Fast, intermediate or slow pyrolysis for fuels
production, power generation from various
biomasses or as pre-conditioning unit for
gasifiers
Imperial College 2008 - London
Prof. Dr. Andreas Hornung – Chemical Engineering and Applied Chemistry - CEAC
Limited Resources
Fossil fuels
- World – potential and availability
250
6%
Produktion till
200
Resources: existent but not
economic
Resources
76 Gt
100%
2025 in case
of increase of
4%
150
2%
Gt
Reserves: possible to be
realized
100
Reserves
152 Gt
0%
50%
50
01/01/2000
0
12/31/1999
50
Production
122 Gt
-100
0%
-150
Quelle
: BGR
Natural gas
- World - potential and availability
400
Produktion till
100%
2025 in case
Resources
of increase of
300
Resources
222 Bill. m³
Bill. m³
200
Reserves
6%
100
50%
4%
Reserves
153 Bill. m³
0
Production
65 Bill. m³
2%
0%
01/01/2000
12/31/1999
0%
-100
Quelle
: BGR
Sustainable supply?
Prof. Dr. Andreas Hornung – Chemical Engineering and Applied Chemistry - CEAC
Natural Gas 1999
Norwegen
Großbritannien
Russland
3.000 km
Niederlande
1.000 km
Deutschland
2.000 km
Kasachstan
Ukraine
Usbekistan
Frankreich
Rumänien
Aserbaidschan
Turkmenistan
Algerien
Libyen
Ägypten
Datenquelle: Prof. Vahrenholt, RE Power Systems
Natural Gas 2010
Norwegen
Großbritannien
Russland
3.000 km
Niederlande
2.000 km
Kasachstan
1.000 km
Ukraine
Usbekistan
Aserbaidschan
Turkmenistan
Algerien
Libyen
Ägypten
Datenquelle: Prof. Vahrenholt, RE Power Systems
Natural Gas 2025
Russland
3.000 km
2.000 km
1.000 km
Turkmenistan
Datenquelle: Prof. Vahrenholt, RE Power Systems
Pyrolysis
Prof. Dr. Andreas Hornung – Chemical Engineering and Applied Chemistry - CEAC
Pyrolysis
Various reactors and three main pyrolysis procedures in practice
Fast pyrolysis
Intermediate pyrolysis
Slow pyrolysis
Most significant difference is the residence time of the solid phase
within the reactor – seconds, minutes, up to hours and correlated
energy transfer and temperature distribution
Gas phase residence times for fast and intermediate pyrolysis are
usually below 2s
Fast Pyrolysis Reactors
Rotating cone
Fluidised bed
HeissZyklon
Sand-Loop
Biobrennstoff
• Öl
• Gas
•Heiss-Zyklon
•Kondensator
Biobrennstoff
kalter
Biobrennstoff
Dampf
Koks
Sand
Bett
Öl, Gas
heisse Scheibe
Sand Loop
Koksverbrennung
zum
von
Koksverbrennung
siehe auch
Vortex Reaktor
rotierende, heisse
Scheibe, Zylinder,
Messer
Gas-Loop
Circulated fluidised bed
HeissZyklon
SandLoop
Koks
Koksverbrennung
Gas-Loop
Twin screw
• Öl
• Gas
zirkulierende Wirbelschicht
Bio brennstoff
ablative reactor
Heizer im Sand-Loop
LR-Mischreaktor
Kondensator
Biobrennstoff
Heiss-Zyklon
Gas
Öl
Koks
Vakuumpyrolyse
Twin screw reactor
LR-
-
Fast pyrolysis setup
A.V. Bridgwater*, P. Carson and M. Coulson
A comparison of fast and slow pyrolysis liquids from mallee
Int. J. Global Energy Issues, Vol. 27, No. 2, 2007
Slow pyrolysis setup
A.V. Bridgwater*, P. Carson and M. Coulson
A comparison of fast and slow pyrolysis liquids from mallee
Int. J. Global Energy Issues, Vol. 27, No. 2, 2007
A.V. Bridgwater*, P. Carson and M. Coulson
A comparison of fast and slow pyrolysis liquids from mallee
Int. J. Global Energy Issues, Vol. 27, No. 2, 2007
Conclusion from recent literature!
...
...
A.V. Bridgwater*, P. Carson and M. Coulson
A comparison of fast and slow pyrolysis liquids from mallee
Int. J. Global Energy Issues, Vol. 27, No. 2, 2007
to be agreed upon, but only for woody biomass
Intermediate Pyrolysis
Prof. Dr. Andreas Hornung – Chemical Engineering and Applied Chemistry - CEAC
Intermediate Pyrolysis – Haloclean ®
•
Flexible feed
stock (different
biomass, shapes
and mixtures of
those
Balls transfer
Balls cycle
Haloclean
•
High quality
pyrolysis
products and
variable yields of
products
•
Economic plant
size at 12,000 t/a
– 20,000 t/a
Ball mill
Model of the Haloclean reactor
Investigated materials
Feed
Yield
Energy (MJ/kg)
Tempera
ture
Coke
Liquids
Gas
Coke
Liquid
Olive stones 169,3 kg
450°C
30%
47%
23%
30
Oil: 30 Water: 10
Rice husk 86,3 kg
450°C
41%
41%
18%
21
Oil: 27 Water: 10
15
450°C
33%
57%
10%
30
Oil: 34 Water: 2
26
500°C
15%
52%
33%
26
Oil: 35 Water: 2,5
26
450°C
38%
45%
17%
24
Oil: 16 Water: 2,5
19
550°C
25%
50%
25%
24
450°C
23%
56%
21%
500°C
21%
57%
22%
Coco nut 13 kg
450°C
34%
52%
14%
Rice bran
500°C
20%
38%
42%
Brewers grain 2 kg
450°C
23%
51%
26%
Wheat straw >15t
(2005)
450°C
30%
50%
20%
Amount
RawMat
Rape seeds 611,15 kg
Rape residues 1292 kg
19
Beechwood 148,7 kg
3 kg
22
25
Oil: 21 Water: 6
16
intermediate
Mallee, fast pyrolysis at 500 °C
75 % Liquid, 9 % Char, 11 % Gas
Beach wood
450 °C
Wheat straw
450 °C
fast
Wheat straw
500 °C
Mallee, slow
500 °C
A.V. Bridgwater*, P. Carson and M. Coulson
A comparison of fast and slow pyrolysis liquids from mallee
Int. J. Global Energy Issues, Vol. 27, No. 2, 2007
Due to increased
fragmentation reactions
instead of pyrolysis
the amount of high tars
incrases in liquid
phases from fast pyrolysis
Fast or intermediate?
Fast pyrolysis seems to be a good approach for wood
Non-woody biomass:
Liquids itself can be bituminuous, depending on feedstock
The separation from solid phase from liquid and gas phase is not yet solved
In using slurry all (most) solid ingredients persist in the mixture which limits
their application for different gasifier types
Feedstock has to be well prepared, usually fine particles
Feedstock with elevated moisture content is not suitable
Scale for a single pyrolysis units of several hundred to power gasifiers up to
5 GW are described to have up to 220000 t/a throughput for economic
reasons – logistic and technical challenge
Simulation of tar formation
Prof. Dr. Andreas Hornung – Chemical Engineering and Applied Chemistry - CEAC
Experimental setup
TG
Returns the information about the
Returns the information about the
sample volatilization in terms of relative
sample volatilization in terms of relative
quantities and rate
quantities and rate
MS
Returns the relative amount of ion
Returns the relative amount of ion
intensity currents (fragments of the
intensity currents (fragments of the
evolved gas)
evolved gas)
Results Powdered straw
80
Char %
70
Liquid %
Yields Wt %
60
Gas %
50
Residence time 2 min
40
30
20
10
0
325
350
375
Temperature °C
385
400
Results Straw Pellets
80
Char %
Liquid %
Gas %
Yields Wt %
70
Comparison for different
shaped feedstock
60
50
40
30
20
10
0
375
385
400
450
Temperature °C
500
Reduction of the mass range necessary for interpretation
Integrated Profiles of MS
0,090
0,080
44
4
CO2
Carrier
0,070
0,060
Abaundancy
28 CO
0,050
18
0,040
Evolved Tar Components
0,030
4-(Oxy-allyl)guaiacol
Syringol
0,020
17
16
0,010
HCHO
30
15
1 2
14
29
32
40
31
41
151
155
138
169
124125 136
181
91
94 107108109
153
121
139
55 65 77 79 81 82
110
95
120
165
135
182
92
0,000
m/z
Permanent Gases and Tar Components
System complexity
Different reaction mechanism
and Different Reactants
Oligomers
Chemical Structure
Molecular Weight Distribution
Side
Groups
Propagation
Cellulose
Glucan
Xylan
Chain Fragments
Tar
Modified
Chains
Products
Char
Gas
May cause sensible variation
on the overall kinetic rate
parameters as change the
operative conditions
Each biomass component is
considered as structural reactant
with an average chemical
composition
Lignin
Each
Eachpolymer
polymertype
typehas
hasits
itsown
ownthermo
thermo
chemical
characteristics
and
must
chemical characteristics and mustbe
be
considered
separately
considered separately
The
Theaim
aimofofthis
thiswork
workisisaadistinct
distinct
description
of
the
thermal
description of the thermal
decomposition
decompositionbehavior
behaviorofoflignin
lignin
Hypothesis on reactivity
Aromatic Nuclei
νB
νB
Peripheral groups
Labile Bridges
Char Links
Spontaneous Dissociation
kB
kB
Spontaneous Condensation
kR
kR
Bimolecular Condensation
kG
kG
Peripheral Group Release
Niksa, S.; Kerstein, A. R. Energy Fuels 1991, 5, 647.
Pseudo Linear Chains
Description of the overall kinetic rate by meaning of TGA experiments
Instantaneous evaporation of metaplast components
Stoichiometry and selectivity coefficient calculated by fitting experimental data
Elemental Chemical Reactions
Chemical reactions can affect the polymer repeated units
Chemical reactions can affect the polymer repeated units
Eliminations
Cyclization
Volatile products Char residue
Modified chains
Volatile products
Unsaturation or cross linking
Chain scission
Volatile products
Char
residue
Volatile products
Volatile products
Molecular weight decrease in sample
Chemical reactions can
Chemical reactions can
affect the principal
affect the principal
polymer backbone
polymer backbone
(monomer, dimers, …)
Tars and Waxes
Evolved products
(oligomers and polymer chain fragments)
The
Thepropagation
propagationofofthe
thechemical
chemicalreactions
reactionscan
canaffect
affect
both
the
molecular
weight
distribution
and
the
chemical
structure
both the molecular weight distribution and the chemical structureofofthe
thepolymer
polymer
I.C. McNeill, J. Anal. App. Pyrol, 1997. 40-41: p. 21-41
Overall thermal decomposition process
Gas
Bridge Scission
ν
kB
kB
TAR Evaporation
TAR Evaporation
j<J*
j<J*
B
Char Links
1−νB
kB
kB
Gas
kB
kB
Bridge Scission
kB
kB
Shorter
Shorter
Fragments
Fragments
Condensation
1−νB
νB
Char Links
Reactant
Reactant
Fragments
Fragments
Gas
kR
kR
The kinetic expression for a single reaction depends
on the controlling mechanism
The implementation of the kinetic equations with
statistical moments allow to find a common and
global procedure joining different literature kinetic
models
The mathematical tools characterize the
potential evolution of gas/tar/char from biomass
Evolved Products
Heating rate: 25°C/min
TIC
Experimental DTG
Main Decomposition Step
Low Temperature Step
Tar
Permanent
gas
Water
High Temperature Step
Heating rate: 25°C/min
0.2
0.05
0.18
0.045
H2
O
0.16
0.04
Arbitrary units
(m/z 151)
Arbitrary units
(m/z 155)
0.14
0.12
0.1
0.08
0.06
(m/z 136)
0.04
0
5
10
0.02
0.015
15
20
25
0
30
0
°C/min
0.6
5
10
15
20
25
30
°C/min
0.5
0.02
CO2
Heating rate: 25°C/min
136 - 4-(Hydroxy-prop-2enyl)guaiacol
0.018
0.016
0.4
Arbitrary units
Arbitrary units
0.03
0.025
0.005
0
CO2 (m/z
44)
0.035
0.01
0.02
Water (m/z
18)
(Oxy-allyl)guaiacol
0.3
0.2
0.1
0.014
0.012
0.01
0.008
0.006
0.004
0.002
0
0
5
10
15
20
25
0
30
0
°C/min
5
10
15
20
25
30
°C/min
0.05
0.3
Heating rate: 25°C/min
0.045
CO
0.25
0.04
155 Syringol
CO (m/z 28)
Methane (m/z
15)
Abundance
Arbitrary units
0.035
0.2
0.15
0.025
0.02
0.015
0.1
0.01
0.005
0.05
0
0
0
0
5
10
15
°C/min
32 A. Hornung – ITC-TAB
0.03
20
25
30
10
20
°C/min
30
Transfer to technical units
Single particle
Segregated reactor elements
Process description
T(r)
This offers the understanding for a
Staged release of products
Reduction of tars
Optimized processing of entire plants
Maximum yield of gas or liquid
r Rp-1
Gas
Gas
n
Tar
Tar
4
3
2
1
Char
Char
A detailed understanding of the reactions will help to optimise the yield
Energy content of pyrolysis fractions
of fractions from pyrolysis of different feedstock for specific purpose of
use!
80 % of the energy of the rape
seed can be transfered to the engine
Energiegehalt [%] Biomassepyrolyse
bezogen
auf das
Test
by using
theEinsatzgut
entire rape
plant have been successful
100%
80%
Gas
Gas(Diff.)
60%
Water
Wasser
40%
Oil
Öl
Coke
Koks
20%
0%
Rape
500°C
Rapsf r ucht 5 0 0 °C
Rape 450°CRapspr essr
Rape
residue ReisspelzenRice
husk
ü ckst an d 4 5 0 °C
4 5 0 °C
Rapsf r ucht 4 5 0 °C
Straw
pellets
St r ohpele
l t s 4 5 0 °C
Technical scale
and industrial application
Prof. Dr. Andreas Hornung – Chemical Engineering and Applied Chemistry - CEAC
High flexibility in terms of yield
of favoured
fractions
Amount
of pyrolysis
oil, coke and gas
can be easily controlled
Yield %
80
Pyrolysis of straw
60
40
20
0
325 °C
350 °C
375 °C
385 °C
400 °C
Coke
wt%%
Koks
Gew.
73
48
38,2
36,2
33,5
wt%%
Öl Oil
Gew.
18
34
37,7
41,6
34,6
GasGew.
wt% %
Gas
9
18
24,1
22,2
31,9
Hot gas filtration of pyrolysis vapours is offering biofuels of high quality
Filtration unit
Filtration take place at 420°C, filter cake is dry
due to low dust & tar content of the pyrolysis vapours
The testing plant for 500 kg/h at Forschungszentrum Karlsruhe
Community engagement!
3/4.11.07
------------------------Advertising for green tires
Michelin is realising in Karlsruhe a Biomass Plant
The director of Michelin Germany, Austria and
Swiss, Jürgen Eitel, anounced for the site at
Karlsruhe to establish until end of next year an
Innovative unit for application of biomass.
Michelin is realising the project together with
Stadtwerke Karlsruhe and the energy provider
Evonik. The investment will be in a range of
10 M€.
……. Haloclean pyrolysis has been developed.
The European Bioenergy
Research Institute
Prof. Dr. Andreas Hornung – Chemical Engineering and Applied Chemistry - CEAC
European Energy Parks in
Germany
Hungary
and UK
Prof. Dr. Andreas Hornung – Chemical Engineering and Applied Chemistry - CEAC
Three different solutions for three different
environments
Urban, suburban and country side
Thermal load of the systems about 20 MW
Coupling of the Güssing gasifier with an intermediate
AER-CFB-Gasification
pyrolysis to enable runs with ash rich material
H2, Syngas
Flue Gas, CO2
Cyclone
Cyclone
Gasifier
Combustor
Pyrolysis
of ash rich
feedstocks
CaO
CaCO3,
Char
Steam
Air
Source: Battelle-Columbus Laboratories,
ZSW
TheGüssing
Güssing gasifier
for gasification of
wood chips
Source: www.tuwien.act.at/forschung/nachrichten/a-guessing.htm
The scopes of application of products from intermediate pyrolysis
Biomass (primary or waste), Energy grass,
Jatropha and others
Intermediate
Pyrolysis
Process energy (optional)
Coke
Fuel
oil
Gas
30 kW to 20 MW
(option)
Co
generation
Bio refining
Gasification
of ash free
Energy conversion “premium”
(combustion)
fuel
Grate or dust burner
Co combustion in wood
chip driven power plants
De-centralised use
(from 0 through 100%)
Electric
Heat
power
Integrated co-generation
liquids and
gases
Birmingham city CHP
concept
Gas engine
fuel cell