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From fast pyrolysis oilto transportation fuel:

pathwaysand

obstacles

Wolter Prinsand

Frederik Ronsse

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Fast Pyrolysis Summary

dp < 3 mm / 500 oC / 1 atm.

pyr = 1 to 30 s / pyr < 2 s

15 wt.% gas15 wt.% char70 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 content1 and the vapor residence time2

2Hoekstra et al., AIChE Journal 2012, 8 (9) 2830-28421 Oasmaa et al, Energy & Fuels 2010, 24, 1380-1388

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Fast Pyrolysis

EMPYROHengelo NL

start: now5 ton/hr wood wasteBTG technology

bio-oil for Campinasteam for Akzo Nobel

other large units: Ensyn, Renfrew Ontario Canada Fortum / Valmet / VTT in Joensuu Finland

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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) 9688-9699

www.btgworld.com

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2. Pyrolytic sugars to alkanes: APR

sorbitol

C7 to C15

H2 / CO2

intermediatesdehydration hydrogenation

SiO2/Al2O3 Pt, Pd

n

reforming

Pt, Ni-Sn alloys

aldol condensation?

C1 to C6

G.W. Huber, R.D. Cortright and J.A. Dumesic, Angew. Chem. Int. Ed. 2004, 43, 1549-1551

225 oC35 bar

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3. Bio-oil for marine engines

fast pyrolysis

bio-oil stabilizatio

n

emulsification

blending

marine engine fuel is obtained after stabilization (e.g. esterification) and either 1. blending with diesel and alcohols or2. emulsification with diesel and surfactantshttp://www.pfi.no/Biorefinery/Biorefinery-Projects/

ReShip/

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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, 2nd 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 2014

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4. Bio-oil gasification

bio-oil gasifiersyngas

cleaningfuel

synthesis

Entrained Flow Gasification• non-slagging or• slagging for bio-oil char

slurries• 40 to 60 bar; 1250 to 1450 oC• co-feeding possible

Auto-thermal Catalytic Reforming• 1 bar; 850 oC• metal catalyst• low minerals content required

Fischer Tropsch diesel• iron or cobalt as catalysts• 10 to 60 bar; 200 to 300 oC

DME • diesel substitute• further synthesis to gasoline

Alcohols• methanol, ethanol, butanol • gasoline substitute

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

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5. Catalytic Fast Pyrolysis

Reactions dehydration, decarboxylation, decarbonylation isomerization, cracking, oligomerization

Products light alkanes, furans, phenols, (poly)aromatics + coke + CO + CO2 + H2O

Catalysts FCCexamined H-forms of zeolites: Beta, Y, ZSM-5

alumina and silica aluminatransition metal catalysts (Fe/Cr)metal doped MCM-41 mesoporous

Yields organic liquids: 15 to 20 wt.% on water 30biomass basis gases 30

char 15coke on catalyst 5 to 10

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5. Catalytic Fast Pyrolysis

Critical issues arehydrogen deficiency in feedlow hydrocarbon yieldincreased coke on catalystcatalyst regeneration procedurecatalyst poisoning (minerals)

Research should focus on understanding catalystperformance, and onexperimentation in mini-plantsenabling full mass and elementalbalances plus a proper productanalysis

Ex-situ catalysisseems more appropriate

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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 H20 rather than by CO2 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 bartemperatures: up to 275 oC in a first stabilization step (mild HDO)

up to 400 oC in a second finishing step (full HDO)catalysts: Ru/C, CuNi/δ-Al2O3 in the first step

CoMo, NiMo on γ-alumina in the 2nd step

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6. Catalytic hydrodeoxygenation

oxygen content

type of fraction

distillate fraction% w/w

C

% w/w

H

% w/w

O

% w/w

8 wt.% lights 5.3 72.8 11.9 14.2

naphtha 19.7 73.7 11.5 14.4

jet 18.7 77.8 11.0 11.9

diesel 17.2 82.4 10.7 7.5

gasoil 30.3 84.6 10.4 5.3

0.4 wt.% lights 13.9 85.9 14.6 0.3

naphtha 30.2 86.3 13.3 0.3

jet 22.0 87.0 12.3 0.7

diesel 20.6 88.4 11.4 0.5

gasoil 13.5 88.6 11.5 0.4

Christensen et al., Energy Fuels 2011, 25, 5462-5471

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5/6. CFP and HDO

Venderbosch, ChemSusChem 2015

bio-butanol

bio-ethanol

100 % iso-energy line

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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 2015

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Technology Readiness Levels

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

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THE END

Wolter Prins and Frederik Ronsse

Laboratory for Thermochemical Conversion of BiomassUniversity of Ghent, Belgiumhttp://www.ugent.be/bw/biosysteemtechniek/en

Wolter.Prins@UGent.beFrederik.Ronsse@UGent.be