Effective Fractionation of Lignocellulose Using a Mild Acetone-based Organosolv Process
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1 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 European Biomass Conference & Exhibition Stockholm
2 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,
3 Organosolv pretreatment Cellulose microfibril Lignin Hemicellulose T t H +
4 Organosolv process Pulp Biomass Lignin Sugars / acids / derivatives
5 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
6 Mild acetone organosolv
7 wt% xylan conversion Development - fractionation Organosolv fractionation of wheat straw: 100 Ethanol 210⁰C Acetone 205⁰C < 10% hemicellulose products 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% to furfural to ethylated xylose to monomeric xylose to oligomeric xylose in pulp
8 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
9 Product distribution C6 sugars (wt% initial polymeric C6) Cellulose Enzymatic cellulose digestibility (10 FPU/g) to LA to HMF to monomeric sugars in pulp Decent cellulose recovery Rest monomeric sugars Limited HMF formation Enzymatic cellulose digestibility: Herbaceous > hardwood >> softwood
10 Product distribution C5 sugars (wt% initial polymeric C5) Hemicellulose % w/w C5 hydrolysis to furfural to monomeric sugars in pulp High C5 hydrolysis High C5 sugar yield except for softwood Gap in mass balance
11 Product distribution lignin (wt% initial polymeric lignin) Lignin % w/w delignification precipitated in pulp High level of delignification for herbaceous and hardwood Low level of delignification for softwood
12 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),
13 Conclusion Herbaceous biomass and hardwood - Yield C5 sugars - Cellulose digestibility - Lignin yield and characteristics Softwood - Cellulose digestibility - Lignin yield
14 Acetone self-condensation
15 Acetone self-condensation diacetyl alcohol mesityloxide Organosolv experiments with and without wheat straw at varying conditions
16 Acetone stability Fractionation conditions Nr: Temp (ᵒC) Time (min) Free H 2 SO 4 (mm) General fractionation data C6 recovery C5 hydrolysis delignification
17 Acetone stability Fractionation conditions Nr: Temp (ᵒC) Time (min) Free H 2 SO 4 (mm) wt% C5 conversion in pulp to monomeric sugars to furfural
18 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, ,67 2, ,74 1, ,61 0, ,16 0,54 0,71 1,16 1,24 1,28 blanc straw
19 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
20 New developments
21 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
22 Thank you for your attention! For more information: ECN Westerduinweg 3 P.O. Box LE Petten 1755 ZG Petten The Netherlands The Netherlands T F info@ecn.nl
23 ECN Westerduinweg 3 P.O. Box LE Petten 1755 ZG Petten The Netherlands The Netherlands T F info@ ecn.nl ECN-L Fout! Geen tekst met de opgegeven stijl in het document. 3
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