Production at neutral ph -> salt (gypsum) as by-product Strains isolated with high tolerance to lactic acid and sugar (glucose + xylose) at low ph on mineral medium Best strain: Monascus ruber Engineered from rapid lactic acid consumer into rapid lactic acid producer

33 Biobased Antifungals/Antimicrobials Protective Cultures Direct application in food, on crops Protective cultures for ingredient production Protective cultures for Ferment production Antifungals from abundant biomass Various (modified) chitosans from chitin Aromatics (ferulic acid, cinnamic acid, etc) Plant components (terpenes/polyphenols)

34 Protective cultures for Strawberry Juice

35 Conclusions Biorefinery industries exits and there is more focus on chemicals and materials Development of sustainable processes is key Combination of enzymatic and chemical pretreatments gives benefits Mixture of products is possible and key Lignin has large potential to be used in materials and for chemicals Need for larger volume lignin production at reasonable costs Focus both on bulk and niche (high value) applications Fermentation processes can be tuned to produce biobased chemicals (fatty acids, organic acids, alcohols) from waste/side streams

36 Thank you! For collaboration or more information please contact:

Lignin valorization towards materials, chemicals and energy

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