Secondary vapor phase reactions of lignin derived oligomers obtai

Engineering Conferences International ECI Digital Archives BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals Proceedings Spring 6-10-2013 Secondary vapor phase reactions of lignin derived oligomers obtained by fast pyrolysis of pine wood Shai Zhou Washington State University Brannan Pecha Washington State University Armando McDonald University of Idaho Sascha Kersten University of Twente Roel Westerhof University of Twente See next page for additional authors Follow this and additional works at: http://dc.engconfintl.org/bioenergy_iv Part of the Chemical Engineering Commons Recommended Citation Shai Zhou, Brannan Pecha, Armando McDonald, Sascha Kersten, Roel Westerhof, and Manuel Garcia-Perez, "Secondary vapor phase reactions of lignin derived oligomers obtained by fast pyrolysis of pine wood" 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-Watt University, United Kingdom Paul de Wild, Biomass & Energy Efficiency, ECN, The Netherlands Eds, ECI Symposium Series, (2013) http://dc.engconfintl.org/bioenergy_iv/4 This Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives It has been accepted for inclusion in BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals by an authorized administrator of ECI Digital Archives For more information, please contact franco@bepress.com Authors Shai Zhou, Brannan Pecha, Armando McDonald, Sascha Kersten, Roel Westerhof, and Manuel Garcia-Perez This conference proceeding is available at ECI Digital Archives: http://dc.engconfintl.org/bioenergy_iv/4 SECONDARY VAPOR PHASE REACTIONS OF LIGNIN DERIVED OLIGOMERS OBTAINED BY FAST PYROLYSIS OF PINE WOOD SHUAI ZHOU , BRENNAN PECHA , ARMANDO MCDONALD , SASCHA R.A KERSTEN , ROEL J.M WESTERHOF , MANUEL GARCIA-PEREZ WASHINGTON STATE UNIVERSITY, UNIVERSITY OF IDAHO, UNIVERSITY OF TWENTE OUTLINE  Introduction  Objective  Materials and Methods  Analysis of Results  Conclusions INTRODUCTION Lignin structure (Softwood lignin) Ether linkages: -O-4, -O-4, and 4-O-5 C-C linkages: -5, 5-5, -1, and - INTRODUCTION Lignin  The only renewable phenolic resource and second abundant polymer in nature Pyrolysis  High temperature process (300-600oC) in which biomass is rapidly heated in the absence of oxygen Monomeric lignols (10-20%) Pyrolysis Lignin Lignin oligomers (Pyrolytic lignin) (20-40%) Char + Gases (difference) INTRODUCTION Lignin Pyrolysis: History and Current status  Feedstock: Organosolv lignin; Kraft Lignin; Model compounds  Pyrolysis reactors: Py-GC/MS; Thermogravimetric Analyzer; Fluidized bed reactor; Auger reactor, Tubular reactor  Products studied: Mainly mono-phenols (very limited studies on lignin oligomers)  Kinetic studies: (Phillip Britt (ORNL 1995-2007); Michael T Klein (MIT-U Delaware 1983-2009); Kawamoto – Saka (Kyoto U 2007-2011) (Models only describe the formation of monomers)  Lignin oligomer characterization: (Dietrich Meier (U Hamburg 1987-2010))  Identification of lignin oligomers as one of the most reactive fractions during the pyrolysis of lignocellulosic materials (M Garcia – C-Z Li – S Kersten- R Westerhof) (2005-2012) INTRODUCTION THERMO-CHEMICAL REACTIONS  PRIMARY THERMOCHEMICAL REACTIONS Cellulose Lignin Hemicellulose Interactions REACTIONS IN SOLID PHASE  SECONDARY THERMOCHEMICAL REACTIONS INTRA-PARTICLE (WITHIN A PARTICLE) REACTIONS INTER PARTICLE REACTION (BETWEEN PARTICLES) HOMOGENEOUS REACTIONS HETEROGENEOUS REACTIONS HETEROGENEOUS REACTIONS HOMOGENEOUS REACTIONS IN VAPOR PHASE INTRODUCTION Our current View of Lignin Pyrolysis Lignin Structure Clusters with one aromatic ring Lignin monomers O Lignin Oligomers Clusters 2-5 aromatic rings O Cluster 6> aromatic rings Low Temperature Reactions (180-300 oC) ?? ?? ?? ?? Lignin liquid intermediate Cross-linked lignin ?? Lignin monomers ? Lignin Solid Residue Char + CH3OH + formaldehyde High Temperature Reactions (300-600 oC) OBJECTIVE Study of Secondary Reactions in Vapor Phase Objectives:  To study the effect of secondary reactions in vapor phase on the yield and composition of lignin oligomer Research questions to be answered:  The nature of the transformations happening to the structure of lignin oligomers during secondary reactions in vapor phase MATERIAL AND METHODS Study of Secondary Reactions in Vapor Phase Vapors Pine Wood Fluidized bed reactor (at 500°C) Tubular reactor Residence time: 0-15 s Temperature: 400, 500, 550°C Pyrolysis oils Pyrolytic Lignin Analysis (UV-Fluo, TGA, Py-GC/MS, FTIR, ESI-MS and 1H-NMR) Fluidized Bed and Tubular Reactor (University of Twente) MATERIAL AND METHODS Pyrolytic lignin (lignin oligomer) extraction and analysis Py-GC/MS ESI-MS Cold Water Precipitation UV-Fluorescence Bio-oil Pyrolytic Lignin Extraction FTIR TG NMR ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Yield of lignin oligomers 18 Yield of pyrolytic lignin (wt %) 16 14 12 10 400°C 500°C 550°C 0 (Westerhof et al 2011) 10 Vapor residence time (s) 12 14 (Westerhof et al 2011) One of the main causes for the effect of residence time on the yield of bio-oil is the dramatic effect of this variable on the yield of pyrolytic lignin Based on this result we decided to study the effect of secondary homogeneous reactions in vapor phase on the composition of pyrolytic lignin Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Analysis of lignin oligomer by Py-GC/MS : Guaiacols 12000 25000 400°C 500°C 400°C 550°C 550°C 20000 4-Methyl guaiacol (peak area/µg PL) Guaiacol (peak area/µg PL) 10000 500°C 8000 6000 4000 15000 10000 5000 2000 0 10 15 Vapor residence time (s) 20 10 15 Vapor residence time (s) 20 Demethoxylation of Pyrolytic lignin Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Analysis of lignin oligomer by Py-GC/MS : CO2 and Acetone 2000 25000 400°C 500°C 550°C 20000 500°C 550°C 1600 Acetone (peak area/µg PL) Carbon dioxide (peak area/µg PL) 400°C 1800 15000 10000 5000 1400 1200 1000 800 600 400 200 0 10 12 Vapor residence time (s) 14 16 10 15 Vapor residence time (s) 20 Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Analysis of lignin oligomer by 1H NMR analysis 0.9 Protons in methoxyl groups 0.8 Methoxyl ‘H’ 13 12 11 10 f1 (ppm) -1 -2 -3 0.7 0.6 0.5 0.4 0.3 400°C 0.2 500°C 0.1 550°C 0 10 12 Vapor residence time (s) 14 16 Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Analysis of lignin oligomer by TGA 0.005 B Weight loss/min g biomass Weight loss/min g biomass 0.005 0.004 400°C, 1.3s 400°C, 3.3s 400°C, 14.7s 0.003 C 0.002 A 0.001 B 0.004 500°C, 1.2s 0.003 C 500°C, 2.9s 500°C, 9.3s 0.002 500°C, 12.8s A 0.001 0 200 400 Temp (°C) 600 800 200 400 Temp (°C) 600 800 Weight loss/min g biomass 0.005 0.0045 B 0.004 0.0035 0.003 C 0.0025 0.002 A 0.0015 550 oC, s 550°C, 1.1s 550°C, 2.73s 550°C, 8.75s 550°C, 12s 0.001 0.0005 0 200 400 Temp (°C) 600 800 Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Analysis of lignin oligomer by TGA 400°C 1.6E-03 500°C 5.0E-03 550°C 1.4E-03 1.2E-03 1.0E-03 8.0E-04 6.0E-04 4.0E-04 2.0E-04 Peak A 0.0E+00 400°C 4.5E-03 500°C 550°C 4.0E-03 3.5E-03 3.0E-03 2.5E-03 2.0E-03 1.5E-03 1.0E-03 Peak B 5.0E-04 0.0E+00 3.0E-03 Weight loss/min g biomass Weight loss/min g biomass Weight loss/min g biomass 1.8E-03 10 15 Vapor residence time (s) 400°C 500°C 20 10 15 Vapor residence time (s) 20 550°C 2.5E-03 2.0E-03 1.5E-03 1.0E-03 5.0E-04 Peak C 0.0E+00 10 15 Vapor residence time (s) 20 Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Analysis of lignin oligomer by UV-Fluorescence 3 B 1.5 C A 0.5 B 2.5 Intensity Intensity 2.5 400°C, 1.3 s 400°C, 3.3 s 400°C, 14.7 s 1.5 C A 0.5 500°C, 1.2 s 500°C, 2.9 s 500°C, 9.3 s 500°C, 12.8 s 200 300 400 Wavelength (nm) 500 600 200 300 400 Wavelength (nm) 500 600 B Intensity 2.5 1.5 C A 0.5 550°C, s 550°C, 1.1 s 550°C, 2.73 s 550°C, 8.75 550°C, 12 s 200 300 400 Wavelength (nm) 500 600 Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Analysis of lignin oligomer by UV-Fluorescence 0.4 400°C 500°C 550°C 0.35 400°C 500°C 550°C 2.5 0.25 Intensity Intensity 0.3 0.2 0.15 1.5 0.1 0.5 0.05 Peak A 0 0.8 10 15 Vapor residence time (s) 400°C 500°C 20 Peak B 0 10 15 Vapor residence time (s) 20 550°C 0.7 Intensity 0.6 0.5 0.4 0.3 0.2 0.1 Peak C 0 10 15 Vapor residence time (s) 20 Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Analysis of lignin oligomer by ESI-MS 1000 1200 400°C 500°C 400°C 550°C 550°C 900 1000 Mn (Negative ion) Mw (Negative ion) 1100 500°C 900 800 700 800 700 600 500 600 400 500 10 15 Vapor residence time (s) 20 10 15 Vapor residence time (s) 20 Energy Fuels 2013, 27, 1428−1438 ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Reaction mechanism of lignin oligomer secondary reactions OH + CH4 O + CH3OH OH O HO O OH HO + H2 O O O OH OH OH O O + HO O O CO2 O OH O O O + Energy Fuels 2013, 27, 1428−1438 INTRODUCTION Our current View of Lignin Pyrolysis Lignin Structure Clusters with one aromatic ring Lignin monomers O Lignin Oligomers OK Perhaps over 500 oC OK Clusters 2-5 aromatic rings O Cluster 6> aromatic rings Low Temperature Reactions (180-300 oC) Lignin liquid intermediate Cross-linked lignin OK Lignin monomers Lignin Solid Residue Char + CH3OH + formaldehyde High Temperature Reactions (180-300 oC) CONCLUSIONS Study of Secondary Reactions in Vapor Phase Conclusions:  When pyrolytic lignin is exposed to temperatures over 500 °C in vapor phase, secondary reactions occurs resulting in the reduction of the yield of this fraction  Vapor temperature and residence time are the main parameters affecting conversion of the pyrolytic lignin  In the range of temperatures studied (400-550 °C) cracking (responsible for the reduction of molecular weight) and polycondensation reactions (responsible for the increase in molecular weight) compete Energy Fuels 2013, 27, 1428−1438 THANK YOU! & QUESTIONS? ... transformations happening to the structure of lignin oligomers during secondary reactions in vapor phase MATERIAL AND METHODS Study of Secondary Reactions in Vapor Phase Vapors Pine Wood Fluidized bed reactor... UV-Fluorescence Bio-oil Pyrolytic Lignin Extraction FTIR TG NMR ANALYSIS OF RESULTS Study of Secondary Reactions in Vapor Phase Yield of lignin oligomers 18 Yield of pyrolytic lignin (wt %) 16 14 12 10... Reactions in Vapor Phase Objectives:  To study the effect of secondary reactions in vapor phase on the yield and composition of lignin oligomer Research questions to be answered:  The nature of the