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--11-065 JUNE 2011
Catalytic Lignin Depolymerization in the BioCore Project Jaap W. van Hal, Jelle Wildschut and Andre van Zomeren www.ecn.nl
BI-CMMDITY REFINING June 6, 2011 2
A 4-YEAR EU PRJECT 24 partners - 13 countries - 5 SMEs 4 MNI Cost : 20 274 484 EU contribution : 13 920 238 June 6, 2011 Coordination : ( M. Donohue) 3
EURPE WRKING TGETHER FR TMRRW S BIECNMY June 6, 2011 4
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, 2011 5
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, 2011 6
Petten: energy research capital of Europe 7 June 6, 2011
Petten: energy research capital of Europe JRC-IE (275) NRG (370) CVIDIEN (290) ECN (570) 8 June 6, 2011
Core competence Universities Industry Cooperation and worldwide networks 9 June 6, 2011
R&D units Solar energy Biomass Wind energy Efficiency & Infrastructure Policy Studies 10 June 6, 2011
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
Chemicals from biomass by biorefining Source: DE 12 June 6, 2011
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, 2011 13
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), 456-466 June 6, 2011 14
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, 2011 15
The Structure of Lignin H R CH 3 R H H H CH 3 June 6, 2011 16
The Structure of Lignin C CH H 3 C H H CH 3 June 6, 2011 17
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, 2011 18
The Structure of Lignin R H R' CH 3 H R H H R' CH 3 June 6, 2011 19
The Structure of Lignin CH H 3 C CH 3 H CH H CH 3 June 6, 2011 20
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, 2011 21
The Structure of Lignin R' H H H 3 C R CH 3 R' H H 3 C R June 6, 2011 22
The Structure of Lignin H June 6, 2011 23
Fed Batch setup June 6, 2011 24
Fed Batch Setup June 6, 2011 25
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
Analysis Gas - 2, C 2, C, online (analyzer) Solids: - SEC Liquid fraction - GC-MS, SEC (of the solids) 27 June 6, 2011
nline gas data from Biocore lignin oxidation at 220 C, 30 bar and 8 % water 25.0% 4000 3500 20.0% 3000 15.0% 2500 2000 10.0% 1500 5.0% 1000 500 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 % 2 PPM C 28 June 6, 2011
Monomeric phenols from oxidation of Biolignin in acetic acid T ( C) Time (min.) Gas Catalyst system Code Vanillin Syringaldehyde 4-hydroxybenzaldehy de 220 120 N 2 None 100909 74 50 20 220 120 air None 100910 56 30 13 220 120 air 0.015M Co/Mn IL 100928 27 21 0.0 180 120 air 0.015M Co/Mn IL 101001 382 301 89 150 120 air 0.015M Co/Mn IL 100930 433 255 94 180 120 air 6.9 mm Co, 6.9mM Mn, 0.69 mm Zr, 13.8 mm IL 101004 365 222 91 June 6, 2011 29
Signal (AU) Results from the allcell lignin oxidation in 10% formic acid/ acetic acid 1.20 1.00 0.80 0.60 0.40 0.20 0.00 10 100 1000 10000 100000 1000000 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
Signal (AU) Comparison of no catalyst, single component and triple component catalyst at 220 C, 30 bar, 120' 1000 900 800 700 600 500 400 300 200 100 0 10 100 1,000 10,000 100,000 1,000,000 10,000,000 Mw (LG) CIMV 07-10 Biolignin No catalyst 0.015 M Co 0.015 M Mn 0.015 M Br 100917 0.015 M: Co Mn Br 31 June 6, 2011
Blank (no lignin) and lignin oxidation, 0.045 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
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 % 2 220 C Biolignin % C2 220 C Allcell % 2 220 C Allcell % C2 220 C ECN % 2 220 C ECN 33 June 6, 2011
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, 2011 34
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)224-564297 vanhal@ecn.nl www.ecn.nl http://www.biocore-europe.org/ 35 June 6, 2011