1. Daniel J. Nowakowski BERG lignin seminar Analytical (PY-GC-MS) pyrolysis of lignin

2. BioEnergy Research Group seminar  17 th September 2007 2/9 Lignin is usually considered as a polyphenolic material having an amorphous structure, which arises from an enzyme-initiated dehydrogenative polymerisation of coniferyl (a), sinapyl (b) and trans-p-coumaryl (c) alcohols. Lignin chemistry Structure of plant cell wall

3. Lignin chemistry Dimmers and trimeres structures of lignin with the main types of linkages connecting phenylpropane units BioEnergy Research Group seminar  17 th September 2007 3/9

4. BioEnergy Research Group  17 th September 2007 4/9 Main degradation products of Organosolv lignin: - 1,2,3-trimethoxybenzene - 2,6-dimethoxy phenol - 2-methoxy-4-methyl phenol - 2-methoxy phenol - furanaldehyde and carboxfuranaldehyse - 1,2,3-trimethoxy-5-methylbenzene - 2,6-dimethoxy-4-(2-propenyl)-phenol C14-C22 acids, its methyl or ethyl esters PY-GC-MS analysis of Organosolv lignin [commercially available lignin] Py-GC-MS chromatogram, pyrolysis at 600 o C, pyrolysis time 15 sec.

5. Main degradation products of Etek lignin: - 2-methoxy-4-methyl phenol - 2-methoxy phenol - 2-methoxy-4-vinylphenol - 4-hydroxy-2-methoxy-benzaldehyde - furfural, cyclopentane/hexane derivatives - levoglucosan - anhydrosugars (traces) [ commercially available lignin, by-product from EtOH production] PY-GC-MS analysis of Etek lignin BioEnergy Research Group seminar  17 th September 2007 5/9

6. BioEnergy Research Group  17 th September 2007 6/9 [by-product from paper industry] PY-GC-MS analysis of Asian lignin Main pyrolysis products of Asian lignin: - 2-methoxy-4-vinyl phenol - 2-methoxy-4-methyl phenol - 2-methoxy phenol - 2,6-dimethoxy phenol - 1,2,3-trmethoxybenzene - 1,2,3-trimethoxy-5-methylbenzene - 2,6-dimethoxy-4-(2-propenyl)-phenol - 2,5-dimethyl furan

7. PY-GC-MS analysis of bio-oil from fast pyrolysis of: Etek lignin Asian lignin Main compounds identified in liquids: - acetic acid - 2-cyclopentane-1,4-dione - 2-hydroxy-2-cyclopenten-1-one - phenol - 2-methoxy phenol - levoglucosan + traces of anhydro- and dianhydro- sugars - phenol - 2-methoxy phenol - 4-ethyl phenol - 4-ethyl-2-methoxy phenol BioEnergy Research Group seminar  17 th September 2007 7/9

8. BioEnergy Research Group  17 th September 2007 8/9 > Characterisation of lignin samples using pyrolysis-gas chromatography-mas spectrometry (PY-GC-MS) at different temperatures (400 o C & 500 o C; Lignovalue project) > Pyrolysis studies of lignin samples using thermogravimetric analysis (TGA) up to 900 o C, heating rates: 5 and 25 o C/min. Future work DTG profile for lignin (Organosolv) pyrolysis; TGA pyrolysis, 25oC/min. in nitrogen > Problems: Bio-oil (liquid products) analysis: RTX 1701 column (14% cyanopropylphenyl, 86% dimethylpolysiloxane; 60 m, 0.25 mm id.) TGA is not working (will be repaired within two weeks) > In situ studies of monomeric phenols production (HCl pre-treatment, (CH 3 COO) 2 Ca, ZnCl 2 )

9. Thank you for your attention