Pyrolysis of biomass

2.2.2016
Anja Oasmaa, Yrj Solantausta, Ville Paasikallio
VTT Technical Research Centre of Finland

Thermal conversion of biomass

Oxygen
Combustion

Controlled amount of oxygen

Gasification

High temperature
Inert
atmosphere
01/02/2016

Thermal decomposition

Content
Thermal fast pyrolysis
Catalytic fast pyrolysis
Wet pyrolysis, Hydrothermal Liguefaction (HTL)
Slow pyrolysis

01/02/2016

Fast pyrolysis

Pyrolysis processes can be classified according

to residence time

Fast pyrolysis provides the highest liquid yield and has thus been the
main focus for the production of fuels.

01/02/2016

Bridgwater AV, Review of fast pyrolysis of biomass and product

upgrading, Biomass and Bioenergy (2011)

Fast pyrolysis of biomass

Rapid (1-2 s) thermal (about 500C) degradation of biomass under inert
atmosphere into bio-oil, gases, and char
Yields (of dry feed): 76 wt% bio-oil, 12 wt% char, 12 wt% gas
100

Yield wt% based on

dry feed

80
CHAR
60

GAS
WATER
PYRWAT
ORG

40

20

Organic liquid
product

0
PINE
01/02/2016

BIO-OIL
6

Pyrolysis process

Feedstock
preparation

Drying
Grinding

Conversion

Evaporation of volatile components

Decomposition reactions

Solids
separation

Separation of char
Separation of heat transfer material

Bio-oil
collection

Quenching/condensation of
vapors

Integrated Fast Pyrolysis

VTT Technology
Patents FI20125210, FI20075721,
FI20075720

Pyrolysis yields

Yield wt% based on dry feed

Pyrolysis Liquid Yields from Biomass

80
60
Water
Organic

40
20
0

Ref pine

Eucalyptus

Forest res

Grass

Straw

Water

12,0

11,3

11,3

15,1

16,0

Organic

61,6

59,5

53,0

37,4

36,0

Higher liquid yields from sawdust than forest residues or grass/straw

8

Thermal decomposition of individual biomass

components results in a very complex mixture
Bio-oil contains hundreds of organic compounds:
4 6 wt-% carboxylic acids
15 20 wt-% aldehydes, ketones, furans,
pyrans, monomeric phenols, etc.
25 35 wt-% carbohydrates, sugars
20 30 wt-% water
20 25 wt-% pyrolytic lignin, extractives, solids (incl. ash),
polymerisation products
What do all of these organic compounds have in common?
What kind of fuel properties does this have when compared
with conventional fuels?
01/02/2016

Energy and fuels, vol. 17, 2, ss. 433 443, vol. 22, 6, ss. 4245 4248

Bio-oil chemical composition defines its fuel

properties
Effect

Cause

Low heating value (13-18 MJ/kg) Water content, elemental composition

Acidic, pH 2.5-3

Carboxylic acids

High density and viscosity

High molecular weight compounds

Polymerizes slowly,
slowly (unstable)
exothermic

Reactive oxygenates

Water content 20-35 wt%

Biomass moisture, reaction water

Not soluble in mineral oils

Highly polar composition

The properties of bio-oil must be improved if it is to be used in

advanced fuel applications

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10

The challenging properties of bio-oil are

obvious when compared to light fuel oil

http://www.vtt.fi/inf/pdf/publicati
ons/2010/P731.pdf
01/02/2016

Oasmaa et al. Energy Fuels 2012, 26, 24542460

11

Fast pyrolysis industrial

developments
Fortum plant in Joensuu

Why Fast Pyrolysis of Biomass?

What makes biomass pyrolysis interesting?

Substantial energy densification compared to solid biomass
Easier logistics and handling for liquids
High retention of biomass carbon and energy in liquid form
Relatively simple operation at atmospheric pressure
Feasible at relatively small scale favorable feedstock logistics
and capital expenses
Product bio-oil can be used as it is or further upgraded into
value-added products

01/02/2016

14

Starting point: Occidential Petroleum in

California During the 70s

1.11.2010 - 15

Fast Pyrolysis for Bio-Fuel Oil - Scale-Up

FORTUM, PORVOO, FINLAND

FORTUM DEMONSTRATION - JOENSUU, FINLAND

UNION
FENOSA, SPAIN

ENEL, BASTARDO, ITALY

IEA BIOENERGY
COLLABORATION

1985

VALMET, TAMPERE, FINLAND

1990

1995

2000

2005

2010

2015

2020

2025

SCALE-UP 2004 - 2015

EARLY FAST PYROLYSIS
BENCH-SCALE
o CANADA, USA
o IEA BIOENERGY ASSESSMENTS

FIRST EUROPEAN PILOTS 1994-2000

o TWO CANADIAN, ONE FINNISH TECHNOLOGY
o CONTINUOUS OPERATION VERIFIED
o OPERATED BY EUROPEAN UTILITIES

o
o
o
o
o

ENSYN IN CANADA
BTG IN MALAYSIA
VALMET 2008FORTUM DEMONSTRATION 2014
BTG DEMONSTRATION 2015
16

Fast Pyrolysis Pilot Plants in Europe 1990 - 2002

WFPP

Fortum

Ensyn

WFPP - Union Fenosa,

Spain
Ensyn - ENEL, Italy
Forestera Fortum, Finland

Continuous pilot, 0.5 tpd at VTT, Espoo since 1996

Integrated Fast Pyrolysis

VTT Technology
Patents FI20125210, FI20075721,
FI20075720

18

Integrating fast pyrolysis to fluidized-bed boilers (FBB)

FBB

Flue gases
Fluid bed boiler

Heat and Power

Boiler
fuel
Sand +
char
Pyrolysis
fuel

FPO

Hot sand

Fast Pyrolysis

VTT has been developing an integrated

concept, in which fast pyrolysis is integrated
to a fluidized-bed boiler for example at pulp
and paper plant.
Integration is considered to bring in technical
and economic advantages:
(1) a high overall efficiency compared to
stand-alone pyrolysis concepts;
(2) lower investment costs due to no need for
a specific char combustor;
(3) lower operating costs than stand-alone
pyrolysis due to reduced man-power;
(4) operating flexibility due to full exploitation
of byproduct in the main boiler; and
(5) operation is easier, because there is no
need to combust by-product char in a
small suboptimal boiler, which often
would be needed to generate plant energy
requirements.

Pilot Plant, Valmet, Tampere, 2009

VTT licensed integrated pyrolysis technology to
Valmet
Valmet built a 0.5 t/h (2 MWth) pilot which uses
forest residues and sawdust as feed
VTT participated in operation and was
responsible for product analyses

Fluidised
bed boiler

Pyrolysis unit

20

Integrated bio-oil production

One of the critical features of pyrolysis is the ability to maintain constant
reactor temperature during operation. Since the pyrolysis reactor is
integrated directly to the boiler, there is an interest to find out how boiler
temperature variations effect pyrolysis temperature.
It may be seen that
850C
pyrolysis temperature
control handles rapid
changes of boiler sand
temperature smoothly
800C
A sand temperature drop of
50C in just 20 minutes
didnt cause noticeable
disturbances in pyrolysis
750C
reactor
temperature.
21

550C

Boiler temperature

500C

Pyrolysis reactor temperature

450C

Bio oil production technology

Metso DNA automation system

High pressure steam

Turbine
Electricity

District heat

Forest residue

Non-condensible gas

Drying
Condenser

Fluidized bed boiler

Pyrolysis unit

Crusher

Bio-oil

Vlimki, E, Autio, J, Oasmaa, A., 2014. Lignocellulosic Fuel from Wood Residues: Industrial Demonstration. 22nd European Biomass
Conference and Exhibition "Setting the Course for a Biobased Economy", EUBCE 2014, 23 - 26 June 2014, Hamburg, Germany: ETAFlorence Renewable Energies. Conference proceedings, pp. 1654 - 1656. ISBN 978-88-89407-52-3

Fortum Joensuu: an Integrated

Bio-Oil Demonstration Plant
Bio-oil capacity
Annual production
Start-up
Feedstock

30 MW
50 000 t, 210 GWh
2013 in commissioning 2015
Forest residues, sawdust

Reactor and pyrolysis oil recovery

inside the boiler building

Fuel receiving,
drying and crushing

VTT along with Fortum, Valmet,

and UPM has developed a
technology which has been
integrated to a CHP (Combined
Heat and Power) plant

Bio-oil tanks

Technology supplied by

23

New plants based on Fortums concept

Bio-oil plant in Estonia's Prnu by 2016
http://www.investinestonia.com/en/about-estonia/news/article/921-fortumplanning-eur-30-mln-bio-oil-plant-in-estonia-s-paernu
http://www.biofuelstp.eu/funding.html#ner3002
The European Union has decided to support the 30 million euro project with 6.9
million euros.

CHP Biomass pyrolysis plant in Latvia

The project concerns fast pyrolysis technology for conversion of woody biomass
to pyrolysis oil in Jelgava, Latvia. The project plant will receive energy inputs
from a CHP plant and deliver by-products of the pyrolysis as inputs to the CHP
plant. Annual output of pyrolysis oil is expected to be 40,000 tonnes. Feedstock
needs are 100,000 t of woodchips/year. The bio-oil will be exported to Sweden
and Finland to replace heavy fuel oil use in energy installations.

Fast Pyrolysis demonstration Plant

EMPYRO demo-plant:
Location Hengelo (NL)
5 t/hr wood input;
3.2 t/hr pyrolysis liquid
(22 kton/yr)

6 MW steam
800 kWe electricity
Planned operation start in 2014
1

KIT, Germany
Bioliq process
Two-stage process to FT-liquids
through pyrolysis and
gasification with LURGI
Straw pyrolysis, capacity 0.5 t/h

Fast pyrolysis bio-oil production processes in

2016 (above 1 t/h)

Operational

27

Combustion and co-firing in boilers

Fast pyrolysis bio-oils may replace fossil fuel
oils in many stationary applications including
boilers and furnaces in the future
These bio-oils are completely different from
petroleum fuels and other bio-oils in the
market
In order to be able to create reliable bio-oil
combustion systems that operate at high
efficiency, bio-oil grades should be
standardized for combustion applications.
Careful quality control, all the way from
feedstock harvesting through production to
end-use is critical.

VTT Technology 87
http://www.vtt.fi/inf/pdf/t
echnology/2013/T87.pdf

Demonstrating the use of bio-oil in district

heating standardization will pave the way for
more widespread use

Valmets pyroHOB
pyrolysis oil burner 2014

All rights Valmet

29

Standards and norms for FPBO

Standards, specifications and guidelines are needed
to help to establish markets
VTT Publication 731
ASTM/EN standard test methods have been
systematically tested and modified for fast pyrolysis
bio-oils several guide books
Two ASTM bio-oil burner fuel grades approved (ASTM
D7544), in EU standardisation work is going on
In the EU registration under REACH has to be made if
bio-oil is produced or imported to the EU
ASTM D7544

http://www.vtt.fi/inf/pdf/publicat
ions/2010/P731.pdf

The catalytic fast

pyrolysis process

Why catalytic instead of thermal pyrolysis?

The primary aim of catalytic fast pyrolysis

(CFP) is the reduction of bio-oil oxygen
content and consequent improvement in
the bio-oil properties.

Partially upgraded bio-oil is easier to

process into transportation fuels.

01/02/2016

32

Two process alternatives for achieving this

catalytic transformation
Integrated approach
Pyrolysis + catalysis

Catalyst as heat transfer material

Decoupled approach

01/02/2016

Pyrolysis

Catalysis

Inert heat transfer

material

Upgrading
catalyst
33

The essence of catalytic fast pyrolysis

3. Upgraded products
+ H2O, COx, coke

Bio-oil quality
improves at the
expense of quantity

2. Catalytic upgrading
Catalyst bed
1. Thermal decomposition

Biomass
01/02/2016

34

Zeolites are the most widely studied catalyst

for biomass CFP
Key features
Solid acid catalysts (SiO2/Al2O3)
Shape selectivity due to well defined
pore structure
Conversion of oxygenates to
aromatic hydrocarbons (HZSM-5)

Other catalytic materials, e.g. different oxides, are also studied as

alternatives for zeolites.
01/02/2016

35

Catalyst deactivation is the largest difference

between thermal and catalytic fast pyrolysis
Operation in a bubbling fluidized bed reactor (30 min)
250-100 m2/g

300-350 m2/g

Catalyst deactivation
0 wt% coke

5-10 wt% coke

Significant coke deposition and decline in catalyst performance after 30

minutes of continuous CFP operation in a bubbling fluidized bed reactor
01/02/2016

36

Catalyst regeneration is the key for maintaining

a stable level of performance

Deactivation via coke formation

How long should each

reaction-regeneration
cycle be?

Regeneration via coke combustion

01/02/2016

37

Use of catalysts causes a significant change in

the overall product distribution
70

Non-catalytic

63

Catalytic

Yield (wt %, dry basis)

60
50

In oil fraction 18 wt %
In aqueous fraction 14 wt %

40
32

27

30
21

19

20
10

10

Water

Gases

18

0
Organics

01/02/2016

Char/coke

38

Bio-oil from catalytic fast pyrolysis has low

water and high carbon content

Property
Water
Carbon
Hydrogen
Oxygen
Higher heating value
Total acid number

Unit
(wt %)
(wt %, dab)
(wt %, dab)
(wt %, dab)
(MJ/kg, dab)
(mg KOH/g)

Non-catalytic
23.9
53.4
6.5
40.0
22.2
71

Catalytic
8.3
72.0
6.4
21.5
30.4
30

dab = dry ash free basis

01/02/2016

39

Water-insolubles in oil fraction,

water-solubles in aqueous fraction
100
Acids, aldehydes, ketones,
alcohols, phenols

90
80

Sugar-type compounds

Weight %

70
60

Water

50
40

WIS volatiles (aromatics)

30
LMW lignin, extractives

20
10

HMW lignin, polymerization

products, solids

01/02/2016

40
Paasikallio et al., Green Chem., 2014,16, 3549-3559.

KiOR Demonstration of Catalytic Pyrolysis of

Biomass and Hydrotreatment of Bio-Oil

KiOR constructed a production scale

facility (500 dry tons of per day, about 90
MW feed), in Columbus, Mississippi. First
products were shipped early 2013.
The design capacity is over 40 000 t/a
gasoline and diesel blendstocks from
woody biomass.

http://www.kior.com/

Bio-oil upgrading

Fuel production pathways

Primary
conversion

Secondary
upgrading

Final fuel
product

Thermal fast
pyrolysis
Catalytic fast
pyrolysis

Catalytic
conversion
of bio-oil

Hydrothermal
liquefaction

01/02/2016

43

Putting bio-oil upgrading into perspective

The largest fundamental
difference between bio-oil
and petroleum is the oxygen
content (35-40 wt% dry basis)

Bio-oil upgrading mainly

revolves around technologies
capable of heteroatom (O, N, S)
removal
01/02/2016

Fogassy et al. Appl. Catal., B 96 (2010) 476485

44

Challenges with bio-oil hydrotreating

Many bio-oil compounds have insufficient carbon chain length for

forming liquid hydrocarbons
High gas and water yield during hydrotreating of whole bio-oil
hydrogen is wasted on forming methane and light alkanes
Severe processing conditions required: multi-stage, high T and P
Long-term catalyst stability still a question mark
01/02/2016

Howe et al. Energy & Fuels 2015 DOI: 10.1021/acs.energyfuels.5b00304

45

Hydrotreated bio-oil is oxygen free and contains

transportation fuel range hydrocarbons

H/C and O/C axes reversed from

previous figure!
01/02/2016

Zacher et al. Green Chem., 2014, 16, 491 / Elliott et al. Energy Fuels 2012, 26, 38913896

46

Wet pyrolysis, Hydrothermal

Liquefaction (HTL)

Hydrothermal liquefaction (HTL)

Medium temperature / high pressure conversion of organic
molecules in an aqueous medium
Target product: biocrude, i.e. carbon-rich oil-like product which
can be further upgraded into e.g. transportation fuels
Typical feedstocks: lignocellulosic biomass, algae, lignin,
aqueous sludges
Feedstock does not require extensive drying prior to conversion
Solids loading must be kept low (5-12 wt%) to retain a
pumpable/mixable slurry for continuous operation

01/02/2016

48

Comparison of fast pyrolysis and HTL

Conditions
feedstock
operating temperature
environment
catalyst
operating pressure
residence time
carbon yield to bio-oil

Fast pyrolysis

Hydrothermal liquefaction

Dry Biomass
450-500C
inert gas
none
1 atm
< 1 sec
70%

Wet biomass
350C
aqueous condensed phase
alkali reagent
200 atm
5 to 30 min
35%

14.5 MJ/kg
38%
25%
low (50 cSt)
no

31.0 MJ/kg
12%
5%
high (4,000 cSt)
yes

oil product quality

Lower heating value
oxygen content, dry basis
water content
viscosity@40 C
thermal stability

Biomass carbon distributed between four

different product fractions
Non-condensable gases: 11.8 % C
Aqueous
feedstock slurry

HTL:
350 C
200 bar
5-30 min

Water-soluble organics: 39.9 % C

Biocrude: 45.3 % C
Solid residue: 2.8 % C

Target: maximum retention of carbon and energy in biocrude fraction

Rejection of oxygen as CO2 and H2O
Recycling of aqueous fraction (water + water-soluble organics) into the
HTL process
HTL biocrude is easier to hydrotreat than fast pyrolysis bio-oil
01/02/2016

Carbon balance from Zhu et al. Applied Energy 129 (2014) 384394

50

Hydrothermal liquefaction (HTL)

Hydrothermal processing is promising for very wet feedstocks, such as
algae or water hyacinth
wet wastes from food or other agricultural processing (sludges):
Grain wet-milling by-products
Food-processing sludge
Paper-mill sludge
Animal manures (in the USA: over 30 million dry tons per year)
Wastewater treatment sludges

http://www.ieabioenergy.com/publications/iea-bioenergy-task42-biorefining/

HTL - History/State of Technology 1/2

HTL technology was developed mainly in Germany before World War II
Further development in 1970s
Demonstrated on pilot-scale (1 ton/day), at Albany, Oregon, USA
PERC - bio-oil recycle & with CO reducing gas
LBL - aqueous process, acid pretreatment, no recycle, 18 wt% slurry

Albany plant, USA

HTL - History/State of Technology 2/2

Other limited pilot scale testing in US, Canada and Europe
HTU (1990s) aqueous process, thermal softening, no
alkali
CatLiq (Catalytic Liquefaction), Denmark
Sewage sludge, 100 kg/h continuous, 250 bar, 300-370C,
homogenous (alkali) and heterogenous catalysts (Zirconia)
No commercial-scale HTL operations
Challenges for commercialization include:
continuously feeding wet biomass slurry at pressure
Continuous-flow reactor design
Utilization of biocrude and upgrading to fuels

Slow pyrolysis

Pyrolysis processes can be classified according

to residence time

Fast pyrolysis provides the highest liquid yield and has thus been the
main focus for the production of fuels.

01/02/2016

Bridgwater AV, Review of fast pyrolysis of biomass and product

upgrading, Biomass and Bioenergy (2011)

55

Slow pyrolysis
Slow pyrolysis means thermal decomposition of wood in the absence of oxygen at
elevated temperatures (450-500 0C)
The main product is charcoal and byproducts are liquids (wood vinegar, tar) and
gases
In Finland, today nearly all charcoal is used as barbeque coke. Normally the liquids
and gases are used as a heat source of retorts. Some extra wood is needed for
heating, too
Wood chips or hogged fuel or even tiny wood stems from forestry thinnings are used
as a raw material for slow pyrolysis. Charcoal is produced normally from birch or
alder or mixture of them
Old technology, which is already in a commercial use
Main product (biochar, charcoal) is used mainly as barbeque coke or as a reductant
in metallurgy (Brazil). It can be used as a soil amendment and fertilizer (new). Wood
vinegar, tar and gas are formed as byproducts.
The production capacity of a single plant varies from about 100 t/a (batchwise
retorts) to about 10 000 t/a (continuous retorts).
01/02/2016

56

Concluding remarks
61

Summary for fast pyrolysis

Thermal decomposition of biomass under a non-oxidative
atmosphere; 500 C, atmospheric pressure, 1-2 s reaction time
bio-oil (organics + H2O), gases and char
Bio-oil is a very complex mixture with hundreds of different
oxygenate compounds
Chemical composition challenging fuel properties
Bio-oil can be combusted using suitable equipment
Fast pyrolysis has reached an industrial demonstration stage in
Finland, Netherlands and north America

62

Summary for catalytic fast pyrolysis

Catalytic pyrolysis can be used for producing a partially upgraded
bio-oil with reduced oxygen content and otherwise improved
properties
Bio-oil quality improves at the expense of quantity
Less oil, more gases, water and coke
Catalyst deactivation a challenge
Continuous catalyst regeneration is required to overcome
reversible catalyst deactivation caused by coke formation
Different deactivation phenomena become relevant during
long-term operation with continuous regeneration
Long-term catalyst stability is a key question
No break-through yet in catalytic fast pyrolysis, extensive research,
KioR plant is not operated currently
01/02/2016

63

Summary for HTL

Hydro Thermal Liquefaction is under extensive study in utilisation of
aqueous waste streams and materials, like algee
Conceptually simple (feed preparation, pump, heated pipe, gravity
separable bio-oil)
Robust and can be applied to wide range of feedstocks at similar
identical processing conditions
HTL bio-oil is thermally stable and can be readily upgraded
No commercial-scale HTL operations
Challenges for commercialization include continuously feeding wet
biomass slurry at pressure

01/02/2016

64

Summary for bio-oil upgrading

Target is fuel range hydrocarbons bio-oil oxygen removal
Upgrading using existing oil refining technologies:
hydrotreatment and fluid catalytic cracking
Bio-oil more challenging to process compared to petroleum
distillates manifests as severe coking + other issues
Hydrotreatment: possible to produce pure hydrocarbons for e.g.
blending purposes
Fluid catalytic cracking: blending bio-oil with petroleum
biogenic carbon gets distributed among the different product
fractions

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65