Bettahar, M.

Dufour, A.

Francois, J.

Olcese, R.

Petitjean, D.

Shrestha, B.

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital ArchivesBioEnergy IV: Innovations in Biomass Conversionfor Heat, Power, Fuels and Chemicals ProceedingsSpring 6-11-2013Green aromatic bulk-chemicals from ligninpyrolysis vapoursB. ShresthaCNRSR. OlceseCNRSJ. FrancoisCNRSM. BettaharCNRSD. PetitjeanCNRSSee next page for additional authorsFollow this and additional works at: http://dc.engconfintl.org/bioenergy_ivPart of the Chemical Engineering CommonsThis Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion inBioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals by an authorized administrator of ECI Digital Archives. Formore information, please contact franco@bepress.com.Recommended CitationB. Shrestha, R. Olcese, J. Francois, M. Bettahar, D. Petitjean, and A. Dufour, "Green aromatic bulk-chemicals from lignin pyrolysisvapours" in "BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals", Manuel Garcia-Perez,Washington State University, USA Dietrich Meier, Thünen Institute of Wood Research, Germany Raffaella Ocone, Heriot-WattUniversity, United Kingdom Paul de Wild, Biomass & Energy Efficiency, ECN, The Netherlands Eds, ECI Symposium Series, (2013).http://dc.engconfintl.org/bioenergy_iv/28AuthorsB. Shrestha, R. Olcese, J. Francois, M. Bettahar, D. Petitjean, and A. DufourThis conference proceeding is available at ECI Digital Archives: http://dc.engconfintl.org/bioenergy_iv/28- 1 -Green aromatic bulk-chemicals from lignin pyrolysis vapoursR. Olcese, B. Shrestha, J. Francois, M. Bettahar, D. Petitjean, A. DufourCNRS, Université de LorraineOOHOHOOOHOHLigninOCH3OOCH3OOHLignin CH3OCH3OHOHOLigninCH3OHROHCH3AlkylAlkylLigninH2 + Iron catalystAromatics for polymers and fuels- 2 -The production of aromatics from lignin is an important challenge for biorefineryOMACs = Oxygenated Mono Aromatics CompoundsFractionationPurificationHemicelluloseCelluloseLigninBiomassFermentation or other processes ChemicalsDirect applicationFibers, paper, etc.Direct application PlasticizerChemicalsConversion (such as oxidation)OMACsDepoly-merizationBTXHydrotreatmentH2-rich syngasGasificationFrame of this workOHOCH3OHOHOCH3OHOHOH CH3CH3CH3OOHOHOOOHOHLigninOCH3OLigninOOCH3OOHLigninCH3CH3OHOOOHOCH3OHOOHOHOHOHn- 3 -Aromatics could be produced by gas-phase hydrodeoxygenation (HDO) of pyrolysis vapoursOOHOHOOOHOHLigninOCH3OOCH3OOHLignin CH3OCH3OHOHOLigninCH3OHOHCH3OHOCH3OHOCH3OOHROHCH3AlkylAlkylLigninOxygenated unstable aromaticsPyrolysis+ Char + Lignin oligomers+ CH4, CO2, COH2HDO over green Fe-based catalystGreen distillable aromatics for polymers and fuels- 4 -A green and cheap catalyst is looked for a selective HDO of oxygenated pyrolysis products00.10.20.30.40.50.4 0.9 1.4 1.9 2.4H/CO/CLigninsPyrolytic oilCyclo- hexanolAlkanesBTXOOHOHOOOHOHLigninOCH3OLigninOOCH3OOHLigninCH3CH3OOHCH3CH3 CH3CH3CH3CH3Desired routeUndesired routePyrolysisGuaiacolOlcese et al. App. Catal. B. 115 (2012) 63- 5 -The HDO of guaiacol, a surrogate of pyrolysis products, has been studied over iron-based catalysts. +H2 OHOCH3 OHPhenol +H2 BT +nH2 Ring  hydrogenated +nH2 Methanol CO, PAH, coke CH3Only for Cobalt catalyst Alkanes, CH4 Guaiacol CH4 -H2O Desired products +H2 -H2O Olcese et al. App. Catal. B. 115 (2012) 63- 6 -Fe/SiO2is a selective catalyst for the HDO of guaiacol into benzene and tolueneMass residence time= 1/WHSV = g catalyst/(g guaiacol/h)- 7 -Catalytic mechanism of guaiacol HDO over Fe/SiO2Olcese et al. App. Catal. B. 116 (2012) 63-73OHOCH3Si O Si O Si O SiOHFe Si O Si O Si O SiOHCH3 OOHH HSpill-overI) II)H2 (gas)- 8 -Gas composition has an effect on selectivityOlcese et al. App. Catal. B. 129 (2013) 528- 9 -Gas composition has an effect on iron speciation and on « coke » composition App. Catal. B. 129 (2013) 528Coke analysed by Temperature Programmed OxidationIron speciation analysed by XRD & Mössbauer- 10 -A kinetic model has been developped and included under Aspen Plus for process modelingOlcese et al. Energy Fuels 27 (2013) 975- 11 -Mass balance of the whole lignin to BTX process is modeledOlcese et al. Energy Fuels 27 (2013) 975Char and oligomers represent a key issue to improve lignin conversion yields into aromatics- 12 -Experiments have also been conducted on REAL pyrolysis vapoursOlcese et al. Energy Fuels 27 (2013) 2135A selective HDO has been obtained by iron-based catalysts- 13 -GC*GC and high resolution mass spectrometry (« Petroleomic ») are complementary methodsGC for light, petroleomic for heavier speciesOlcese et al. Energy Fuels 27 (2013) 2135- 14 -Coke formed by real lignin vapours is very different than coke from guaiacol HDOOlcese et al. ChemSusChem, in pressCoke plugged micropores of activated carbon but not mesopores of silica050100150200250303 503 703 903010203040500 1 2 3 4Stack 1Stack 2Stack 3Stack 4% of CdepositCO2 flow (µ mol/(min.gcat)Temperature (K)Stack number% of Carbon depositCoke analysed along the length of the fixed bed (profile in coke composition)- 15 -The mechanism of coke formation during the HDO of real vapours has been revealedOlcese et al. ChemSusChem, in pressTEM, TPO, Petroleomic, GC*GC, N2sorption (etc.) were used to reveal this mechanism- 16 -Iron is a selective and cheap catalyst for the HDO of lignin into aromaticsWorks are conducted from molecular mechanisms to process integrationThank you for your attentionbinod.shrestha@univ-lorraine.franthony.dufour@univ-lorraine.fr- 17 -Related papers1. Olcese et al., Applied Catalysis B 115-116, pp. 63-73, 2012.Effect of temperature, H2pressure and contact time on guaiacol HDO over Fe/SiO22. Olcese et al., Applied Catalysis B 129, pp. 528-538, 2013.Effect of iron loads, support type (SiO2or carbon) and gas composition on guaiacol HDO3. Olcese et al., Energy and Fuels 27 (2), pp. 975-984, 2013.Kinetics and Aspen Plus model of integrated lignin to BTX process4. Olcese et al., Energy and Fuels 27 (4), pp. 2135-2145, 2013.GC*GC and petroleomic analysis on real lignin vapours HDO5. Olcese et al., ChemSusChem, in pressMechanisms of HDO of real lignin vapours over Fe/SiO2and Fe/activated carbon, deactivation and coke formation- 18 -Simplified scheme of the experimental set-up for guaiacol HDO over a fixed bed of catalyst2 impingerswith propanol(-60°C)TVentµGC - 4 modulesOn-line analysis (CH4, H2, CO, etc.) To off-line GC/FID-MSanalysis of liquid solutionsHeated linesCatalyst bedSyringe pumpOvenFrittedMass Flow ControllersH2N2COCH44 ways valve6 ways heated valveTo on-line GC/FIDanalysis (heated sample loop)- 19 -Simplified scheme of the experimental set-up for real lignin vapours HDOBatch lignin pyrolysis connected to an horizontal fixed bed of catalyst, with stacks to investgate the profile of coke deposit along the fixed bed length

Green aromatic bulk-chemicals from lignin pyrolysis vapours

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Green aromatic bulk-chemicals from lignin pyrolysis vapours

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