Bio-oil for the Future

Fast Pyrolysis Liquids as Energy Carriers

Technology supplied by

Integrated Fast Pyrolysis – VTT Technology The first integrated industrial plant will be the demonstration by Fortum Power and Heat in Finland in 2014 at the scale of 50 000 t/a of bio-oil. Bio-oil will be used in district heat production replacing fossil fuels.

Metso DNA automation system High pressure steam Turbine

Electricity

Non-condensible gas

District heat

Condenser Crusher

Drying

Forest residue

Fluidized bed boiler Pyrolysis unit Bio-oil

PYROLYSIS LIQUID

WATER SOLUBLES WATER INSOLUBLES

DCM-SOLUBLES DCM-INSOLUBLES

ETHER SOLUBLES ETHER INSOLUBLES

WATER EXTRACTION

DICHLOROMETHANE EXTRACTIONETHER EXTRACTION

OH O

H2C - CH

HOOH OH

OCH 3

O CHO

O

OH OH

OH

O

O

CH2

C - CH3

HO

OC - H

HO

O

H3C - OH

ACIDS, ALCOHOLS BY GC/FID

SOLIDS AS METHANOL/DCM INSOLUBLES

EXTRACTIVES AS HEXANE-SOLUBLES

WATER

BY KF

ALDEHYDES, KETONES

PHENOLS

FURANS

‘SUGARS’

OH O

H2C - C - CH3LIGNIN

Ether-soluble compounds can be identified by GC/MSD

MM 400 Da 1050 Da

Bio-Oil Chemical Composition

• Heating value 13-18 MJ/kg (LHV)

• Water content 20-35 wt%

• Viscosity between that of light and heavy fuel oils

• High ignition temperature

• Acidic, pH 2.5 - 3

• Does not sustain combustion

• Density 1.17-1.22 kg/l

• Polymerizes slowly

• Not soluble in mineral oils

Bio-Oil Composition and Fuel Oil Properties

0

10

20

30

40

50

60

70

80

90

100

Pyrolysis liquid

Aldehydes, ketones

Acids

'Sugars'

Water

Extractives

LMM lignin

HMM lignin

Wei

ght

%

Test run period 11/1996 – 9/2012 Time of operation > 3700 h Production 45 t liquids total Typical run 0.3-1 t a week

The VTT Fast Pyrolysis Process Development Unit

Capacity 20 kg/h feed, Oil 10-15 kg/h

0

200

400

600

800

1000

1200

1400

1600

1800

Pro

du

ctio

n k

g

Crop

Filter

Wood

Analysis and Design of Bioenergy Processes Using Computational Fluid Dynamics (CFD) Validated with Experimental Data

Performance Balance Assessment – AspenPlus Steady-State-Models Validated with Experimental Data

D UPL

D UPL

Q

D UPL

D UPL

D UPL

D UPL

W

D UPL

W

D UPL

FUEL

RAW MATERIAL

Power inputHeat loss

Power output

District heat

Power input

Heat loss

CFD-models are used to improve fast pyrolysis designs. From left: Computed temperature distribution (K), rate of release of bio-oil components (red indicates large rate, blue low rate) during pyrolysis, and some wood particle tracks coloured by initial size (blue indicates small size, red large size: 0.125 mm-5 mm).

AspenPlus-models may be used to evaluate industrial plant mass and energy balances, which enables industry to evaluate preliminary economic feasibility of fast pyrolysis for their specific cases.

Pilot-Scale Test Rig for Pumping, Filtration, Homogenisation of Bio-Oils

PC

PC

FC

300 bar

H2

H2 Compressor

100-200 bar

H2

Storage

350 bar

270 bar

HPLC

pump

Pyro oil

Furnace 1

20 cm / 12 mm ID

Furnace 2

30 cm / 12 mm ID

Steam

trap

Gas To GC

Liquid

MAT-Reactor for Co-Refining Development Small Continuous Hydrotreatment System

High Pressure Batch Autoclaves 0.5 – 1 l

Recent VTT Publications on Fast Pyrolysis of Biomass

Lehto, Jani; Oasmaa, Anja; Solantausta, Yrjö; Kytö, Matti; Chiaramonti, David. 2013. Fuel oil quality and combustion of fast pyrolysis bio-oils. Espoo, VTT. 79 p. VTT Technology; 87

Oasmaa, Anja, Kuoppala, Eeva, Elliott, Douglas, C.. 2012. Development of the basis for an analytical protocol for feeds and products of bio-oil hydrotreatment: ACS. Energy & Fuels, Vol. 26, Nr. 4, Pp. 2454-2460

Oasmaa, Anja, Källi, Anssi, Lindfors, Christian, Elliott, D.C., Springer, D., Peacocke, C., Chiaramonti, D.. 2012. Guidelines for transportation, handling, and use of fast pyrolysis bio-oil. 1. Flammability and toxicity. Energy & Fuels, Vol. 26, Nr. 6, Pp. 3864 – 3873

Elliott, D.C., Oasmaa, Anja, Preto, F., Meier, D., Bridgwater, A.V.. 2012. Results of the IEA round robin on viscosity and stability of fast pyrolysis bio-oils. Energy & Fuels, Vol. 26, Nr. 6, Pp. 3769 – 3776

Elliott, D.C. et al. Results of the IEA Round Robin on Viscosity and Aging of Fast Pyrolysis Bio-oils: Long-Term Tests and Repeatability, Energy & Fuels ASAP, 2012

Elliott, D.C., Hart, T.R., Neuenschwander, G.G., Rotness, L.J., Olarte, M.V., Zacher, A.H., Solantausta, Yrjö. 2012. Catalytic hydroprocessing of fast pyrolysis bio-oil from pine sawdust: ACS. Energy & Fuels, Vol. 26, Nr. 6, Pp. 3891 - 3896

Solantausta, Yrjö, Oasmaa, Anja, Sipilä, Kai, Lindfors, Christian, Lehto, J., Autio, J., Jokela, P., Alin, J., Heiskanen, J.. 2012. Bio-oil production from biomass: Steps toward demonstration: ACS. Energy & Fuels, Vol. 26, Nr. 1, Pp. 233-240

Yrjö Solantausta, yrjo.solantausta@vtt.fi Anja Oasmaa, anja.oasmaa@vtt.fi

Lars Kjäldman, lars.kjaldman@vtt.fi VTT Synfuels

Biologinkuja 3-5 PO Box 1000 FI-02040 VTT

Finland www.vtt.fi

VTT Offers

• Research services through the whole value-chain from biomass procurement to bio-oil:

– Feedstock characterization and assessment of its value as bio-oil production feed

– Bio-oil production in bench (1 kg/h) or pilot-scale (20 kg/h feed) in catalytic or non-catalytic operation modes

– Bio-oil quality assessment (physical and chemical properties), and assessment of its suitability to different end-use applications including further upgrading

– Bio-oil upgrading tests (HDO) with a continuous lab-scale catalytic upgrading unit

– Hydrothermal liquefaction (HTL) experiments in a 1 liter batch unit (Tmax 350°C, Pmax 250 bar)

• Techno-economic assessments and consulting services :

– Techno-economic assessments of bioenergy concepts employing AspenPlus® modelling software to determined process lant performance

– Computational Fluid Dynamics (CFD) analysis of bioenergy systems

– Green House Gas (GHG) balances for bioenergy concepts