termochemical 2 biomass processing · biodiesel, green gasoline and diesel, biomethanol…. --it is...
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Termochemical biomass processing
Buenos Aires (2013)
Dr. Mariano Martín Assistant professor
University of Salamanca (Spain)
H2
H2
H2
H2
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Overview
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Introduction Energy in the world Biomass as raw material Approach to process synthesis Gasification based Hydrogen from switchgrass Bioethanol from switchgrass (2nd generation) Via gasification FT diesel from switchgrass Pyrolysis based Conclusions
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Introduction
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Energy in the world: Contribution of renewables[1]
[1] BP annual report
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Alternatives
Primary building blocks
BioOil
Gasification
Pyrolysis
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Gasification
GASIFICATION of
Lignocellulosic materials
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Biomass (Energy) CO + H2
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Gasification
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Gasification
Uses Air Two chambers Higher conc. HBC
Requires O2
One chamber High pressure Lower conc. HBC
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
CO2
CO H2
H2O CH4
C2H2
C2H4
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Reforming
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Steam reforming Higher hydrogen production Endothermic reaction. Lower energy available within the process
Partial oxidation Lower hydrogen production Exothermic reaction. More energy within the process
Gasification
1) Steam reforming 2) Partial oxidation 3) Autoreforming 4) Dry reforming (CO2)
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
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Clean up
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Water
Gasification
Solids Ammonia
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
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Water Gas Shift Reactor
9 Ji, P., Feng, W., & Chen, B. (2009a). Chem. Eng. Sci. 64, 582–592
H2O + CO H2+CO2
Production of HYDROGEN from Switchgrass
Gasification - Hydrogen
Martín, M., Grossmann, I.E. doi:10.1016/j.compchemeng.2011.03.002
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Gasification - Hydrogen
Optimal flowsheet for the production of HYDROGEN from Switchgrass
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$0.68/kg, $148MM
Martín, M., Grossmann, I.E. doi:10.1016/j.compchemeng.2011.03.002
TARGET (DOE) $1.68/kg
Mathematical programming techniques Superstructure optimization
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CO/H2 Adj.
WGSR
H2 PSA
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Water
Ratio H2/CO from 1:1 Ethanol 1.7-2: FT 2: Methanol
Gasification
H2
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
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Sour gases removal CO2 & H2S
MEA Removal of CO2 and H2S
PSA Removal of CO2
Membrane Porous to CO2
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Gasification
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
Other methods -Rectisol (p>50bar) -CaO + CO2 CaCO3
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Fermentation
3CO+3H2 CH3CH2OH + CO2
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Gasification- Bioethanol
Huge energy consumption
Production of BIOETHANOL via gasification of Switchgrass
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
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Production of BIOETHANOL via gasification of Switchgrass
Fermentation
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
Gasification- Bioethanol
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Rectification
Ads Corn Grit.
Molecular Sieves
Pervaporation
Ethanol dehydration
15 Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
Gasification- Bioethanol Production of BIOETHANOL via gasification of Switchgrass
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To cleanup Catalysis
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From sour gas removal
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
Gasification- Bioethanol
Production of BIOETHANOL via gasification of Switchgrass
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Optimal flowsheet for the production of BIOETHANOL via gasification of Switchgrass
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$0.41/gal, $335MM
Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
H2
Major savings due to income from excess of H2
TARGET (DOE) $1/gal
Gasification- Bioethanol
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18 Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: 10.1002/aic.12544
Energy consumption: Bioethanol
Water consumption: Bioethanol
Martín, M.; Ahmetovic, E.; Grossmann, I.E. (2011) Ind. Eng. Chem Res DOI: doi: 10.1021/ie101175p
Gasification- Bioethanol
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FT reactor operating conditions to optimize Diesel production
( )( )( )2
0.2332* 0.633 * 1 0.0039* T _ Synthesis 273 533 CO
H CO
yy y
α = + − + − +
The product distribution depends on H2/CO ratio Operating temperature Operating Pressure
Song Hyun-Seob, S et al Korean J. Chem., 2004, 21, 308-317.
Production of FT DIESEL AND GREEN GASOLINE via gasification of Switchgrass
Gasification- FT liquids
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Hydrocracking operating conditions to optimize Diesel production
Hydrocracking in the FT- fuels production: Using the experimental values from an hydrocracking reactor we develop correlations to predict the conversion as function of the temperature
Bezergianni, S et al. Bioresour. Technol. 2009, 100, 3036–3042
Gasification- FT liquids
Production of FT DIESEL AND GREEN GASOLINE via gasification of Switchgrass
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Optimal flowsheet for the production of FT Diesel via gasification of Switchgrass
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$0.72/gal, $212MM
Martín, M., Grossmann, I.E. (2011) Ind Eng. Chem Res. 50 (23),13485–13499
Gasification- FT liquids
$0.72/gal
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Gasification Summary
Trade-offs Investment vs operation cost
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Pyrolysis
Fast Pyrolysis of Lignocellulosic
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We do not break down the biomass to syngas Lower operating temperature We obtain a wide range of products
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24 Bridgewater biomass and bioenergy 38 (2012) 68-94
Bubbling fluid bed reactor
Circulating fluid bed reactor
Pyrolysis
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25 Brown et al Biofuels. Bioprod. Biorefin. 2012, 6 (1), 73−87.
Pyrolysis
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26 Brown et al Biofuels. Bioprod. Biorefin. 2012, 6 (1), 73−87.
Capital costs from $99 MM to $112 MM and operating costs from $70 MM/yr to $90 MM /yr . Hydrotreatment is needed for a positive internal rate of return (IRR)
Pyrolysis
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Conclusions
--Biomass and waste are promising raw material for biofuels. --The range of biofuels is broad: hydrogen, bioethanol, biodiesel, green gasoline and diesel, biomethanol…. --It is feasible to produce second generation of biofuels but further development is required in purification and reaction technologies to increase water recycle and reuse and increase the yield of the processes.
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Ackowledgement: Prof. Ignacio E. Grossmann