Thermal behaviour/treatment of some vegetable residues. Gas chromatographic analysis of pyrolysis products from pine cone

Transcription

1 Thermal behaviour/treatment of some vegetable residues. Gas chromatographic analysis of pyrolysis products from pine cone Mihai Brebu 1, Cornelia Vasile 1, Jale Yanik 2 1 Petru Poni Institute of Macromolecular Chemistry, 7487 Iasi, Romania 2 Ege University, Faculty of Science, 351 Izmir, Turkey bmihai@icmpp.ro

2 Municipal Solid Waste (MSW): ~ 65 wt% lignocellulosic / cellulosic waste ~ 15 wt% synthetic polymer materials ~ 2 wt% inorganic materials Co-pyrolysis: - biomass: ~ wt% C; wt% O; lower thermal stability - plastics: ~ 84 wt% C; 1.5 wt% O; source of H Lignocellulosic materials: - polymeric composites - laminates with plastics for packaging - upgrading by co-pyrolysis / co-gasification Pine cone: - low ash content;

3 Materials pine cones of Pinus pinea L (Pc): polyethylene (PE) - proximate analysis: polypropylene (PP) moisture: 9.6%; ash:.9%; volatiles: 77.8% - elemental analysis: polystyrene (PS) C: 42.62%; H: 5.56%; N:.76%; S:.5%: O: 51.1% cellulose (Cell) - main constituents: cellulose: 32.7%; hemicellulose: 37.6 %; lignin: 24.9%, extractives: 4.8% Condenser Glass reactor (3 mm / 35 mm) Water Furnace (5 C) Sample (15 g) Air trap Teflon bag Water trap Thermocouple Graduated cylinder for liquid products Pyrolysis set-up

4 Abundance 1.4e+7 1.e+7.6e+7.2e+7 1.4e+7 1.e+7.6e+7.2e+7 Extraction of compounds from aqueous phase 12 Heptane extract Benzene extract Lignin aqueous fraction : Furfural 1: Phenol 2: 2-Methylphenol (o-cresol) 3: 4-Methylphenol (p-cresol) 4: 2,6-Dimethylphenol : 2-Ethylphenol 6: 2,3-Dimethylphenol 7: 4-Ethylphenol 8: 2,4,6-Trimethylphenol 9: 2,3-Dihydrobenzofuran 1: 3-Ethyl,5-methylphenol 11: 2-Allylphenol 12: Methanol 13: 1,2-Benzenediol (Pyrocatechol) 14: 3-Methyl,1,2-benzenediol (3-Methylpyrocatechol) 15: 4-Methyl,1,2-benzenediol (4-Methylpyrocatechol) 16: 4,5-Dimethyl,1,3-benzenediol (4,5-Dimethylresorcinol) 17: 4-Ethyl,1,3-benzenediol (4-Ethylresorcinol) 18: 4-Hydroxyacetophenone 19: 4-Hydroxy,3-methylacetophenone e+7 1.e+7 Ethylacetate extract : Pyrrole 21: Hydroquinone & Resorcinol 22: 3,5-Dihydroxytoluene (5-Methylresorcinol) 23: 1,2,3-Benzenetriol (Pyrogallol) 24: 3,5-Dihydroxyacetophenone 25: 3,5-Dihydroxybenzoic acid, methyl ester.6e+7.2e Ethylacetate is suitable solvent Time, min

5 Abundance 1.2e+7 1.e+7.8e+7 GC-MSD analysis of Pine cone pyrolysis products Tar polar O- compounds - similar composition - different distribution.6e e+7.2e Abundance 1.2e+7 1.e+7.8e+7.6e+7.4e+7 ethylacetate solvent Aqueous phase : methanol 1: acetone 2: acetic acid methylester 3: 2,3-butanedione, 2-butanone 2-methylfuran 4: acetic acid 5: propanoic acid methylester 6: 2-butenal 7: 1-hydroxy-2-propanone 3-methyl-3-buten-2-one 8: 2,5-dimethylfuran 9: toluene 1: 3-furaldehyde 11: 2-furancarboxyaldehyde 12: 2-furanmethanol 13: xylene 14: 3,4-dihydro-2H-pyran 5-methyl-2(3H)-furanone 15: α-pinene 16: 5-methyl,2-furancarboxyaldehyde 17: phenol 18: 3-carene 19: 2-cyclopenten-1-one-2-hydroxy-3- methyl (maple lactone - fragrance) 2: 2-methylphenol 21: 3-methylphenol 22: 2-methoxyphenol (o-guaiacol) 23: 2-methylbenzofuran 24: maltol (flavor enhancer) 25: 1,4-dimethoxybenzene (attract bees) 26: 4-methyl-2-methoxyphenol (p-creosol) 27: 4,7-dimethylbenzofuran 5-(hydroxymethyl)-2-furancarboxaldehyde 2,3-dimethoxytoluene 28: 3-methyl-1,2-benzenediol 29: 4-ethyl-2-methoxyphenol (p-ethylguaiacol) 3: 4-methyl-1,2-benzenediol 31: thymol 32: 4-alylguaiacol (eugenol) 33: vanillin 34: isoeugenol 35: acetovanillone.2e Time, min C 5 C 6 C 7 C 8 C 9 C 1 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18

6 Main compounds by GC-MSD Rt (min) Pc tar Pc aq. ph. Rt (min) Pc tar Pc aq. ph. Alcohols Phenols Methanol Phenol Acids Phenol, 2-methyl Formic acid Phenol, 3-methyl Acetic acid Phenol, 2,4-dimethyl Propanoic acid Phenol, 2,3-dimethyl Propenoic acid Guaiacols Aldehydes Guaiacol Hydroxyacetaldehyde Phenol, 2-methoxy-4-methyl Propenal, 2-methyl Phenol, 4-ethyl-2-methoxy Butenal, 2-methyl Eugenol Propanal Phenol, 2-methoxy-4-propyl Benzeneacetaldehyde Vanilin Non aromatic ketones Phenol, 2-methoxy-4-(1-propenyl) Furans Phenol, 2-methoxy-4-(1-propenyl) Furan, 2-methyl Catechols Furaldehyde ,2-Benzenediol, 3-methyl Furancarboxaldehyde ,2-Benzenediol, 3-methoxy Furfuryl alcohol Hydroquinone Furan, 2-ethyl ,2-Benzenediol, 4-methyl Acetylfuran ,5-Dihydroxytoluene (5H)-Furanone Hydroquinone, methyl (5H)-Furanone, 5-methyl ,3-Benzenediol, 4,5-dimethyl Methylfurfural ,3-Benzenediol, 4-ethyl Hydroxymethylfurfural ,3-Benzenediol, 4-propyl acetoxymethyl-2-furaldehyde phenols and quaiacols remain in tar - smaller molecules go to aqueous phase

7 Aplication: co-pyrolysis with PE, PP, PS hemicellulose & cellulose lignin & charcoal Dtg, a.u. 1 8 ~ 65 % Tg, wt % Pine cone PE PP PS ~ 5.6 % Temperature, o C - two steps for pine cone - one step for PE, PP and PS - possible interactions between Pc an polyolefins due to overlapping of degradation steps

8 Pyrolysis mass balance Feed Gas Aqueous phase Tar/Oil Residue Pc PE PP PS Pc/PE (1/1) Pc/PP (1/1) Pc/PS (1/1) Pc/PE/PP/PS (3/4/2/1) Cell/PE/PP/PS (3/4/2/1) increased gas and oils - decreased residue - polyolefins act as source of H - particular behaviour for Cell

9 Abundance 1e+6 5e+6 GC-MSD analysis Pc Tar/oils - particular composition for each polyolefin main lignin peaks 1e+6 Pc/PE homologuous series 5e+6 1e+6 Pc/PP PP oligomers 5e+6 1e+6 Pc/PS PS oligomers 5e+6 Time, min C 5 C 6 C 7 C 8 C 9 C 1 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 2 C 21 C 22 C 23 C 24 C 25 C 26

10 C-NP grams 4 4 GC-MSD area, % 3 2 Pc PE Pc/PE exp Pc/PE calc GC-MSD area, % 3 2 Pc PP Pc/PP exp Pc/PP calc carbon number PS: carbon number GC-MSD area, % 3 2 Pc PS Pc/PS exp Pc/PS calc GC-MSD area, % 3 2 Pc Pc/PE/PP/PS exp Pc/PE/PP/PS calc carbon number carbon number - particular distribution for each pine cone / polyolefin mixture - interactions between pine cone and polyolefins

11 Main compounds by GC-MSD Pc/PE Pc/PP Pc/PS Pc/PE/PP/PS Cell/PE/PP/PS Pc/PE Pc/PP Pc/PS Pc/PE/PP/PS Cell/PE/PP/PS Alcohols Phenols Methanol Phenol Acids Phenol, 2-methyl Formic acid Phenol, 3-methyl Acetic acid Phenol, 2,4-dimethyl Propanoic acid Phenol, 2,3-dimethyl Propenoic acid Guaiacols Aldehydes Guaiacol Hydroxyacetaldehyde Phenol, 2-methoxy-4- methyl Propenal, 2-methyl Phenol, 4-ethyl-2-methoxy Butenal, 2-methyl Eugenol Propanal Phenol, 2-methoxy propyl- Benzeneacetaldehyde Vanilin Non aromatic ketones Phenol, 2-methoxy-4-( propenyl)- Furans Phenol, 2-methoxy-4-(1- propenyl) Furan, 2-methyl Catechols Furaldehyde ,2-Benzenediol, 3-methyl Furancarboxaldehyde ,2-Benzenediol, methoxy- 2-Furfuryl alcohol Hydroquinone Furan, 2-ethyl ,2-Benzenediol, 4-methyl Acetylfuran ,5-Dihydroxytoluene (5H)-Furanone Hydroquinone, methyl (5H)-Furanone, 5-methyl ,3-Benzenediol, 4, dimethyl- 5-Methylfurfural ,3-Benzenediol, 4-ethyl Hydroxymethylfurfural ,3-Benzenediol, 4-propyl acetoxymethyl-2-furaldehyde composition depends on system, due to interactions - PS decresases low Mw compounds and guaiacols; increases phenols - Cell increases furans and kerones; decreases phenols; no lignin compounds

12 Properties of tar/oils and of chars Tar/oils Chars Sample Pc Pc/PE Pc/PP Pc/PS Pc/PE/PP/PS Cell/PE/PP/PS Pc Pc/PE/PP/PS Cell/PE/PP/PS Elemental composition,wt% C H N S O a Water amount, wt% GCV b, kcal/kg n.d a by difference; b gross calorific value - Pc tar: high content of water - Pc char: lower GCV - polyolefin oils: N and S traces - polyolefin chars: higher GCV ; low S

13 Conclusions Gc: suitable method for qualitative/quantitative characterisation of pyrolysis products pine cone tar: mainly lignin- derived compounds pine cone aqueous phase: mainly carbohydrates- derived compounds synergistic effect at co-pyrolysis of biomass and synthetic polymers composition of aqueous phase depends on the lignin/cellulose ratio in biomass composition of oils depends on the type of synthetic polymer Acknowledgements - Inter-academic exchanges program between Romanian and Turkish Academies of Sciences.