Effective Fractionation of Lignocellulose Using a Mild Acetone-based Organosolv Process A.T. Smit W.J.J. Huijgen J.W. van Hal L. Lanting K.J. Damen June 2017 ECN-L--17-016 Presented @25th European Biomass Conference & Exhibition Stockholm
Effective Fractionation of Lignocellulose Using a Mild Acetone-based Organosolv Process. Energy research Centre of the Netherlands, ECN A.T. Smit, W.J.J. Huijgen, J.W. van Hal, L. Lanting, K.J. Damen EUBCE, Stockholm June, 2017 www.ecn.nl
Organosolv pretreatment Cellulose microfibril Lignin Hemicellulose T t H +
Organosolv process Pulp Biomass Lignin Sugars / acids / derivatives
Organosolv products Pulp Sugars / acids / derivatives Lignin Enzymatic hydrolysis Biochemical conversion Platform chemicals Depolymerization PHA FDCA Succinic acid Itaconic acid Lactic acid Furfural HMF Vanillin Phenol
Mild acetone organosolv
wt% xylan conversion Development - fractionation Organosolv fractionation of wheat straw: 100 Ethanol 210⁰C Acetone 205⁰C < 10% hemicellulose products 80 60 Ethanol 190⁰C 30mM H2SO4 Roughly equal Xyl, Et-Xyl and furfural. Ethanol 140⁰C 60mM H2SO4 Reduction of furfural formation Acetone 140⁰C 60mM H2SO4 Yield monomeric xylose: 81% 40 20 0 to furfural to ethylated xylose to monomeric xylose to oligomeric xylose in pulp
Feedstock screening Herbaceous Wheat straw, corn stover Hardwood Beech, poplar, birch Softwood Spruce, pine Extractives 8-9wt% 2-5wt% 4-5wt% Ash 10-14wt% 0.1-1wt% 0.3wt% Cellulose Polymeric glucose Polymeric glucose Polymeric glucose Main hemicellulose sugar polymer Arabinoxylan (C5) arabinoxylan (C5) glucomannan (C6) Main lignin building blocks Guaiacyl (G) Guaiacyl (G) Guaiacyl (G) Syringyl (S) Syringyl (S) p-hydroxyphenyl (H) Fractionation conditions 140⁰C, 120min, 50% w/w aqueous acetone, 40mM Free H 2 SO 4
Product distribution C6 sugars (wt% initial polymeric C6) Cellulose 100 105 107 76 72 89 20 18 Enzymatic cellulose digestibility (10 FPU/g) 80 60 40 20 0 to LA to HMF to monomeric sugars in pulp Decent cellulose recovery Rest monomeric sugars Limited HMF formation Enzymatic cellulose digestibility: Herbaceous > hardwood >> softwood
Product distribution C5 sugars (wt% initial polymeric C5) Hemicellulose 100 97 92 87 94 92 90 89 % w/w C5 hydrolysis 80 60 40 20 0 to furfural to monomeric sugars in pulp High C5 hydrolysis High C5 sugar yield except for softwood Gap in mass balance
Product distribution lignin (wt% initial polymeric lignin) Lignin 100 79 81 79 78 86 30 32 % w/w delignification 80 60 40 20 0 precipitated in pulp High level of delignification for herbaceous and hardwood Low level of delignification for softwood
Remarkable Lignin Characteristics High number β-o-4 ether linkages. Suggests more native lignin. Crucial for many chemocatalytic depolymerisation routes. 11 Constant et al. (2016). New insights into the structure and composition of technical lignins: a comparative characterisation study. Green Chemistry, 18(9), 2651-2665.
Conclusion Herbaceous biomass and hardwood - Yield C5 sugars - Cellulose digestibility - Lignin yield and characteristics Softwood - Cellulose digestibility - Lignin yield
Acetone self-condensation
Acetone self-condensation diacetyl alcohol mesityloxide Organosolv experiments with and without wheat straw at varying conditions
Acetone stability Fractionation conditions Nr: Temp (ᵒC) Time (min) Free H 2 SO 4 (mm) General fractionation data 0 25 50 75 100 1 100 960 180 2 140 120 40 3 140 60 40 4 140 30 80 C6 recovery C5 hydrolysis delignification 5 140 15 120 6 170 60 15
Acetone stability Fractionation conditions Nr: Temp (ᵒC) Time (min) Free H 2 SO 4 (mm) wt% C5 conversion 0 20 40 60 80 100 1 100 960 180 2 140 120 40 3 140 60 40 4 140 30 80 5 140 15 120 6 170 60 15 in pulp to monomeric sugars to furfural
Acetone stability Fractionation conditions Nr: Temp (ᵒC) Time (min) Free H 2 SO 4 (mm) acetone loss wt% 0,00 1,00 2,00 3,00 1 100 960 180 2,67 2,45 2 140 120 40 0,74 1,42 3 140 60 40 0,61 0,96 4 140 30 80 5 140 15 120 6 170 60 15 0,16 0,54 0,71 1,16 1,24 1,28 blanc straw
Process Characteristics T H2SO4 Ethanol 210⁰C 32 bar? All Acetone 205⁰C Ethanol 190⁰C 30mM Ethanol 140⁰C 60mM Acetone 140⁰C 60mM 8 bar -50% ±1% Herbaceous Hardwood
New developments
Ash+rest lignocellulose Feedstock Flexibility: Upgrading Water extractives Solvent extractives Fine chemicals Pharmaceuticals Uniform Fractionation Increased product purity Local recycle of organics, nutrients and minerals
Thank you for your attention! For more information: a.t.smit@ecn.nl ECN Westerduinweg 3 P.O. Box 1 1755 LE Petten 1755 ZG Petten The Netherlands The Netherlands T +31 88 515 49 49 F +31 88 515 44 80 info@ecn.nl www.ecn.nl
ECN Westerduinweg 3 P.O. Box 1 1755 LE Petten 1755 ZG Petten The Netherlands The Netherlands T +31 88 515 4949 F +31 88 515 8338 info@ ecn.nl www.ecn.nl ECN-L--17-016 Fout! Geen tekst met de opgegeven stijl in het document. 3