HYDROCONVERSION OF FAST PYROLYSIS BIO-OIL: UNDERSTANDING AND LIMITING MACROMOLECULES FORMATION. Alain Quignard / IFPEN

Flash Pyrolysis Flash Pyrolysis Flash Pyrolysis 2 step HDT 1) Stabilization 2) Hydroconversion Flash Pyrolysis HYDROCONVERSION OF FAST PYROLYSIS BIO-OIL: UNDERSTANDING AND LIMITING MACROMOLECULES FORMATION Alain Quignard / IFPEN 1

AGENDA IFPEN Context: from FPBO (Fast Pyrolysis Bio-Oil) to biofuels Understanding macromolecule during FPBO 1 st step HDT on representative model compounds on a FPBO from forest residues 2 2016 I F P E N

IFPEN at a glance Who we are? Budget & Funding > 50% The only French public research body to fund more than 50% of its budget using its own resources 3

AGENDA IFPEN Context: from FPBO to biofuels Understanding macromolecule during FPBO 1 st step HDT on representative model compounds on a FPBO (Fast Pyrolysis Bio-Oil) from forest residues Future work 4 2016 I F P E N

CONTEXT Main Issue: thermal instability during the catalytic hydroconversion process Biomass H 2 Ni-Mo heterogeneous catalyst Fast Pyrolysis Bio-Oil: FPBO Step1 Stabilisation 100-250 10-20 MPa Step2 Hydroconversion 250-350 10-20 MPa Aqueous phase Refining Coprocessing 1t biomass (db) 0.6-0.7t FPBO 40-45%O 20-30% wet Unstable, acidic, 100% oxygenates Immiscible in HC Partially De- Oxygenated Oil Stable 0.25-0.3t Fully DeOx. Oil O<5% Stable, neutral Mainly HC based 0.2-0.25t drop-in biofuel 5 2016 I F P E N

Thermal instability during the catalytic hydroconversion process Competition between the HDO pathways and the macromolecules Partial Hydrodeoxygenation (HDO) With catalyst and H 2 Fast (~min), T < 200 C Pyrolysis bio-oil s High molecular weight compounds With/without catalyst and H 2 Very fast (~min), T > 100 C Solid residues /Humins! Catalyst deactivation [R. H. Venderbosch et al. J.Chem.Technol.Biotechnol, 85, pp. 674-686, 2010] [J. Wildschut et al. Environ. Prog. Sustainable Energy, 28, pp. 450-460, 2009] 6 2016 I F P E N

Objective of this study Identifying / understanding phenomena occurring in the stabilization step Undesired reactions leading to high MW compounds (i.e. macromolecules) Desired reactions leading to smaller molecules (deoxygenation/hdo, hydrogenolysis ) 1 st Ph.D. conducted from 2013 to 2016 in IFPEN in collaboration with IRCELyon: Matthieu OZAGAC 7 2016 I F P E N

CHOOSING REPRESENTATIVE MODEL COMPOUNDS FPBO: Chemical Composition Cellulose Hemicellulose Lignin sugars, acids, alcohols furans, acids, alcohols phenols, methoxy-phenols HO HO D-Glucose Levoglucosan O O O Furfural Furan O O O H O 5-HMF O FPBO Chemical composition range Levulinic Acid O O CH HO 3 Acetic Acid O Vanillin OCH 3 1,2-benzenediol O H O C H O 3 Guaiacol 9 2016 I F P E N [Milne et al. A Review of the Chemical Composition of Fast-Pyrolysis Oils from Biomass, in Development in thermal biomass conversion, 1997] [Kersten et al. Catalysis for Renewables,Anonymous, 119-145, 2007] [Oasmaa, D. Meier. "Characterisation, analysis, norms & standards", Fast Pyrolysis of biomass: a handbook Volume 3, pp.19-59, 2005]

REPRESENTATIVE BLEND: 5 MODEL COMPOUND BLEND Acidity (TAN = 70 v/s FPBO: 70-120), water 30% Main chemical function existing in FPBO Similar C/H/O atomic ratio O H O C H 3 FPBO 5 compounds blend O O O H HO HO O Objective Wt % 10 2016 I F P E N

EXPERIMENTAL TOOL & ANALYTICAL PROTOCOL CSTR Batch reactor (500 ml) 150 g feed /15 g Ni-Mo catalyst 13 MPa (H 2 ) 200 C < T < 300 C 0 < t < 3 h 11 2016 I F P E N

EXPERIMENTAL STRATEGY ON MODEL COMPOUNDS Mass Balance : liquid vs. solid Guaiacol 30wt% Water 30wt% Aqueous Solid Furfural 13wt% Acetic acid 7wt% D-Glucose 20wt% Organic Liquid: SEC Solid: 13 C NMR Product Conversion [Ozagac et al. Biomass an Bioenergy 95 (2016) 182-193] 12 2016 I F P E N

MODEL COMPOUND HYDROCONVERSION: 250 C, 1h, 13 MPa C16 50% H 2 O 30% Glucose 20% C16 37% Glucose 20% H 2 0 30% Furfural 13% C16 7% Furfural 13% Guaiacol 30% H 2 0 30% Glucose 20% Acetic Acid 7% Glucose 20% Guaiacol Furfural 30% 13% Water 30% Solid Liquid Gas Experimental losses (after separation) Mass balance (%) 100% 13 2016 I F P E N 80% 60% 40% 20% 0% 100% 80% 60% 40% 20% 0% D-glucose + furfural = High solid production 100% 100% 80% 80% 60% 60% 40% 40% 20% 20% 0% 0% Guaiacol(one organic phase) Limiting residue production

Model compound reactivity at 250 C, 1h, 13 Mpa s characterization by SEC/RI-UV D-Glucose Furfural s Nomalized RI signal t0 t:15min t:30min t:45min t:60min 8 7 6 5 4 3 2 1 0 100 1000 10000 Molecular weight (PS equivalent) [g.mol -1 ] + Guaiacol Solids Solids Low temperature and/or reaction time Soluble in the liquid organic phase High temperature and/or reaction time 14 [Ozagac et al. Biomass an Bioenergy 95 (2016) 194-205]

REPRESENTATIVE FPBO FPBO from forest residues FPBO Analyses 5 model blend FPBO Range[1] Forest Residue FPBO Water (wt%) 30 20 35 26.4 From 20 kg/d VTT PDU at: 480 C / vapor phase residence time < 1s C (wt%) 58.9 48 60 56.4 H (wt%) 6.4 5.9 7.2 6.4 O (wt%) 39.7 34 45 36.7 N (wt%) 0 < 0.3 0.3 Viscosity(cSt) - 10 80 (50 C) 14.9 (40 C) TAN(mg K/g) 70 70 120 91 Ash(wt%) 0 0.02 1.2 0.2 Density(kg/L) - 1.1 1.3 (20 C) 1.2 (20 C) [Bridgwater A.V, Biomass and Bioenergy. 2012, 38, 68-94] 15 2016 I F P E N

EXPERIMENTAL STRATEGY ON FPBO WITH / WITHOUT GUAIACOL Aqueous Organic Liquid: SEC + 13 C NMR Product Conversion 16 2016 I F P E N [Ozagac et al. : Submitted to Biomass an Bioenergy]

FPBO FROM FOREST RESIDUES SEC-RI detector on organic fraction FPBO without guaiacol at 250 C Raw FPBO Heavy compounds (HC) < 3000 g/mole PS eq. (RI detector) Normalized RI signal Raw bio-oil t0 t180min 5 4,5 4 3,5 3 2,5 2 1,5 1 0,5 0 100 1000 10000 Molecular weight (PS equivalent [g/mol]) Aromatic & carbonyl functions: significant part of HC (UV detector) 100% FPBO after hydroconversion Significant quantity of macromolecules from 3000 to 8000 g/mole PS eq. (RI & UV detectors), even at short residence time (t0) Deshydration, aldolization/crotonization favored in acidic medium Aromatic & carbonyl functions constituting part of macromolecules 18 2016 I F P E N

FPBO FROM FOREST RESIDUES SEC-RI detector on organic fraction FPBO without and with guaiacol (50/50wt%) at 250 C Doted lines: FPBO Solid lines : FPBO/guaiacol mixture Normalized RI signal Raw bio-oil t0 t180min t0 t180min 5 4,5 4 3,5 3 2,5 2 1,5 1 0,5 0 100 1000 10000 Molecular weight (PS equivalent [g/mol]) FPBO + Guaiacol (50/50) after hydroconversion s stabilized with guaiacol: HC < 3000 g/mole PS eq. Guaiacol limits macromolecules / HC growth by dilution effect & by reacting with precursors 19 2016 I F P E N

Guaiacol (& methoxy-phenols) favors the conversion to an organic phase, limiting precursors to macromolecules On model Compounds D-glucose + furfural + acetic acid, with water blend Production of macromolecules / humins/solids Solids Enhanced reactions in homogeneous phase Previous blend with guaiacol addition Solid residues production is limited Low temperature Short residence time Soluble in the organic phase Heavy molecules solubilized in the organic phase Guaiacolis stabilizing reactive compounds precursors to solids On FPBO Same trends High temperature Long residence time Solids Guaiacol & products 22 2016 I F P E N

FUTURE WORK: 2 ND PHD: 2015-2018 Bio-oils are a complex oxygenated mixture with an immense reaction network Little in is available on reaction mechanisms and on reactivity. How to understand and develop bio-oil hydrotreating modeling? Option 1: Perform additional experimental work on model compounds & mixtures Option 2: Build a model based on reaction rules and available experimental data - Based on IFPEN knowledge acquired on hydroconversion of heavy petroleum cuts - Using Stochastic Simulation Algorithm & Molecular reconstruction 24 2016 I F P E N

Thanks for your attention! alain.quignard@ifpen.fr Acknowledgements Matthieu Ozagac (CEA) Christophe Geantet (IRCELyon) Celine Bertino Ghera (IFPEN) Dorothée Laurenti (IRCELyon) Denis Uzio (IFPEN) Yrjö Solantausta (VTT) for the BioOil production and kind cooperation 25 2016 I F P E N

26 2016 I F P E N Questions & Discussion?