Biomass gasification to fuels and
chemicals
HighBio-seminar, Nov. 9, 2010, Oulu
Matti Reinikainen, D. Sc. (Chem. Eng.)
Senior research scientist, VTT, Espoo
2
GASIFICATION AND SYNTHETIC FUELS AT VTT
14 M€/year
40% customer projects
Over 15 patent families, 6 international patents and several license and
IPR agreements and well-focused IPR portfolio on fluidized-bed
gasification and hot gas cleaning
45 researchers, of which 20% hold a doctor’s degree
Excellent test facilities from laboratory to pilot scale
The leading research group in Europe in gasification and in fast
pyrolysis concept development. Coordination of over 10 EU and IAE
projects
Customers such as Neste Oil, Stora Enso, Corenso,
Metso Power, Nordkalk, Lahti Energia
3 3
Matti Reinikainen D.Sc.(Chem. Eng.)
Since1987 at VTT
1989-1991 AIST-fellow at NCLI in Tsukuba, Japan (C1-Chemistry
program, FT-pilot plant)
1995 STA-fellow at TNIRI in Sendai, Japan
1995 Licentiate's thesis on Co-catalysts for vapor phase
hydroformylation
1998 Doctor's thesis on Co-Ru-catalysts for FT-sythesis
1996-1999 superintendent of the synthesis pilot-plant (special
chemicals) at VTT
2000 - industrial contract research projects on catalysis
2006 moved to Gasification team
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GAS CLEANING
• TAR & METHANE
REFORMING
• FILTRATION
• DIRTY SHIFT
FT-DIESEL
ULTRA
CLEANUP
SNG
FUEL-FLEXIBLE
FLUIDISED-BED
GASIFICATION
• STEAM/OXYGEN
• PRESSURISED
FT-GASOLINE
METHANOL
HYDROGEN
NEW INNOVATIVE TECHNOLOGY EXISTING & EFFICIENT
BUT EXPENSIVE
TECHNOLOGY
HEAVIER
ALCOHOLS
ETHANOL
FORMALDEHYDE
ACETIC ACID
DME
MTG, MTO
FUEL
CATALYTIC PROCESSES
(Co, Fe, Cu, Zn, Ni, Rh, Ag…)
Synthesis gas route to fuels and chemicals
5
Biomass gasification to chemicals and fuelsPatents and open publications / year (y. = pat., g. = other publ.)
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BIOMASS GASIFICATION PROCESSES
General 3D-View of the Research Landscape
Source: HCAplus database; Publications 1990 - 2010. Visualization by STN AnaVist.
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BIOMASS GASIFICATION PROCESSES”Methanol” highlighted (non-patents; green, patents; yellow
Source: HCAplus database; Publications 1990 - 2010. Visualization by STN AnaVist.
8
OPERATION CONDITIONS FOR CATALYTIC GAS CLEANING
IN BIOMASS GASIFICATION
800 - 900 °C
N2, CO, CO2, CH4,
CxHy, H2, H2O
tar 500 - 15 000 ppm
NH3/HCN 300 - 10 000 ppm
H2S/COS 50 - 500 ppm
HCl
alkali metals
heavy metals
particulates 1 - 10 g/m3n
N2, CO, CO2, CH4,
CxHy, H2, H2O
tar ~0
NH3/HCN ~equilibrium
H2S/COS 50 - 500 ppm
HCl
alkali metals
heavy metals
particulates 1 - 10 g/m3n
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Biomass as a raw material for synthesis gas
In principal, syngas reactions are not dependant on the raw material,
but relevant differences still exist:
There is less experience about biomass gasification:
Biomass gasification plants are principally at least one order
of magnitude smaller than coal or natural gas plants
For instance: Shell-Pearl GTL-plant 140 000 bpd; 400 MW
BTL-plant ca. 4000 bpd
Gasification and gas cleaning constitute a decisive part of
the investment cost
Different kind of impurities (esp. tars)
Variation in the H/C ratio
Product upgrading (best product in small scale?)
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10
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Processes based on biomass gasification
Lähde, TUW
Company Country Product Output [t/a] Total investment Unit Type Status Start-up Year
Chemrec AB Sweden DME; 1 800 28 500 000 EUR pilot under construction 2010
Chemrec AB Sweden methanol; DME;132 000
(Methanol) 250 000 000 EUR demo planned 2013
CHOREN Fuel Freiberg GmbH & Co. KG Germany FT-liquids; 14 000 100 000 000 EUR commercial under construction 2009
CHOREN Industries GmbH Germany FT-liquids; 200 000 commercial planned
CTU - Conzepte Technik Umwelt AG Austria SNG; 576 demo operational 2008
Cutec Germany FT-liquids; 0,02 pilot operational 1990
ECN Netherlands SNG; 346 pilot under construction 2011
ECN Netherlands SNG; 28800 demo planned
Enerkem Canada ethanol; 375 pilot operational 2003
Enerkem Canada ethanol; 4 000 demo under commissioning 2009
Enerkem Canada ethanol; 30 000 70 000 000 CAD commercial announced
Flambeau River Biofuels LLC United States FT-liquids; 51 000 200 000 000 USD pilot planned 2012
Forschungszentrum Karlsruhe GmbH Germany diesel; gasoline type fuel; 608 pilot under construction
GTI Gas Technology Institute United States FT-liquids; 26 pilot under construction 2009
NSE Biofuels Oy, a Neste Oil and Stora Enso JV Finland FT-liquids; 656 demo under construction 2009
NSE Biofuels Oy, a Neste Oil and Stora Enso JV Finland FT-liquids; 100 000 commercial planned
Range Fuels, Inc. United States mixed alcohols; pilot operational 2008
Range Fuels, Inc. United States ethanol; methanol; 300 000 commercial under construction 2010
Research Triangle Institute United States FT-liquids; mixed alcohols; 22 3 000 000 USD pilot planned
Southern Research Institute United States FT-liquids; mixed alcohols; 40 000 000 USD pilot operational
Tembec Chemical Group Canada ethanol; 13 000 demo operational
Vienna University of Technology Austria FT-liquids; 0,20 pilot operational 2005
Alico
NewPage
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Thermochemical / biochemical hybridprocesses
Company Country Product Output [t/a] Total investment Unit Type Status Start-up Year
Coskata United States ethanol; 120 demo under construction 2009
Coskata United States ethanol; 300 000 400 000 000 USD commercial planned
Coskata United States ethanol; pilot operational
Iowa State University United Statesethanol; FT-liquids;
biodiesel; pyrolysis oils;200 18 000 000 USD pilot under commissioning 2009
ZeaChem United Statesethanol; mixed alcohols;
various chemicals;4 500 pilot announced 2010
Abengoa
ICM
Lähde: TUW
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Required gas purity levels
Source: NREL 2003
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Chemicals from methanol
Several important commercial processes:
Formaldehyde
Acetic acid (Monsanto-process)
MTBE
DME
Methylhalides
Also possible to produce gasoline with MTG-process (New Zealand)
ZSM-5 zeolite-catalyst
CH3OH + Gasoline
hydrocarbons
15
MTG-process, TIGAS
Developed by Haldor Topsøe
Methanol/dimethylether synthesis and the
subsequent conversion into gasoline are
combined in a single synthesis loop
Flexible to the variation in H/C-ratio of the
syngas
Desired conversion attained at a fairly low
pressure level
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MTG-processes, TIGAS
8.12.2009 Topsøe published their plan to construct a demo plant in
Des Plaines, USA.
Fuel 25 t of wood / d
Demonstartion for industrial scale of 1000 t wood / d.
Energy efficiency ca. 60%.
Partners UPM-Kymmene and Conoco-Phillips.
”This is the last step before the technology will be made
commercially available.”
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Alcohol mixtures
Preferably higher alcohols, e.h. butanol
Good as a gasoline component
Biochemical routes
Catalytic route from synthesis gas
Direct route (modified methanol catalyst, sulphided Mo-catalyst...)
Olefinic FT-product => (Heterogeneous) hydroformylation
Safol-23-process
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Selectivity of Co2(CO)8 based catalysts
Promoted Co2(CO)8/SiO2. T=523 K, P=2.1 MPa,
GHSV=2000 h-1, CO:H2:Ar=3:6:1. The loading of
the promoters was 25 mmol/100g with the
exception of 43 mmol/100g for Li and 200
mmol/100g for Sr.
none Mg Ca Sr Ba Li Na K Rb Cs0
5
10
15
20
25
30
0
5
10
15
20
25
Promoter
Selectivity, C-% CO conversion, %
Ethanol Acetic acid Acetaldehyde Other oxygenatesCO conversion
SiO2 SiO2-K Al2O3 TiO2 ZrO2 MgO ZnO La2O3 CeO2
0
2
4
6
8
10
12
14
0
5
10
15
20
Support
Selectivity, C-% CO conversion, %
Ethanol Acetic acid Acetaldehyde CO conversion
• The effect of support on the CO hydrogenation
activity of Co2(CO)8 based catalysts with metal
loading of 5 wt.-%. T=523 K (493 K for Al2O3 and
ZnO), P=2.1 MPa, GHSV=2000 h-1,
CO:H2:Ar=3:6:1.
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Moist
feedstockDryer Gasifier Reforming
Heat
Oxygen
Recycle gas
Oxygen
plant
HP
Steam
HT
Shift
LP
Steam
HP
Steam
CombustorHP Steam
Scrubber-
cooler
Regenerative
AbsorberFT synthesis
FT primary liquids (C5+)
LP Steam
FT reforming loop
FT off-gas (purge)
H2O
MP Steam
SeparatorCW
CW
Steam: 0.33 kg/ kg
of dry biomass
Exceptionally high recovery
of exotherm as steam
Process Scheme for Production of FT Liquids
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Challenges of the Fischer-Tropsch-reaction
The selectivity of the FT-reaction is intrinsically bad and only to the admen the reaction product is simply ”diesel”
The product is always a complex mixture and it is necessary to find good use to all of the components
The necessary catalysts (Co, Ru, Fe) are very sensitive to sulphur
The reaction is highly exothermic and one must utilise the reaction heat
Source: Shell
α=0.85, Co-catalyst,
neutral Al2O3-support
T=200°C
α=0.61, Co-catalyst,
acidic Al2O3-support
T=250°C
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Thoughts on a possible research subject
”Badly selective FT-reaction
Aimed at a light FT-products, e.g. (27 % C1-C4; 50 % C5-C12; 16 % C13-C18, 7 % > C18
Fe-catalyst which is not so sensitive to sulphur
Save in the cost of final cleaning of the gas
Once through process – no hydrocracking
Easier to control the reaction heat than in the manufacture of wax
Reforming of the gas is easier since it is not necessary to attain full methane conversion
Methane can possibly be used as SNG. Other light hydrocarbons and the heaviest fraction as energy
Olefins used possibly as chemical raw materials
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VTT-UCG
Optimised
syngas R&D
& PDU-scale
development
Industrial demon-
stration: 10-50 MW- replacement of oil/gas
- start-up in 2009
Further R&D- process optimisation
- waste gasification
- hydrogen technologies
New applications- fuel cells, 2nd gen. IGCC
- hydrogen or methane
- renewable chemicals
R & D on hot filtration
and
catalytic gas cleaning
Biomass/waste
gasification for power
(Lahti, Corenso,
Värnamo, Kokemäki)
Peat
ammonia
plant
Oulu/Finland
Synthesis gas
R&D in Europe
and USA in 1980’s
First synfuel production plant- 200-250 MW feed capacity
- 105 000 tons/a diesel fuel
- 3 % Finnish transport fuel
- start-up in 2012-14
1995 2000 2005 2010 2015 20201985 2025 2030
Biorefineries at pulp and paper mills
and at large CHP plants - diesel production: 70 -150 000 tons/plant
- by-product heat for process steam or
district heating
- high overall efficiency
SYNTHESIS GAS FROM BIOMASSFROM R&D TO INDUSTRIAL SUCCESS
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Forest biomass
in future also
urban waste and straw
- Southern hemisphere
plantations
Biofuel production
Optional Biofuels:
(pellets)
bio crude
EtOH/MeOH
BioDiesel
Wood
residues
Pulp &
Paper Mill
Wood
handling
Bark
boiler
Power
Heat
Power
Steam
Refinery
Crude Oil
OPTIONS FOR FOREST INDUSTRY ? - benefit of raw material, biorefinery and large scale operation -
BioPower
< 500 MWf
< 400 MWf
Paper and
Market pulp
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BEFORE INTRODUCTION OF FT PLANTPower-Boiler Energy flows (LHV basis)
Bark, etc
Black liquor
Purchased biofuel
P&P products
151 MW
Wood for fibre,
purchased fibre
Co-Production of Syngas Derivatives at Pulp and Paper Mills
Power
boiler
Electricity
Primary heat
100 MW
31 MWe
25
Bark, etc
Black liquorP&P products
Purchased electricity FT primary liquids161 MW
25 MW
Wood for fibre,
purchased fibre
25 MWe
Power
boiler
FT
plant
Purchased biofuel 260 MW
Electricity
Primary heat
100 MW
21 MWe
285 MW
Co-Production of Syngas Derivatives
at Pulp and Paper Mills
AFTER INTRODUCTION OF FT PLANT (260 MWfeed)Integration of steam system in conjunction with power boiler rebuild
Secondary heat used for biomass drying
Energy flows (LHV basis)
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Bark, etc
Black liquor
Purchased biofuel
P&P products
Purchased electricity
FT primary liquids
+ 161 MW
+ 134 MW*
Wood for fibre,
purchased fibre
Integrated
Pulp and
Paper Mill
or
Stand-Alone
Paper Mill
+ 35 MWe**
Co-Production of Syngas Derivatives at
Pulp and Paper Mills
* 134 MW = (285 – 151) MW
** 35 MW = (31 – 21 + 25) MW
NET CHANGES WITH INTRODUCTION OF FT PLANT (260 MWfeed)Integration of steam system in conjunction with power boiler rebuild
Secondary heat used for biomass drying
Incremental energy flows (LHV basis)
Nominal overall efficiency = 100 x 161/(134 + 35/0.4) = 73 %
(purchased electricity generated from biomass at 40 % η)
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Estimated Overall EfficienciesEfficiency = 100 x [LHV-energy of main product + high-grade byproduct energy - {electricity / 0.4}]
/ [LHV-energy of as-received feedstock]
Notes: (1) Feedstock drying: from 50 % moisture to 30 % with secondary heat; from 30 % to 15 % with
by-product steam. (2) FT: Fischer-Tropsch primary liquids; reforming loop included.
-40
-20
0
20
40
60
80
100
FT CH3OH SNG H2
Overa
ll E
ffic
ien
cy, %
Primary
energy out
Main product
(Electricity in)
/ 0.4
Integration benefits: large for FT; significant for CH3OH; negligible for SNG; minor for H2
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Equivalent Biomass-to-Pump Costs: Biomass-FT < Biomass-SNG
(and most probably Biomass-FT << Biomass-H2-FC!)
0
20
40
60
80
100
FT SNG
Co
sts
, E
UR
/MW
h
Vehicle-related extra
costs
Distribution costs,
incl. pressurisation for
SNGUpgrading costs (FT)
Production costs
Estimated (Equivalent) Biomass-to-Pump Costs260 MWfeed; Feedstock at 10 EUR/MWh; Interest on capital 10 %, 20 a
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Finnish biodiesel projects
Background: National UCG-project: budget 4 MEUR, duration 2004 –
2007
Wide industrial consortium: Foster-Wheeler, Neste Oil, Andritz-Carbona,
Vapo, PVO, UPM, M-real, Metsä-Botnia and Stora-Enso
Three Finnish consortia have published their biodiesel projects based on
F-T-technology:
Neste Oil + Stora Enso → NSE Biofuels Ltd- joint venture
UPM + Andritz/Carbona (+GTI)
Vapo + Metsäliitto
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NSE Biofuels Demo 1 plant in Varkaus
From Neste Oil and Stora Enso
1. Commissioning as air blown lime
kiln gasifier
2. Testing period as O2/H2O gasifier,
gas cleaning, FT tests
3. Return to lime kiln gasifier
Lime
kiln
5 MW
Gas cleaning
and FT
BiomassSiloKuivuriDryer 12 MW
Gasifier
1. Commissioning as air blown lime
kiln gasifier
2. Testing period as O2/H2O gasifier,
gas cleaning, FT tests
3. Return to lime kiln gasifier
Lime
kiln
5 MW
Gas cleaning
and FT
BiomassSiloKuivuriDryer 12 MW
Gasifier
Lime
kiln
5 MW
Gas cleaning
and FT
BiomassSiloKuivuriDryer 12 MW
Gasifier
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Wood
sourcing
UPM’s 2G BTL Concept
Gasification
& purification
FT-synthesis
& up-grading
Water
treatment
CHP
plant
Pulp & paper mill
Synthetic
biodieselH2+CO
CnH2n+2
Biomass
drying
Pulp,
wood
Bark
Stumps
Residues
Paper mill units
Additional units
Material flow
Energy flow
Gas Technology Institute, Des Plaines, Illinois, US
from: UPM
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UCGFUNDA 2008 - 2011
Biomass gasification for synthesis applications
- fundamental studies supporting industrial development projects
VTT, TKK and Åbo Akademi, total budget 1.5 M€
Financing by Tekes Biorefine, VTT and private companies
(Carbona, Foster Wheeler, Metso Power, Neste Oil, Stora Enso, UPM &
Vapo)
Biomass characterisation for pressurised steam/oxygen-blown gasification:
ash behaviour and reactivity
Filter blinding and catalyst deactivation studies
Tar reactions in non-catalytic and catalytic processes
System studies on BTL-applications and hydrogen production
Development of measuring methods for tars and other gas contaminants
IEA groups: ”Biomass thermal gasification” and ”Biomass Hydrogen”
34
On-line analysis of tars, water and ammonia
35
'Rapid' on-line tar
analysis
Analysis time 15-20 min
Calibrated compounds:
Benzene
Toluene
Naphthalene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Gas phase samples on-line
The results have been in good
agreement with the results from
off-line analysis off the
corresponding samples.
Especially useful in transient
conditions where the gas
composition changes quickly.
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
26.8.2008 20:24 26.8.2008 21:36 26.8.2008 22:48 27.8.2008 0:00 27.8.2008 1:12 27.8.2008 2:24 27.8.2008 3:36 27.8.2008 4:48 27.8.2008 6:00 27.8.2008 7:12
mg
/m3
Naftaleeni
Tolueeni
Bentseeni
Results from BiGPower tests:
air-blown CFB gasification
followed by tar reformer
36
Recent trends based on projects and literature
Fischer-Tropsch BTL-concepts are very similar in the synthesis
step. Product is only ’diesel’.
MTG-route (Methanol To Gasoline) is gaining more interest
Haldor Topsøe’s TIGAS-process is in demonstration step
Skive Fjernvarme (methanol- and methanol to gasoline-process
Chemrec’s black-liquor based process
GTI
Ethanol from synthesis gas is a popular theme in Japan
Thermochemical route to butanol and mixed alcohols wait for an
efficient catalyst
37
Summary
Biofuels are limited by the available raw material – they can not solve the
energy problem
Diesel is not the only possible end product
Total efficiency about 90 % if process thermally integrated, otherwise
below 60 % -> importance of integration
There are plenty of functional options -> complex task to optimize
Raw material, size of plant, integration to other processes, political
decisions
Synthesis gas must be clean and contain a suitable H2/CO ratio
Primary product is has to be upgraded
One must find economical use to all product fractions and reaction heat
Plenty of development needs in gasification, gas cleaning as well as
synthesis steps: solutions for small scale; heat removal from process;
catalyst activity, selectivity and stability; uprading of products…