Post on 17-Aug-2021
KIT – University of the State of Baden-Wuerttemberg and
National Research Center of the Helmholtz Association
Institute for Catalysis Research and Technology
www.kit.edu
The bioliq BTL process for synthetic biofuels and chemicals production
Eckhard Dinjus
IKFT
2 19.09.2012
Motivation
Use of biomass as the only renewable carbon source for production of
fuels and chemicals prior to heat and power generation
Large scale production of energy related products
0
500
1000
1500
1900 1920 1940 1960 1980 2000 2020 2040 2060
noch offen
Geo- / ozeanische
Energie
Solarenergie
Neue Biomasse
Windenergie
Kernkraft
Wasserkraft
Erdgas
Erdöl
Kohle
Trad. Biomasse
Source: Deutsche Shell AG
IKFT
3 19.09.2012
Chemical pathways to synthetic products
Biomass Syngas
Fischer-
Tropsch-
synthesis
Propylene
Ethylene
Gasoline
Acrylic acid
Oxygenates
…….
Gases
LPG
Naphta
Cerosene
Diesel
……….
Dimethyl-
ether DME
Refining
H2 + CO
CH3OH
„C6H9O4“
Direct use (Fuel cell, PME production, …
Hydrogen
Methane (SNG)
CH3-(CH2 )n-CH3
Methanol-
synthesis
IKFT
4 19.09.2012
BTL-projects in Europe
Process Type Capacity Pressure
KIT bioliq, D Fast pyrolysis + high pressure entrained flow
gasification + hot gas celaning + DME and
DtG gasoline synthesis
5 MWth
(2 MWth) 80 bar
Choren Carbo-V, D
(IP now owned by Linde)
CGT pressurized entrained flow gasification,
FT-synthesis, SunFuel, plant mothballed! 45 MWth 4 bar
TBM, D Allothermal fluidized bed, SNG 10 MWth atm.
Biodies, F Planned for Choren-gasification + Rectisol +
GTL.F1-Synthese 45 MWth 4 bar
BioTfueL , F Torrefaction + Uhde Prentflo-gasification, FT-
synthesis 15 MWth n.b.
Güssing, A Staged fluidized bed, electricity,
SNG (1 MW) and FT-synthesis 8 MWth atm.
BioDME, S Black liquor entrained flow gasification,
DME/methanol-synthesis 5 t/d DME 29 bar
Neste Oil, FI Circulated fluidzed bed, FT-Synthese 12 MWth atm.
Värmlands Methanol HTW-gasifier, methanol+heat 111 MWth n.b.
IKFT
5 19.09.2012
Potential feedstocks
Agriculture
Straw, hay, ….
Energy crops
Forestry
Residues (brash, tops, stumps)
Thinnings
Short rotation plantation
Trackside vegetation clearance
Streets, railway tracks
Power transmission lines
Organic residues
Recovered waste wood
Organic waste fractions
IKFT
6 19.09.2012
Decentral-centralized concept
Energy density: 2 GJ/m3 25 GJ/m3 36 GJ/m3
Energy densification of biomass in regional distributed
plants by bioliqSyncrude production
Economic conversion in large scale to syngas and
further refining into fuels & chemicals
IKFT
7 19.09.2012
bioliq® process scheme
bioSyncrude
bioSyncrude
Synfuel
Bio
mass
Syngas
De-central Centralized
Fuel
synthesis
DME
synthesis
Filter Sorption CO2 and water
separation Catalyst
O2 (Steam)
Gas cleaning and conditioning
High pressure
entrained flow
gasification
Slag
Fast pyrolysis
Pre-treatment
IKFT
8 19.09.2012
Bioliq pilot plant
Designed for 1000 h/a operation
500 kg/h biomass input
(50 L/h synfuel output)
Mass and energy balances
Cost estimates
Scale-up considerations
IKFT
9 19.09.2012
State of construction
Stage 1 Stage 2 Stage 3 Stage 4
Process
Fast pyrolysis +
BioSyncrude
production
HP Entrained flow
gasification
Gas cleaning
+ Synthesis I Synthesis II
Product BioSyncrude Synthesis gas DME Gasoline
Capacity 2 MW (500 kg/h) 5 MW (1 t/h) 150 kg/h 50 l/h
Realization 2008 2011 2011 2011
Partner Lurgi + MAT
Mischanlagentechnik Lurgi
MUT Advanced Heating
Chemieanlagenbau Chemnitz
IKFT
10 19.09.2012
Total View of the pilot plant
Mechanical completion: Nov. 2011
IKFT
11 19.09.2012
Fast pyrolysis pilot plant
Biomass preparation
Biosyncrude preparation Feed stock storage
Pyrolysis product recovery Fast pyrolysis
IKFT
12 19.09.2012
Fast pyrolysis
Abrasives
Straw (waf)
WaterAqueous
condensate
Pyrolysis gas
Tar condensate
Solids
Char for
internal
combustion
Ash
Twin screw mixer reactor
Heat carrier loop with sand
Reaction temperature 500 °C
Gas retention time ~3 sec
Gaseous, liquid and solid products
M
M
Cutting
Hot sand
Sand
Flare
Burner
Cycone Filter
Cyclone Quench
Char cooling
Tar condensate Aqueous
condensate
Co
nd
en
ser
I
Air Reactor
Air
Char
Biomass
Silo
Co
nd
en
ser
II
Char Condensate Biosyncrude
85-90% energy conservation!
IKFT
13 19.09.2012
Energy balance of fast pyrolysis
0.0
5.0
10.0
15.0
20.0
25.0
Hartholz (wf) Weichholz (wf) Weizenstroh (wf) Weizenkleie (wf)
En
erg
iein
ha
lt d
er
Pro
du
kte
[M
J/k
g]
19.4120.04
17.55
5.20 4.59 6.62 3.87
0.971.40
1.78
1.35
12.60 13.49 8.31 13.33
0.640.56
0.83
0.76
Ko
ks
Ko
nd
en
sat
Gas
Δh
R
19.31
Heating up to 500 °C and reaction enthalpy: 0,54 – 0,83 MJ/kg
approx. Energy content of pyrolysis gas
Fast pyrolysis PDU
(10 kg/h, 500 °C)
IKFT
15 19.09.2012
Char Condensate Gas Water Ash Beech wood
Wheat straw
Rice straw
Hay
Wheat clay
0 20 40 60 80 100 wt. %
Gas composition:
CO2 50 %, CO 30 – 40 %, CH4 2 – 5 %, C6 3–6 %
Pyrolysis product distribution
Bagasse
IKFT
16 19.09.2012
Char Org. cond. Aqueous.
Cond. Ash
Particle size
d90 (m) 150
Water (wt.%) 4,7 6,4 49,7 0,1
Ash (wt.%) 1,8 0 <0,05
Elemental analysis
C (%) 84,4 58,6 24,3 2,6
H (%) 2,7 6,2 3,8 0,2
O (%) 6 28,4 21,9
N (%) 0,4 0,3 0,3 0,3
S (%) 0,07 <0,05 <0,05 1,0
Product composition of pyrolysis oil and char
Complex mixture of
organic acids, aldehydes,
ketones, furfurales,
phenols, pyrolytic lignin…
COOHCOOH
COOH
O
OH
OH
OH OH
O
CHO
OH
CHO
OH
CHO
O
CHO
O
CH2OH
IKFT
17 19.09.2012
Use of pyrolysis products
Separation of valuable components
Produce BioSyncrude from pyrolysis oil and char
for gasification and synthesis gas generation
Use of char for mono- and co-combustion for
heat and electrical power production
Upgrade of pyrolysis oils for
Fuel production
Refinery crude
Stabilization
H2, catalyst
175-250 °C, 20
MPa, min.
Hydrodexoygenation
H2, catalyst
>250 °C, 20 MPa
min.-hour
Hydrocracking
H2, catalyst
>250 °C, 35 MPa
hour
Stable
fragments
soluble in
water
Non-polar
fragments
insoluble
in water
> 1.0 g cm-3
Non-polar
fragments
insoluble in
water
< 1.0 g cm-3
Pyrolysis
oil
CxHy CxHy
Methanation Methanation
Mild hydro-treating of pyrolysis oils
according to Venderbosch, Prins 2010
IKFT
18 19.09.2012
BioSyncrude preparation
Free flowing suspension
High particle content up to 40wt.%
Stable for storage and transport
Easy to produce by colloidal mixing
Heating value up to 25 MJ/kg
Particle diameter / m
Dis
trib
utio
n s
um
Original char
Colloidal mixed char
IKFT
19 19.09.2012
Effect of energy densification by fast pyrolysis
Transport distance / km
100
50
0
0 100 200 300 400 500
30 km
250 km
Tra
nsp
ort
co
sts
€/t
(w
af)
BioSyncrude
Rail
Truck
Straw
Rail
Tra
ctor
Truck
KIT: Leible et al.
IKFT
20 19.09.2012
Suitable for feeds rich of ash
Gasification with oxygen
Temp. >1200 °C, up to 80 bar
Proof at the 3-5 MWth gasifier of
Future Energy (today Siemens FGT)
Tar free synthesis gas
No syngas compression
High pressure entrained flow gasification
boiler
feedwater
water pipe
gasifier reaction
chamber
> 1500 °C
liquid slag
solid slag
Cooling screen detail refractory
ramming mix
IKFT
21 19.09.2012
High pressure entrained flow gasification
IKFT
22 19.09.2012
Pilot gasifier
IKFT
23 19.09.2012
0
10
20
30
40
50
60
70
80
5 10 15 20 25 30
Co
ld g
as
eff
icie
nc
y /
%
BioSyncrude heating value (MJ/kg)
Pilot gasifier in
Freiberg, Germany
Gasification test campaigns
Komponent Vol.%
H2 20 – 25
CO 25 – 37
CO2 12 - 18
CH4 0 - 1
H2O 25 - 30
O2 0
N2 4 – 15
Typical syngas composition
IKFT
24 19.09.2012
ATMO (1 bar) PAT (up to 20 bar) Spray at 16 bar
Burner development
Liq
uid
feed
Gas
Gas Two-fluid nozzle
T. Kolb, ITC
IKFT
25 19.09.2012
High pressure hot gas cleaning
Hot gas filter for particle removal
Dry sorption for separation of
sour gases and alkali salts
Catalytic decomposition of
organic and nitrogen containing
compounds
CO2-separation (optional)
1000 Nm3/h synthesis gas
(45 Bm³/h at 80 bar, 800 °C)
Successfully verified in bench scale
Energy savings up to 10 %
Potential for process integration
Catalytic
ceramic filter
Raw syngas Syngas
Entrained flow adsorbens
Ceramic
particle filter
Fixed bed
sorption
Catalytic
reactor
Raw syngas Syngas
IKFT
26 19.09.2012
DME and fuel synthesis
DME-synthesis
One step DME synthesis
Innovative isothermal reactor
Temp. of 250 °C, pressure 60 bar
Lower investment costs
Direct use of CO-rich syngas
DtG-synthesis
Zeolithe catalyzed Dehydratization, oligomerization and isomerization
Temp. 350 - 450 °C, pressure 25 bar
Recycling of unconverted gas
Gasoline stabilization
high selectivity towards one product
methanol route useful for oxygenates
Flare
Air
Gasoline
Heavy fractionSeparator
Gasoline reactor
DME-reactor
WGS-reactor
Syngas
Desorber
CO
2 -Ab
so
rbe
r
CO
2 -Ab
so
rbe
r
Process water
Cycle gas
Dis
tilla
tio
n
CO2
IKFT
27 19.09.2012
Synthesis pilot plant
IKFT
28 19.09.2012
Catalyst preparation
Catalyst characterization
Screening in lab scale
Process development unit MOSYS
Syngas MeOH DME Olefins Fuels
EtOH + higher alcohols
Syngas-To-DME (STD) DME-To-Gasoline (DTG)
Syngas-To-Alcohols (STA) Dimethylether-To-Olefins (DTO)
0 10 20 30 40 50 60 70 80 90 100
-50
-25
0
25
50
75
100
125
150
175
200
225
250
275
Ottokraftstoff (DIN EN 228)
MLV1-14
MKL01-11
Tem
pera
tur
/ °C
Verdampfte Menge / Gew.%
Simulated distillation
curves of products
without up-grading
compared to gasoline
R&D on syngas chemistry
IKFT
29 19.09.2012
Process efficiency
To produce 1 t of synthetic biofuel 7 to of air dried biomass are required
Around 45% of the energy initially contained in the biomass remain in
the fuel
Residual heat can be used for electrical power production
Both can be used to make the process nearly energy autarkic
Therefore, the process provides a high CO2 reduction potential
IKFT
30 19.09.2012
Process implementation
Operation of the pilot plant
reliable cost estimate, practical experience
Construction and operation of a demo plant
Complementary R&D in lab and bench scale
Optimisation, process alternatives, new applications
Verification of potential feed stock range and availability
Different types of biomass
Alternative use of biosyncrude for:
Co-combustion (Power plant)
Mono-combustion (CHP)
Upgrading to refinery compatible fuel
Development of new products, e.g. oxygenates
Oxygen is contained in biomass for free!
Biomass much better fits to chemicals than to fuels capacities
Business models in cooperation with industry and other partners
IKFT
31 19.09.2012
„Stone era did not end because a lack of stones, and the oil era will not end up because oil is running out “
Sheich Zaki Yamani, 1974
former minister from Saudi Arab