Production of advanced biofuels:
Co-refining upgraded pyrolysis oil
F. de Miguel Mercader, Kees Hogendoorn (University of Twente)
C. Geantet, G. Toussaint (IRCELYON)
Contents
 Introduction
 Energy scenario
 Co-refining pyrolysis oil (BIOCOUP concept)
 Advanced bio-fuels, advantages co-refining
 Biomass route
 Pyrolysis oil upgrading – Hydrodeoxygenation
 Product yields/properties
 Co-refining upgraded pyrolysis oil
 Conclusions
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Contents
 Introduction
 Energy scenario
 Co-refining pyrolysis oil (BIOCOUP concept)
 Advanced bio-fuels, advantages co-refining
 Biomass route
 Pyrolysis oil upgrading – Hydrodeoxygenation
 Product yields/properties
 Co-refining upgraded pyrolysis oil
 Conclusions
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Energy scenario
200
180
160
140
EJ / year
120
Biofuels
Electricity
100
Gaseous hydrocarbon fuels
Liquid fuels fossil-derived
80
60
40
20
0
2000
2025
2050
 Expected increase in bio-fuels demand
Ref: Shell energy scenarios to 2050 (Shell International BV, 2008)
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Co-refining pyrolysis oil
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Biomass route
Ligno-cellulosic
Biomass (waste)
Pyrolysis oil
~ 50 wt.% oxygen
~20-30 wt.% water
Refinery
Co-refining
Pyrolysis
Upgrading
400-550 ºC
2 seconds
Inert atmosphere
Oil yield: 60-70 wt.%
Energy yield:~ 60-70 %
Hydrodeoxygenation
Reduction Oxygen and Water content
Improve miscibility fossil fuel
Reduce acidity…
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Advanced bio-fuels
 Contribute to secure the supply of fuels
 The reduction of green-house-gas emissions
 Do not compete with the food chain
 Produced from a wider range of ligno-cellulosic biomass
 agricultural waste,
 wood,
 forest residues
 …
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Advantages of co-refining upgraded pyrolysis oil
 The use of decentralised pyrolysis plants that can be near the biomass
production site. This means that only the oil is transported, reducing
transportation costs due to the increase of the volumetric energy of the oil
compared to the original biomass.
 After pyrolysis, large part of the minerals from biomass is not transferred to
the oil but remain as ash. Thus, pyrolysis oil contains less inorganic
material that could poison subsequent catalytic processes. Moreover, the ash
can be returned to the soil as fertiliser.
 As the upgrading plant would be next to (or inside) the refinery, all the
necessary utilities would be already available and the product obtained after
co-refining could use the existing distribution network.
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Is co-refining possible?
 What should the upgrading severity be?
 How much oxygen removal?
 How much hydrogen is need for upgrading?
 In which refinery unit should the oil be co-refined?
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Contents
 Introduction
 Energy scenario
 Co-refining pyrolysis oil (BIOCOUP concept)
 Advanced bio-fuels, advantages co-refining
 Biomass route
 Pyrolysis oil upgrading – Hydrodeoxygenation
 Product yields/properties
 Co-refining upgraded pyrolysis oil
 Conclusions
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Upgrading treatment – Hydrodeoxygenation (HDO)
Rupture
disc
TI
TI
C
TI PI
H2 supply vessel
400 bar
PI
N2 – Low pressure
supply line (10 bar)
Vent
Gas sample
 Active catalyst (Ru/C)
 Long residence time (>4h)
 High H2 pressure
 200-400 °C, >200 bar.
 Batch autoclave 5L
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Upgrading Products
Oil Phase
dry yield: 47-50 wt.%
Energy yield: 55-68 %
(MJ HDO oil / MJ PO+H2)
Gas Phase
+ H2
dry yield: 3-9 wt.%
Pyrolysis oil
HDO
Final T: 230-340 °C
Aqueous Phase
dry yield: 39-14 wt.%
P: 290 bar
Produced water
dry yield: 9-19 wt.%
F. De Miguel Mercader et al. Applied Catal. B 96 (2010) 57-66
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Oil properties and H2 consumption
Feed oil
HDO oils
C dry (wt.%)
54
63-74
H dry (wt.%)
7
9-10
O dry (wt.%)
39
28-16
Water (wt.%)
25
16-2
HHV (MJ/kg)
17
25-35
MCRT dry (wt.%)
27
14-2
Temperature (°C)
230
260
300
330
340
NL H2/kg feed oil
232
237
290
297
326
NL H2/MJ of product
21.6
22.0
22.3
21.8
23.6
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Contents
 Introduction
 Energy scenario
 Co-refining pyrolysis oil (BIOCOUP concept)
 Advanced bio-fuels, advantages co-refining
 Biomass route
 Pyrolysis oil upgrading – Hydrodeoxygenation
 Product yields/properties
 Co-refining upgraded pyrolysis oil
 Conclusions
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Where should HDO oil be co-refined?
 Two refinery units have been evaluated
 Fluid catalytic cracking (FCC)
 Used to treat heavy refinery feedstocks to lighter more useful fractions
such as gasoline, LCO,…
 Pyrolysis oil contains heavy molecules
 Hydrodesulphurisation
 Used to remove sulphur from fossil fuel to meet environmental
specifications
 Similar to HDO process
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Catalytic cracking
 Lab-scale FCC reactor – MAT-5000 - 520 ºC
 Equilibrium catalyst from Shell’s FCC units
 Co-refining 20 wt.% HDO oils + 80 wt.% Long Residue
 Complete solubility
 Successful processing without plugging of lines
 Product near oxygen free (some phenolics remaining)
 Product analysed by true boiling point fractions
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Co-refining product yields
100
90
Catalytic cracking yields (wt.%)
80
70
Other
60
Coke yield
Drygas yield
50
LCO yield
Gasoline yield
40
LPG yield
30
20
10
0
Long residue
20% HDO oil (230 C)
20% HDO oil (300 C)
20% HDO oil (340 C)
 Product yields (corrected by water production) independent of HDO severity
F. De Miguel Mercader et al. Applied Catal. B 96 (2010) 57-66
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Influence of blending
110
Catalytic cracking yields (wt. %)
100
90
80
Others
Coke
Dry gas
LCO
Gasoline
LPG
70
60
50
40
30
20
10
0
Long residue HDO 300 °C
reference extrapolated
HDO 300 °C
measured
 Coke yields much higher when HDO oil processed undiluted
 Hydrogen transfer from long residue required for good product distribution
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Quality parameters
30
25
20
O dry (wt.%)
15
MCRT (wt.%)
MCRT blend (wt.%)
10
H/Ceff = H - 2*O
1.8
5
1.6
0
1.4
230 °C
260 °C
300 °C
330 °C
340 °C
H/Ceff blend
1.2
H/Ceff
1
0.8
0.6
230 °C
260 °C
300 °C
330 °C
340 °C
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Biomass route
Mass (g)
Biomass
Pyrolysis oil
HDO oil
Gasoline,
LPG & LCO
100
65
26
20
Average yields (%)
65
40
75
1.5 g H2 / 100 g biomass
Carbon (g)
Average yields (%)
Biomass
Pyrolysis oil
HDO oil
Gasoline,
LPG &LCO
100
61
38
32
61
63
85
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Hydrodesulphurisation unit (HDS)
 Lab-scale HDS reactor – Co-refining model compounds
100
90
80
conversion (%)
70
crude GO
60
50
5000 ppm
guaiacol
40
30
20
10
0
280
300
320
340
360
reaction temperature (°C)
Inhibition at low temperature
Constant Oxygen content 0.5 wt%
Competition HDS/HDO
WGS, methanation competition
Bui V. N., Toussaint G., Laurenti D., Mirodatos,
C. Geantet C., Catal. Today 143 (2009) 172.
Pinheiro A., Hudebine D., Dupassieux N. and Geantet C.
Energy Fuels 2009, 23(2) 1007.
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Hydrodesulphurisation unit (HDS)
S content after HDS, O content and H2O content of biooils
 Lab-scale HDS reactor – Co-refining HDO oils
80
SRGO/HDO oil/i-propanol
80/10/10
Two phases obtained
Co-refining only soluble part
70
60
50
BIO OIL O%w
40
BIO OIL H2O %w
S*10 m/kg after HDS
360 °C, 4 MPa, LHSV 2h-1
30
20
Initial catalyst activity
recovered after co-processing
10
0
crude
SRGO
SRGO 10% SRGO 10% SRGO 10%
HDO330
318C HDO
HDO 300
527T
529B
HDO
C HDO
HDO 270
C
C. Geantet, G. Toussaint, L. Braconnier, C. Mirodatos, F. De Miguel Mercader, J. A. Hogendoorn et al. (IRCELYON and University
of Twente): Co-processing of SRGO and hydrotreated bio-oils.
The 5th International symposium of molecular aspects of catalysis by sulphides (MACS V). 30 May to 3 June 2010. Copenhagen
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Contents
 Introduction
 Energy scenario
 Co-refining pyrolysis oil (BIOCOUP concept)
 Advanced bio-fuels, advantages co-refining
 Biomass route
 Pyrolysis oil upgrading – Hydrodeoxygenation
 Product yields/properties
 Co-refining upgraded pyrolysis oil
 Conclusions
Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010
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Conclusions
 Increasing HDO severity
 Increases carbon/energy recovery
 Reduces oxygen and water content
 Successful catalytic cracking co-refining of HDO oil (with high oxygen content)
with Long Residue
 Gasoline, LCO and LPG yields remain similar to reference
 The presence of fossil feed appears to be very important
 HDS inhibition is detected for certain oxygenated model compounds and for
HDO oils
 The molecular composition or water content of the HDO oils do not drastically
affect the performances of the catalysts.
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Acknowledgments
 All BIOCOUP partners
 Special thanks to N.W.J. Way & C.J. Schaverien from Shell Global
Solutions International BV.
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Thank you for you attention!