Transcript Production of advanced biofuels: Co-refining upgraded
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 2
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 3
Energy scenario
200 180 160 140 120 100 80 60 40 20 0 2000 2025 Expected increase in bio-fuels demand Ref: Shell energy scenarios to 2050 (Shell International BV, 2008) 2050 Biofuels Electricity Gaseous hydrocarbon fuels Liquid fuels fossil-derived Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010 4
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
400 550 ºC 2 seconds Inert atmosphere Oil yield: 60-70 wt.% Energy yield:~ 60-70 %
Upgrading
Hydrodeoxygenation Reduction Oxygen and Water content Improve miscibility fossil fuel Reduce acidity… Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010 6
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 7
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
.
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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?
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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 10
Upgrading treatment – Hydrodeoxygenation (HDO)
Rupture disc H2 supply vessel 400 bar TI PI N2 – Low pressure supply line (10 bar) TI TI C PI Active catalyst (Ru/C) High H 2 pressure Vent Gas sample Long residence time (>4h) 200-400 °C, >200 bar.
Batch autoclave 5L Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010 11
Upgrading Products
Pyrolysis oil + H 2
HDO
Final T: 230-340 °C P: 290 bar
F. De Miguel Mercader et al. Applied Catal. B 96 (2010) 57-66
Oil Phase dry yield: 47-50 wt.% Energy yield: 55-68 % (MJ HDO oil / MJ PO+H 2 ) Gas Phase dry yield: 3-9 wt.% Aqueous Phase dry yield: 39-14 wt.% Produced water dry yield: 9-19 wt.% Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010 12
Oil properties and H
2
consumption
C dry (wt.%) H dry (wt.%) O dry (wt.%) Water (wt.%) HHV (MJ/kg) MCRT dry (wt.%) Feed oil 54 7 39 25 17 27 HDO oils 63-74 9-10 28-16 16-2 25-35 14-2 Temperature ( °C) NL H 2 /kg feed oil NL H 2 /MJ of product 230 232 21.6
260 237 22.0
300 290 22.3
330 297 21.8
340 326 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 14
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 Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010 15
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 16
Co-refining product yields
30 20 10 0 100 60 50 40 90 80 70 Other Coke yield Drygas yield LCO yield Gasoline yield LPG yield 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
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Influence of blending
110 100 90 80 70 60 50 40 30 20 Others Coke Dry gas LCO Gasoline LPG 10 0 Long residue reference HDO 300 °C 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 18
Quality parameters
10 5 0 30 25 20 15 230 °C 260 °C 1.8
1.6
300 °C 1.4
1.2
330 °C 1 0.8
0.6
230 °C 340 °C 260 °C O dry (wt.%) MCRT (wt.%) MCRT blend (wt.%) 300 °C 330 °C H/Ceff = H - 2*O 340 °C H/Ceff blend H/Ceff Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010 19
Biomass route
Mass (g) Biomass 100 Pyrolysis oil 65 HDO oil 26 Gasoline, LPG & LCO 20 Average yields (%) 65 40 1.5 g H2 / 100 g biomass 75 Carbon (g) Average yields (%) Biomass 100 61 Pyrolysis oil 61 63 HDO oil 38 85 Gasoline, LPG &LCO 32 Neue Biokraftstoffe 2010 – Berlin, 23-24 Juni 2010 20
Hydrodesulphurisation unit (HDS)
Lab-scale HDS reactor – Co-refining model compounds 100 90 80 70 60 50 40 30 20 10 0 280 300 320
reaction temperature (°C)
340 360 Inhibition at low temperature Competition HDS/HDO
Bui V. N., Toussaint G., Laurenti D., Mirodatos, C. Geantet C., Catal. Today 143 (2009) 172.
crude GO 5000 ppm guaiacol
Constant Oxygen content 0.5 wt% WGS, methanation competition
Pinheiro A., Hudebine D., Dupassieux N. and Geantet C.
Energy Fuels 2009, 23(2) 1007.
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Hydrodesulphurisation unit (HDS)
Lab-scale HDS reactor – Co-refining HDO oils 80 70 60 50 40 30 20 10 0 crude SRGO SRGO 10% SRGO 10% HDO 527T SRGO 10% HDO 529B SRGO/HDO oil/i-propanol 80/10/10 Two phases obtained Co-refining only soluble part BIO OIL O%w BIO OIL H2O %w S*10 m/kg after HDS 360 °C, 4 MPa, LHSV 2h -1 Initial catalyst activity recovered after co-processing
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
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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 23
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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