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Title: Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration

Abstract

Catalytic fast pyrolysis (CFP) has emerged as an attractive process for the conversion of lignocellulosic biomass into renewable fuels and products. Considerable research and development has focused on using circulating-bed reactors with zeolite catalysts (e.g., HZSM-5) for CFP because of their propensity to form gasoline-range aromatic hydrocarbons. However, the high selectivity for aromatics comes at the expense of low carbon yield, a key economic driver for this process. In this contribution, we evaluate non-zeolite catalysts in a fixed-bed reactor configuration for an integrated CFP process to produce fuel blendstocks from lignocellulosic biomass. These experimental efforts are coupled with technoeconomic analysis (TEA) to benchmark the process and guide research and development activities to minimize costs. The results indicate that CFP bio-oil can be produced from pine with improved yield by using a bifunctional metal-acid 2 wt% Pt/TiO 2 catalyst in a fixed-bed reactor operated with co-fed H 2 at near atmospheric pressure, as compared to H-ZSM5 in a circulating-bed reactor. The Pt/TiO 2 catalyst exhibited good stability over 13 reaction-regeneration cycles with no evidence of irreversible deactivation. The CFP bio-oil was continuously hydrotreated for 140 h time-on-stream using a single-stage system with 84 wt% of the hydrotreated product having a boilingmore » point in the gasoline and distillate range. This integrated biomass-to-blendstock process was determined to exhibit an energy efficiency of 50% and a carbon efficiency of 38%, based on the experimental results and process modelling. TEA of the integrated process revealed a modelled minimum fuel selling price (MFSP) of $4.34 per gasoline gallon equivalent (GGE), which represents a cost reduction of $0.85 GGE -1 compared to values reported for CFP with a zeolite catalyst. TEA also indicated that catalyst cost was a significant factor influencing the MFSP, which informed additional CFP experiments in which lower-cost Mo2C and high-dispersion 0.5 wt% Pt/TiO 2 catalysts were synthesized and evaluated. These materials demonstrated CFP carbon yield and oil oxygen content similar to those of the 2 wt% Pt/TiO 2 catalyst, offering proof-of-concept that the lower-cost catalysts can be effective for CFP and providing a route to reduce the modelled MFSP to $3.86–3.91 GGE -1. This report links foundational science and applied engineering to demonstrate the potential of fixed-bed CFP and highlights the impact of coupled TEA to guide research activities towards cost reductions.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1468521
Alternate Identifier(s):
OSTI ID: 1465598; OSTI ID: 1490208; OSTI ID: 1492554
Report Number(s):
NREL/JA-5100-71877; PNNL-SA-136791
Journal ID: ISSN 1754-5692
Grant/Contract Number:  
AC36-08GO28308; AC02-06CH11357; AC06-76RL01830; AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 10; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; catalytic fast pyrolysis; biomass; bio-oil

Citation Formats

Griffin, Michael B., Iisa, Kristiina, Wang, Huamin, Dutta, Abhijit, Orton, Kellene A., French, Richard J., Santosa, Daniel M., Wilson, Nolan, Christensen, Earl, Nash, Connor, Van Allsburg, Kurt M., Baddour, Frederick G., Ruddy, Daniel A., Tan, Eric C. D., Cai, Hao, Mukarakate, Calvin, and Schaidle, Joshua A. Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration. United States: N. p., 2018. Web. doi:10.1039/C8EE01872C.
Griffin, Michael B., Iisa, Kristiina, Wang, Huamin, Dutta, Abhijit, Orton, Kellene A., French, Richard J., Santosa, Daniel M., Wilson, Nolan, Christensen, Earl, Nash, Connor, Van Allsburg, Kurt M., Baddour, Frederick G., Ruddy, Daniel A., Tan, Eric C. D., Cai, Hao, Mukarakate, Calvin, & Schaidle, Joshua A. Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration. United States. doi:10.1039/C8EE01872C.
Griffin, Michael B., Iisa, Kristiina, Wang, Huamin, Dutta, Abhijit, Orton, Kellene A., French, Richard J., Santosa, Daniel M., Wilson, Nolan, Christensen, Earl, Nash, Connor, Van Allsburg, Kurt M., Baddour, Frederick G., Ruddy, Daniel A., Tan, Eric C. D., Cai, Hao, Mukarakate, Calvin, and Schaidle, Joshua A. Tue . "Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration". United States. doi:10.1039/C8EE01872C. https://www.osti.gov/servlets/purl/1468521.
@article{osti_1468521,
title = {Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration},
author = {Griffin, Michael B. and Iisa, Kristiina and Wang, Huamin and Dutta, Abhijit and Orton, Kellene A. and French, Richard J. and Santosa, Daniel M. and Wilson, Nolan and Christensen, Earl and Nash, Connor and Van Allsburg, Kurt M. and Baddour, Frederick G. and Ruddy, Daniel A. and Tan, Eric C. D. and Cai, Hao and Mukarakate, Calvin and Schaidle, Joshua A.},
abstractNote = {Catalytic fast pyrolysis (CFP) has emerged as an attractive process for the conversion of lignocellulosic biomass into renewable fuels and products. Considerable research and development has focused on using circulating-bed reactors with zeolite catalysts (e.g., HZSM-5) for CFP because of their propensity to form gasoline-range aromatic hydrocarbons. However, the high selectivity for aromatics comes at the expense of low carbon yield, a key economic driver for this process. In this contribution, we evaluate non-zeolite catalysts in a fixed-bed reactor configuration for an integrated CFP process to produce fuel blendstocks from lignocellulosic biomass. These experimental efforts are coupled with technoeconomic analysis (TEA) to benchmark the process and guide research and development activities to minimize costs. The results indicate that CFP bio-oil can be produced from pine with improved yield by using a bifunctional metal-acid 2 wt% Pt/TiO2 catalyst in a fixed-bed reactor operated with co-fed H2 at near atmospheric pressure, as compared to H-ZSM5 in a circulating-bed reactor. The Pt/TiO2 catalyst exhibited good stability over 13 reaction-regeneration cycles with no evidence of irreversible deactivation. The CFP bio-oil was continuously hydrotreated for 140 h time-on-stream using a single-stage system with 84 wt% of the hydrotreated product having a boiling point in the gasoline and distillate range. This integrated biomass-to-blendstock process was determined to exhibit an energy efficiency of 50% and a carbon efficiency of 38%, based on the experimental results and process modelling. TEA of the integrated process revealed a modelled minimum fuel selling price (MFSP) of $4.34 per gasoline gallon equivalent (GGE), which represents a cost reduction of $0.85 GGE-1 compared to values reported for CFP with a zeolite catalyst. TEA also indicated that catalyst cost was a significant factor influencing the MFSP, which informed additional CFP experiments in which lower-cost Mo2C and high-dispersion 0.5 wt% Pt/TiO2 catalysts were synthesized and evaluated. These materials demonstrated CFP carbon yield and oil oxygen content similar to those of the 2 wt% Pt/TiO2 catalyst, offering proof-of-concept that the lower-cost catalysts can be effective for CFP and providing a route to reduce the modelled MFSP to $3.86–3.91 GGE-1. This report links foundational science and applied engineering to demonstrate the potential of fixed-bed CFP and highlights the impact of coupled TEA to guide research activities towards cost reductions.},
doi = {10.1039/C8EE01872C},
journal = {Energy & Environmental Science},
number = 10,
volume = 11,
place = {United States},
year = {2018},
month = {8}
}

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Works referenced in this record:

Chemical Titration and Transient Kinetic Studies of Site Requirements in Mo 2 C-Catalyzed Vapor Phase Anisole Hydrodeoxygenation
journal, June 2015


Late-Transition-Metal-Modified β-Mo 2 C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation
journal, November 2017

  • Baddour, Frederick G.; Witte, Vanessa A.; Nash, Connor P.
  • ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 12
  • DOI: 10.1021/acssuschemeng.7b02544

Catalytic routes for the conversion of biomass into liquid hydrocarbon transportation fuels
journal, January 2011

  • Serrano-Ruiz, Juan Carlos; Dumesic, James A.
  • Energy Environ. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C0EE00436G

Role of Oxophilic Supports in the Selective Hydrodeoxygenation of m-Cresol on Pd Catalysts
journal, September 2014


Zeolite-catalyzed biomass conversion to fuels and chemicals
journal, January 2011

  • Taarning, Esben; Osmundsen, Christian M.; Yang, Xiaobo
  • Energy Environ. Sci., Vol. 4, Issue 3
  • DOI: 10.1039/C004518G

Catalytic Pyrolysis of Pine Over HZSM-5 with Different Binders
journal, October 2015

  • Iisa, Kristiina; French, Richard J.; Orton, Kellene A.
  • Topics in Catalysis, Vol. 59, Issue 1
  • DOI: 10.1007/s11244-015-0509-3

Experimental and Computational Investigation of Acetic Acid Deoxygenation over Oxophilic Molybdenum Carbide: Surface Chemistry and Active Site Identity
journal, January 2016

  • Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.
  • ACS Catalysis, Vol. 6, Issue 2
  • DOI: 10.1021/acscatal.5b01930

Catalytic Hydroprocessing of Fast Pyrolysis Bio-oil from Pine Sawdust
journal, May 2012

  • Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G.
  • Energy & Fuels, Vol. 26, Issue 6
  • DOI: 10.1021/ef3004587

Selective Hydrodeoxygenation of Guaiacol Catalyzed by Platinum Supported on Magnesium Oxide
journal, August 2012


Characterization and Catalytic Upgrading of Aqueous Stream Carbon from Catalytic Fast Pyrolysis of Biomass
journal, November 2017


Role of Keto Intermediates in the Hydrodeoxygenation of Phenol over Pd on Oxophilic Supports
journal, January 2015

  • de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P.
  • ACS Catalysis, Vol. 5, Issue 2
  • DOI: 10.1021/cs501853t

In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System
journal, December 2015


Hydrocarbon Liquid Production from Biomass via Hot-Vapor-Filtered Fast Pyrolysis and Catalytic Hydroprocessing of the Bio-oil
journal, August 2014

  • Elliott, Douglas C.; Wang, Huamin; French, Richard
  • Energy & Fuels, Vol. 28, Issue 9
  • DOI: 10.1021/ef501536j

Selective conversion of furfural to cyclopentanone or cyclopentanol using different preparation methods of Cu–Co catalysts
journal, January 2015

  • Li, Xing-Long; Deng, Jin; Shi, Jing
  • Green Chemistry, Vol. 17, Issue 2
  • DOI: 10.1039/C4GC01601G

Quantitative 13 C NMR characterization of fast pyrolysis oils
journal, January 2016

  • Happs, R. M.; Iisa, K.; Ferrell III, J. R.
  • RSC Advances, Vol. 6, Issue 104
  • DOI: 10.1039/C6RA24044E

Reactive catalytic fast pyrolysis of biomass to produce high-quality bio-crude
journal, January 2017

  • Wang, Kaige; Dayton, David C.; Peters, Jonathan E.
  • Green Chemistry, Vol. 19, Issue 14
  • DOI: 10.1039/C7GC01088E

Fast pyrolysis oil from pinewood chips co-processing with vacuum gas oil in an FCC unit for second generation fuel production
journal, January 2017


Catalytic Fast Pyrolysis: Influencing Bio-Oil Quality with the Catalyst-to-Biomass Ratio
journal, July 2016

  • Paasikallio, Ville; Kalogiannis, Konstantinos; Lappas, Angelos
  • Energy Technology, Vol. 5, Issue 1
  • DOI: 10.1002/ente.201600094

Conversion of Guaiacol over Supported Ru Catalysts
journal, June 2013


Oxygen removal from intact biomass to produce liquid fuel range hydrocarbons via fast-hydropyrolysis and vapor-phase catalytic hydrodeoxygenation
journal, January 2015

  • Venkatakrishnan, Vinod Kumar; Delgass, W. Nicholas; Ribeiro, Fabio H.
  • Green Chemistry, Vol. 17, Issue 1
  • DOI: 10.1039/C4GC01746C

Product quality and catalyst deactivation in a four day catalytic fast pyrolysis production run
journal, January 2014

  • Paasikallio, Ville; Lindfors, Christian; Kuoppala, Eeva
  • Green Chemistry, Vol. 16, Issue 7
  • DOI: 10.1039/c4gc00571f

Production of low-oxygen bio-oil via ex situ catalytic fast pyrolysis and hydrotreating
journal, November 2017


Overview of Applications of Biomass Fast Pyrolysis Oil
journal, March 2004

  • Czernik, S.; Bridgwater, A. V.
  • Energy & Fuels, Vol. 18, Issue 2, p. 590-598
  • DOI: 10.1021/ef034067u

Red Mud Catalytic Pyrolysis of Pinyon Juniper and Single-Stage Hydrotreatment of Oils
journal, July 2016


Thermochemical wastewater valorization via enhanced microbial toxicity tolerance
journal, January 2018

  • Jayakody, Lahiru N.; Johnson, Christopher W.; Whitham, Jason M.
  • Energy & Environmental Science, Vol. 11, Issue 6
  • DOI: 10.1039/C8EE00460A

Integrated hydropyrolysis and hydroconversion (IH ) for the direct production of gasoline and diesel fuels or blending components from biomass, Part 2: continuous testing
journal, November 2013

  • Marker, Terry L.; Felix, Larry G.; Linck, Martin B.
  • Environmental Progress & Sustainable Energy, Vol. 33, Issue 3
  • DOI: 10.1002/ep.11906

Integration of catalytic fast pyrolysis and hydroprocessing: a pathway to refinery intermediates and “drop-in” fuels from biomass
journal, January 2016

  • Mante, Ofei D.; Dayton, David C.; Gabrielsen, Jostein
  • Green Chemistry, Vol. 18, Issue 22
  • DOI: 10.1039/C6GC01938B

Historical Developments in Hydroprocessing Bio-oils
journal, May 2007

  • Elliott, Douglas C.
  • Energy & Fuels, Vol. 21, Issue 3, p. 1792-1815
  • DOI: 10.1021/ef070044u

Advances in the study of coke formation over zeolite catalysts in the methanol-to-hydrocarbon process
journal, June 2016


Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating
journal, August 2017


An investigation into support cooperativity for the deoxygenation of guaiacol over nanoparticle Ni and Rh 2 P
journal, January 2017

  • Griffin, Michael B.; Baddour, Frederick G.; Habas, Susan E.
  • Catalysis Science & Technology, Vol. 7, Issue 14
  • DOI: 10.1039/C7CY00261K

Direct catalytic upgrading of biomass pyrolysis vapors by a dual function Ru/TiO 2 catalyst
journal, February 2013

  • Wan, Shaolong; Pham, Trung; Zhang, Sarah
  • AIChE Journal, Vol. 59, Issue 7
  • DOI: 10.1002/aic.14038

Mo2C catalyzed vapor phase hydrodeoxygenation of lignin-derived phenolic compound mixtures to aromatics under ambient pressure
journal, January 2016


Integrated Biorefining: Coproduction of Renewable Resol Biopolymer for Aqueous Stream Valorization
journal, July 2017

  • Wilson, A. Nolan; Price, Mariel J.; Mukarakate, Calvin
  • ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 8
  • DOI: 10.1021/acssuschemeng.7b00864

Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part I: Conversion over various catalysts
journal, December 1995


Field-to-Fuel Performance Testing of Lignocellulosic Feedstocks: An Integrated Study of the Fast Pyrolysis–Hydrotreating Pathway
journal, April 2015


Selective vapor-phase hydrodeoxygenation of anisole to benzene on molybdenum carbide catalysts
journal, November 2014


Production of green aromatics and olefins by catalytic fast pyrolysis of wood sawdust
journal, January 2011

  • Carlson, Torren R.; Cheng, Yu-Ting; Jae, Jungho
  • Energy Environ. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C0EE00341G

Real-time monitoring of the deactivation of HZSM-5 during upgrading of pine pyrolysis vapors
journal, January 2014

  • Mukarakate, Calvin; Zhang, Xiaodong; Stanton, Alexander R.
  • Green Chem., Vol. 16, Issue 3
  • DOI: 10.1039/C3GC42065E

Synthesis of α-MoC 1− x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation
journal, June 2016

  • Baddour, Frederick G.; Nash, Connor P.; Schaidle, Joshua A.
  • Angewandte Chemie International Edition, Vol. 55, Issue 31
  • DOI: 10.1002/anie.201602878

Selective Conversion of Furfural to Cyclopentanone with CuZnAl Catalysts
journal, September 2014

  • Guo, Jianhua; Xu, Guangyue; Han, Zheng
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 10
  • DOI: 10.1021/sc5003566

Experimental and Theoretical Insights into the Hydrogen-Efficient Direct Hydrodeoxygenation Mechanism of Phenol over Ru/TiO 2
journal, October 2015


Experimental and First-Principles Evidence for Interfacial Activity of Ru/TiO 2 for the Direct Conversion of m -Cresol to Toluene
journal, July 2017

  • Omotoso, Taiwo O.; Baek, Byeongjin; Grabow, Lars C.
  • ChemCatChem, Vol. 9, Issue 14
  • DOI: 10.1002/cctc.201700157

Integrated hydropyrolysis and hydroconversion (IH2) for the direct production of gasoline and diesel fuels or blending components from biomass, part 1: Proof of principle testing
journal, December 2011

  • Marker, Terry L.; Felix, Larry G.; Linck, Martin B.
  • Environmental Progress & Sustainable Energy, Vol. 31, Issue 2
  • DOI: 10.1002/ep.10629

Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m -Cresol over Pt/C and Pt/TiO 2 Catalysts
journal, March 2016


Co-processing raw bio-oil and gasoil in an FCC Unit
journal, March 2015

  • Pinho, Andrea de Rezende; de Almeida, Marlon B. B.; Mendes, Fabio Leal
  • Fuel Processing Technology, Vol. 131
  • DOI: 10.1016/j.fuproc.2014.11.008

Catalytic pyrolysis of biomass for biofuels production
journal, January 2010


Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass
journal, January 2016

  • Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar
  • Green Chemistry, Vol. 18, Issue 20
  • DOI: 10.1039/C6GC01189F

Catalytic fast pyrolysis of glucose with HZSM-5: The combined homogeneous and heterogeneous reactions
journal, March 2010


Effective hydrodeoxygenation of biomass-derived oxygenates into unsaturated hydrocarbons by MoO3 using low H2 pressures
journal, January 2013

  • Prasomsri, Teerawit; Nimmanwudipong, Tarit; Román-Leshkov, Yuriy
  • Energy & Environmental Science, Vol. 6, Issue 6, p. 1732-1738
  • DOI: 10.1039/c3ee24360e

Upgrading of lignin-derived bio-oils by catalytic hydrodeoxygenation
journal, January 2014

  • Saidi, Majid; Samimi, Fereshteh; Karimipourfard, Dornaz
  • Energy Environ. Sci., Vol. 7, Issue 1
  • DOI: 10.1039/C3EE43081B

Catalytic upgrading of biomass fast pyrolysis vapors with titania and zirconia/titania based catalysts
journal, August 2010


Reactivity and stability investigation of supported molybdenum oxide catalysts for the hydrodeoxygenation (HDO) of m-cresol
journal, November 2015


Hydrodeoxygenation of Phenol over Zirconia-Supported Catalysts: The Effect of Metal Type on Reaction Mechanism and Catalyst Deactivation
journal, June 2017

  • Teles, Camila A.; Rabelo-Neto, Raimundo C.; Jacobs, Gary
  • ChemCatChem, Vol. 9, Issue 14
  • DOI: 10.1002/cctc.201700047

2016 Billion-Ton Report: Advancing Domestic Resources for a Thriving Bioeconomy
report, July 2016

  • Langholtz, M. H.; Stokes, B. J.; Eaton, L. M.
  • DOE/EE-1440
  • DOI: 10.2172/1271651