Catalytic Lignin Depolymerization in the BioCore Project J.W. van Hal J. Wildschut A. van Zomeren

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1 Catalytic Lignin Depolymerization in the BioCore Project J.W. van Hal J. Wildschut A. van Zomeren Presented at the 22nd North American Catalysis Society Meeting (NAM22), Detroit MI, USA, June 6, 2011 (Conference 5-10 June 2011) ECN-L JUNE 2011

2 Catalytic Lignin Depolymerization in the BioCore Project Jaap W. van Hal, Jelle Wildschut and Andre van Zomeren

3 BI-CMMDITY REFINING June 6,

4 A 4-YEAR EU PRJECT 24 partners - 13 countries - 5 SMEs 4 MNI Cost : EU contribution : June 6, 2011 Coordination : ( M. Donohue) 3

5 EURPE WRKING TGETHER FR TMRRW S BIECNMY June 6,

6 PTIMAL BIMASS CRACKING CIMV rganosolv Uses a formic/acetic peracid system Produces three useable fractions beys the «whole biomass principle» Produces valuable lignins and partially depolymerized hemicellulose Pilot operation underway since 2006 June 6,

7 Final products Application sectors 2 nd generation fuels Ethanol Thermoplastics Energy PVC, polyolefins, polyurethanes, polyesters Materials Varied biomass Fractionation Intermediates Chemistry Biotechnology Packaging Cereal byproducts Hemicellulose Resins/Adhesives Food additives Building Forestry waste Cellulose Detergents SRC wood Lignin Wood panels Adhesives and paints June 6,

8 Petten: energy research capital of Europe 7 June 6, 2011

9 Petten: energy research capital of Europe JRC-IE (275) NRG (370) CVIDIEN (290) ECN (570) 8 June 6, 2011

10 Core competence Universities Industry Cooperation and worldwide networks 9 June 6, 2011

11 R&D units Solar energy Biomass Wind energy Efficiency & Infrastructure Policy Studies 10 June 6, 2011

12 Biomass, Coal and Environmental research Heat and Power - Co-firing, B2 torrefaction, CHP, Syn-gas and SNG - Milena gasification, lga tar removal,.. Carbon Capture Technologies - C 2 capture, H 2 production,.. RISMIL - Leaching, N x emissions,.. 11 June 6, 2011

13 Chemicals from biomass by biorefining Source: DE 12 June 6, 2011

14 Aim: Adapt MCC process to lignin Selective liquid phase oxidation of lignin Similar to oxidation of p-xylene to teraphtalic acid (BP/Amaco Midcentury Process, MCC) Solvents of choice: - Acetic acid/formic acid (mixtures) - CIMV Pulping Liquid - Compare with acetic acid - Compare lignins June 6,

15 Lignin xidation in Acetic Acid Batch, No Continuous Air Feed Products - Vanillin - Vanillic acid - Syringaldehyde - Syringic acid - Furfural - Etc. Ref: Partenheimer, Adv. Synth. Cat., 2009, 351(3), June 6,

16 The Structure of Lignin R' H H 3 C CH 3 H H H H H 3 C R H 3 C H H CH 3 H CH 3 CH 3 CH 3 CH 3 H H 3 C H H CH 3 June 6,

17 The Structure of Lignin H R CH 3 R H H H CH 3 June 6,

18 The Structure of Lignin C CH H 3 C H H CH 3 June 6,

19 The Structure of Lignin R' H H 3 C CH 3 H H H H H 3 C R H 3 C H H CH 3 H CH 3 CH 3 CH 3 CH 3 H H 3 C H H CH 3 June 6,

20 The Structure of Lignin R H R' CH 3 H R H H R' CH 3 June 6,

21 The Structure of Lignin CH H 3 C CH 3 H CH H CH 3 June 6,

22 The Structure of Lignin R' H H 3 C CH 3 H H H H H 3 C R H 3 C H H CH 3 H CH 3 CH 3 CH 3 CH 3 H H 3 C H H CH 3 June 6,

23 The Structure of Lignin R' H H H 3 C R CH 3 R' H H 3 C R June 6,

24 The Structure of Lignin H June 6,

25 Fed Batch setup June 6,

26 Fed Batch Setup June 6,

27 Experimental matrix Effect of Lignin - Allcell, CIMV, ECN Effect of solvent - Formic acid, water Effect of temperature Effect of flow Effect of stir speed Effect of catalyst Effect of reaction time 26 June 6, 2011

28 Analysis Gas - 2, C 2, C, online (analyzer) Solids: - SEC Liquid fraction - GC-MS, SEC (of the solids) 27 June 6, 2011

29 nline gas data from Biocore lignin oxidation at 220 C, 30 bar and 8 % water 25.0% % % % % % 0 0:00 0:28 0:57 1:26 1:55 2:24 2:52 3:21 3:50 4:19 4:48 % C2 % 2 PPM C 28 June 6, 2011

30 Monomeric phenols from oxidation of Biolignin in acetic acid T ( C) Time (min.) Gas Catalyst system Code Vanillin Syringaldehyde 4-hydroxybenzaldehy de N 2 None air None air 0.015M Co/Mn IL air 0.015M Co/Mn IL air 0.015M Co/Mn IL air 6.9 mm Co, 6.9mM Mn, 0.69 mm Zr, 13.8 mm IL June 6,

31 Signal (AU) Results from the allcell lignin oxidation in 10% formic acid/ acetic acid Mw Allcell Lignin Air 180 C no cat Air 220 C no cat Air 220 C Mn Co no Br cat 30 June 6, 2011

32 Signal (AU) Comparison of no catalyst, single component and triple component catalyst at 220 C, 30 bar, 120' ,000 10, ,000 1,000,000 10,000,000 Mw (LG) CIMV Biolignin No catalyst M Co M Mn M Br M: Co Mn Br 31 June 6, 2011

33 Blank (no lignin) and lignin oxidation, M catalyst, 220 C, 30 bar 25.0% 20.0% 15.0% 10.0% 5.0% 0.0% 0:00 0:28 0:57 1:26 1:55 2:24 2:52 3:21 3:50 4:19 4:48 % C2 N lignin % 2 N lignin % C2 with lignin % 2 with lignin 32 June 6, 2011

34 Effect of lignin source at 220 C 25.0% 20.0% 15.0% 10.0% 5.0% 0.0% 0:00 0:28 0:57 1:26 1:55 2:24 2:52 3:21 3:50 4:19 4:48 % C2 220 C Biolignin % C Biolignin % C2 220 C Allcell % C Allcell % C2 220 C ECN % C ECN 33 June 6, 2011

35 Trends Need three/four component catalyst - Co(Ac) 2, Mn(Ac) 2, Br -, optional Zr(Ac) 4 Higher reaction temperatures lead to more depolymerization Longer reaction times lead to more depolymerization More catalyst leads to more depolymerization Reaction is effective even with lignin slurry Significant acetic acid burn Monomeric phenols only at low temperatures June 6,

36 Further information Jaap W. van Hal The Energy Research Center of the Netherlands (ECN) Biomass, coal and environmental research Transportation fuels and chemical P.. Box 1, 1755 ZG Petten +31-(0) June 6, 2011