From fast pyrolysis oil to transportation fuel: pathways and obstacles Wolter Prins and Frederik Ronsse 1

ga s Fast Pyrolysis Summary 2 d p < 3 mm / 500 o C / 1 atm.  pyr = 1 to 30 s /  pyr < 2 s 15 wt.% gas 15 wt.% char 70 wt.% liquid typical for pine wood acids, esters, aldehydes, ketones and hydroxy-carbonyls, furans, sugars and anydrosugars, phenols and substituted aromatics acidic, unstable, oxygenated, aqueous, particulates, 50 % unknown, immiscible with HC’s, 50 % vac. distill. residue regarding the oil yield and quality, critical issues are the biomass ash content 1 and the vapor residence time 2 2 Hoekstra et al., AIChE Journal 2012, 8 (9) Oasmaa et al, Energy & Fuels 2010, 24,

ga s Fast Pyrolysis EMPYRO Hengelo NL start: now 5 ton/hr wood waste BTG technology bio-oil for Campina steam for Akzo Nobel other large units:Ensyn, Renfrew Ontario Canada Fortum / Valmet / VTT in Joensuu Finland 3

1. Pyrolytic sugars to bioethanol: fermentation sugar phase organic acids pyrolytic lignin aqueous phase l pyrolysis oil sugar phase can be fermented to bioethanol, after acid hydrolysis, detoxification, neutralization and filtration Jieni Lian et al., Bioresource Technology 101 (2010)

ga s 2. Pyrolytic sugars to alkanes: APR sorbitol C 7 to C 15 H 2 / CO 2 intermediates dehydration hydrogenation SiO 2 /Al 2 O 3 Pt, Pd n reforming Pt, Ni-Sn alloys aldol condensation ? C 1 to C 6 G.W. Huber, R.D. Cortright and J.A. Dumesic, Angew. Chem. Int. Ed. 2004, 43, o C 35 bar 5

3. Bio-oil for marine engines fast pyrolysis bio-oil stabilization emulsificati on blending marine engine fuel is obtained after stabilization (e.g. esterification) and either 1. blending with diesel and alcohols or 2. emulsification with diesel and surfactants / 6

ga s 4. Bio-oil gasification fast pyrolysis is a cheap pretreatment method bio-oil is easy to handle problems due to feedstock variations are avoided pressurization of bio-oil is easy bio-oil contains no ash energy efficiencies > 80 % decoupling of bio-oil production and (large-scale) gasification is attractive bio-oil gasification has been demonstrated at a significant scale Venderbosch and Prins, Handbook of Biomass Gasification, 2 nd edition, H.A.M. Knoef (ed.), Ch. 8, pp 222 to 250 Gas composition from wood-derived bio-oil gasification in ECT’s 0.4 MW pilot plant in Sweden. Leijenhorst et al., Biomass & Bioenergy 2014, special issue of the European Biomass Conference held in Hamburg, June

4. Bio-oil gasification bio-oil gasifier syngas cleaning fuel synthesis Entrained Flow Gasification non-slagging or slagging for bio-oil char slurries 40 to 60 bar; 1250 to 1450 o C co-feeding possible Auto-thermal Catalytic Reforming 1 bar; 850 o C metal catalyst low minerals content required Fischer Tropsch diesel iron or cobalt as catalysts 10 to 60 bar; 200 to 300 o C DME diesel substitute further synthesis to gasoline Alcohols methanol, ethanol, butanol gasoline substitute 8

5. Catalytic Fast Pyrolysis The purpose of CFP is to produce a stable, largely de-oxygenated liquid, enabling the co-processing in a petrochemical refinery. At severe conditions, BTX is produced at low mass yields 9

ga s 5. Catalytic Fast Pyrolysis Reactions dehydration, decarboxylation, decarbonylation isomerization, cracking, oligomerization Productslight alkanes, furans, phenols, (poly)aromatics + coke + CO + CO 2 + H 2 O Catalysts FCC examinedH-forms of zeolites: Beta, Y, ZSM-5 alumina and silica alumina transition metal catalysts (Fe/Cr) metal doped MCM-41 mesoporous Yieldsorganic liquids:15 to 20 wt.% on water30 biomass basisgases30 char15 coke on catalyst5 to 10 10

ga s 5. Catalytic Fast Pyrolysis Critical issues are hydrogen deficiency in feed low hydrocarbon yield increased coke on catalyst catalyst regeneration procedure catalyst poisoning (minerals) Research should focus on understanding catalyst performance, and on experimentation in mini-plants enabling full mass and elemental balances plus a proper product analysis Ex-situ catalysis seems more appropriate 11

ga s 6. Catalytic hydrodeoxygenation Purpose: removing oxygen, reducing average molecular weight, and increasing H/C Conditions are much more severe than in catalytic fast pyrolysis. Naphta like product, obtained by H 2 0 rather than by CO 2 rejection. Complete deoxygenation can be achieved, but oxygen removal is not always the ultimate goal; the oil should be made non-acid, stable and distillable. hydrogen:up to 600 L/kg bio-oil pressures: up to 200 bar temperatures:up to 275 o C in a first stabilization step (mild HDO) up to 400 o C in a second finishing step (full HDO) catalysts: Ru/C, CuNi/δ-Al 2 O 3 in the first step CoMo, NiMo on γ-alumina in the 2 nd step 12

ga s 6. Catalytic hydrodeoxygenation oxygen content type of fraction distillate fraction % w/w C % w/w H % w/w O % w/w 8 wt.%lights naphtha jet diesel gasoil wt.%lights naphtha jet diesel gasoil Christensen et al., Energy Fuels 2011, 25,

ga s 5/6. CFP and HDO Venderbosch, ChemSusChem 2015 bio-butanol bio-ethanol 100 % iso-energy line 14

ga s 7. FCC co-processing Petrobras-Six 200 kg/hr FCC demo unit in São Mateus do Sul, Brazil Co-processing 3 ton of pine derived, crude pyrolysis oil from BTG 10/90 and 20/80 bio-oil-VGO mixtures; 400 hrs. of total testing time Good quality gasoline/diesel with more phenols Coke on catalyst increased with no more than15 % 30 % renewable carbon in the liquid product Co-production of renewable fuel gas and LPG Presented by Marlon Almeida at the Empyro Symposium, May

Technology Readiness Levels 16 fast pyrolysis fermentation of pyrolytic sugars autocatalytic reforming of bio-oil bio-oil entrained flow gasification fuel for marine engines catalytic fast pyrolysis and HDO aqueous phase reforming of pyrolytic sugars co-processing of bio-oil in FCC

ga s THE END Wolter Prins and Frederik Ronsse Laboratory for Thermochemical Conversion of Biomass University of Ghent, Belgium 17