Termochemical biomass processing

Transcription

1 Termochemical biomass processing H2 H2 H2 H2 Buenos Aires (2013) Dr. Mariano Martín Assistant professor University of Salamanca 1 (Spain)

2 Overview Introduction Energy in the world Biomass as raw material Approach to process synthesis Gasification based Hydrogen from switchgrass Bioethanol from switchgrass (2 nd generation) Via gasification FT diesel from switchgrass Pyrolysis based Conclusions 2

3 Introduction Energy in the world: Contribution of renewables[1] [1] BP annual report 3

4 Alternatives Primary building blocks Pyrolysis BioOil Gasification 4

5 Gasification GASIFICATION of Lignocellulosic materials Biomass (Energy) CO + H2 5

6 Gasification Gasification Uses Air Two chambers Higher conc. HBC CO2 CO H2 H2O CH4 C2H2 C2H4 Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic Requires O2 One chamber High pressure 6 Lower conc. HBC

7 Gasification Reforming Steam reforming Higher hydrogen production Endothermic reaction. Lower energy available within the process Partial oxidation 1) Steam reforming 2) Partial oxidation 3) Autoreforming 4) Dry reforming (CO2) Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic Lower hydrogen production Exothermic reaction. More energy within the process 7

8 Gasification Clean up Solids Ammonia Water Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic

9 Gasification - Hydrogen Production of HYDROGEN from Switchgrass Water Gas Shift Reactor H2O + CO H2+CO2 Martín, M., Grossmann, I.E. doi: /j.compchemeng Ji, P., Feng, W., & Chen, B. (2009a). Chem. Eng. Sci. 64,

10 Gasification - Hydrogen Optimal flowsheet for the production of HYDROGEN from Switchgrass Mathematical programming techniques Superstructure optimization TARGET (DOE) $1.68/kg $0.68/kg, $148MM Martín, M., Grossmann, I.E. doi: /j.compchemeng

11 Gasification CO/H2 Adj. WGSR H2 Ratio H2/CO from 1:1 Ethanol 1.7-2: FT 2: Methanol Water H2 PSA Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic

12 Gasification MEA Removal of CO2 and H2S Sour gases removal CO2 & H2S PSA Removal of CO2 Membrane Porous to CO2 Other methods -Rectisol (p>50bar) -CaO + CO2 CaCO3 Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic

13 Gasification- Bioethanol Production of BIOETHANOL via gasification of Switchgrass Fermentation Huge energy consumption 3CO+3H2 CH3CH2OH + CO2 Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic

14 Gasification- Bioethanol Production of BIOETHANOL via gasification of Switchgrass Fermentation Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic

15 Gasification- Bioethanol Production of BIOETHANOL via gasification of Switchgrass Rectification Ethanol dehydration Ads Corn Grit. Molecular Sieves Pervaporation Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic

16 Gasification- Bioethanol Production of BIOETHANOL via gasification of Switchgrass To cleanup Catalysis From sour gas removal Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic

17 Gasification- Bioethanol Optimal flowsheet for the production of BIOETHANOL via gasification of Switchgrass Major savings due to income from excess of H2 H2 TARGET (DOE) $1/gal $0.41/gal, $335MM Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic

18 Gasification- Bioethanol Energy consumption: Bioethanol Water consumption: Bioethanol Martín, M., Grossmann, I.E. (2011) AIChE J. DOI: /aic Martín, M.; Ahmetovic, E.; Grossmann, I.E. (2011) Ind. Eng. Chem Res DOI: doi: /ie101175p 18

19 FT reactor operating conditions to optimize Diesel production Gasification- FT liquids Production of FT DIESEL AND GREEN GASOLINE via gasification of Switchgrass The product distribution depends on H2/CO ratio Operating temperature Operating Pressure α yco = * * * T _ Synthesis yh + y 2 CO ( (( ) )) Song Hyun-Seob, S et al Korean J. Chem., 2004, 21,

20 Gasification- FT liquids Production of FT DIESEL AND GREEN GASOLINE via gasification of Switchgrass 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,

21 Gasification- FT liquids Optimal flowsheet for the production of FT Diesel via gasification of Switchgrass $0.72/gal, $212MM $0.72/gal Martín, M., Grossmann, I.E. (2011) Ind Eng. Chem Res. 50 (23),

22 Gasification Summary Trade-offs Investment vs operation cost 22

23 Pyrolysis Fast Pyrolysis of Lignocellulosic We do not break down the biomass to syngas Lower operating temperature We obtain a wide range of products 23

24 Pyrolysis Bubbling fluid bed reactor Circulating fluid bed reactor Bridgewater biomass and bioenergy 38 (2012)

25 Pyrolysis Brown et al Biofuels. Bioprod. Biorefin. 2012, 6 (1),

26 Pyrolysis 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) Brown et al Biofuels. Bioprod. Biorefin. 2012, 6 (1),

27 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. Ackowledgement: Prof. Ignacio E. Grossmann 27