skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

Abstract

Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalytic fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysismore » and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

Authors:
ORCiD logo [1];  [1];  [2];  [2];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Johnson Matthey Technology Centre, Billingham (United Kingdom)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1413902
Report Number(s):
NREL/JA-5100-68436
Journal ID: ISSN 1463-9262; TRN: US1800467
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 20; Journal Issue: 3; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; catalytic fast pyrolysis; vapor phase upgrading; liquid phase upgrading

Citation Formats

Iisa, Kristiina, Robichaud, David J., Watson, Michael J., ten Dam, Jeroen, Dutta, Abhijit, Mukarakate, Calvin, Kim, Seonah, Nimlos, Mark R., and Baldwin, Robert M. Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading. United States: N. p., 2017. Web. doi:10.1039/C7GC02947K.
Iisa, Kristiina, Robichaud, David J., Watson, Michael J., ten Dam, Jeroen, Dutta, Abhijit, Mukarakate, Calvin, Kim, Seonah, Nimlos, Mark R., & Baldwin, Robert M. Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading. United States. https://doi.org/10.1039/C7GC02947K
Iisa, Kristiina, Robichaud, David J., Watson, Michael J., ten Dam, Jeroen, Dutta, Abhijit, Mukarakate, Calvin, Kim, Seonah, Nimlos, Mark R., and Baldwin, Robert M. Fri . "Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading". United States. https://doi.org/10.1039/C7GC02947K. https://www.osti.gov/servlets/purl/1413902.
@article{osti_1413902,
title = {Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading},
author = {Iisa, Kristiina and Robichaud, David J. and Watson, Michael J. and ten Dam, Jeroen and Dutta, Abhijit and Mukarakate, Calvin and Kim, Seonah and Nimlos, Mark R. and Baldwin, Robert M.},
abstractNote = {Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalytic fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.},
doi = {10.1039/C7GC02947K},
url = {https://www.osti.gov/biblio/1413902}, journal = {Green Chemistry},
issn = {1463-9262},
number = 3,
volume = 20,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The universal character of the Mars and Van Krevelen mechanism
journal, November 2000


Catalytic effect of tin oxide nanoparticles on cellulose pyrolysis
journal, May 2016


Ordered mesoporous materials
journal, February 1999


Second-generation biofuels by co-processing catalytic pyrolysis oil in FCC units
journal, February 2014


Heterogeneous catalysts for advanced bio-fuel production through catalytic biomass pyrolysis vapor upgrading: a review
journal, January 2015


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


Hydrodeoxygenation of Furfural Over Supported Metal Catalysts: A Comparative Study of Cu, Pd and Ni
journal, March 2011


Recent Advances in Catalysis Over Mesoporous Molecular Sieves
journal, December 2009


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


Hydrotreatment of Fast Pyrolysis Oil Using Heterogeneous Noble-Metal Catalysts
journal, December 2009

  • Wildschut, Jelle; Mahfud, Farchad H.; Venderbosch, Robbie H.
  • Industrial & Engineering Chemistry Research, Vol. 48, Issue 23, p. 10324-10334
  • https://doi.org/10.1021/ie9006003

Integration of C–C coupling reactions of biomass-derived oxygenates to fuel-grade compounds
journal, February 2010


Atmospheric Hydrodeoxygenation of Biomass Fast Pyrolysis Vapor by MoO 3
journal, August 2016


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


Pilot-scale validation of Co-ZSM-5 catalyst performance in the catalytic upgrading of biomass pyrolysis vapours
journal, January 2014


Catalytic fast pyrolysis of lignocellulosic biomass
journal, January 2014


Pyrolytic behavior of cellulose in presence of montmorillonite K10 as catalyst
journal, November 2012


Effect of cellulose crystallinity on the formation of a liquid intermediate and on product distribution during pyrolysis
journal, March 2013


Upgrading of bio-oil distillation bottoms into biorenewable calcined coke
journal, October 2015


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


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


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


Catalytic Conversion of Guaiacol Catalyzed by Platinum Supported on Alumina: Reaction Network Including Hydrodeoxygenation Reactions
journal, August 2011


Historical Developments in Hydroprocessing Bio-oils
journal, May 2007


Characterization, synthesis and catalysis of hydrotalcite-related materials for highly efficient materials transformations
journal, January 2013


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


Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis: A review
journal, January 2014


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


Catalytic Hydroprocessing of Chemical Models for Bio-oil
journal, February 2009


Catalytic Fast Pyrolysis of Lignin over High-Surface-Area Mesoporous Aluminosilicates: Effect of Porosity and Acidity
journal, April 2016


Biomass to fuels: The role of zeolite and mesoporous materials
journal, October 2011


Catalytic conversion of biomass pyrolysis vapors into hydrocarbon fuel precursors
journal, January 2015


Carbon–carbon bond formation for biomass-derived furfurals and ketones by aldol condensation in a biphasic system
journal, December 2008


Accumulation of Inorganic Impurities on HZSM-5 Zeolites during Catalytic Fast Pyrolysis of Switchgrass
journal, November 2013


Catalyst-Free Synthesis of Multiwalled Carbon Nanotubes via Microwave-Induced Processing of Biomass
journal, September 2014


Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion
journal, October 2013


Liquid–Liquid Equilibrium Measurements for Model Systems Related to Catalytic Fast Pyrolysis of Biomass
journal, November 2016


Catalysis for conversion of biomass to fuels via pyrolysis and gasification: A review
journal, August 2011


Catalytic conversion of biomass pyrolysis products by mesoporous materials: Effect of steam stability and acidity of Al-MCM-41 catalysts
journal, November 2007


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


Aqueous Phase Hydroalkylation and Hydrodeoxygenation of Phenol by Dual Functional Catalysts Comprised of Pd/C and H/La-BEA
journal, November 2012


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


An overview of aqueous-phase catalytic processes for production of hydrogen and alkanes in a biorefinery
journal, January 2006


Aromatic Production from Catalytic Fast Pyrolysis of Biomass-Derived Feedstocks
journal, January 2009


A review and perspective of recent bio-oil hydrotreating research
journal, January 2014


Direct conversion of carboxylic acids (C n ) to alkenes (C 2n−1 ) over titanium oxide in absence of noble metals
journal, May 2016


Conversion of Guaiacol on Noble Metal Catalysts: Reaction Performance and Deactivation Studies
journal, March 2014


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


Stabilization of Softwood-Derived Pyrolysis Oils for Continuous Bio-oil Hydroprocessing
journal, October 2015


Condensation reactions of propanal over CexZr1−xO2 mixed oxide catalysts
journal, September 2010


Influence of aluminosilicate materials on the peat low-temperature pyrolysis and gas formation
journal, November 2009


Solid Lewis Acids Catalyze the Carbon–Carbon Coupling between Carbohydrates and Formaldehyde
journal, January 2015


High-pressure fast-pyrolysis, fast-hydropyrolysis and catalytic hydrodeoxygenation of cellulose: production of liquid fuel from biomass
journal, January 2014


A perspective on oxygenated species in the refinery integration of pyrolysis oil
journal, January 2014


Ex situ hydrodeoxygenation in biomass pyrolysis using molybdenum oxide and low pressure hydrogen
journal, January 2016


Production of Stable Biomass Pyrolysis Oils Using Fractional Catalytic Pyrolysis
journal, July 2010


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


Hydrodeoxygenation of guaiacol
journal, January 2011


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


Analysis of Oxygenated Compounds in Hydrotreated Biomass Fast Pyrolysis Oil Distillate Fractions
journal, November 2011


Conversion of Guaiacol over Supported Ru Catalysts
journal, June 2013


Evaluate Impact of Catalyst Type on Oil Yield and Hydrogen Consumption from Mild Hydrotreating
journal, April 2014


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


Catalytic fast pyrolysis of lignocellulosic biomass in a process development unit with continual catalyst addition and removal
journal, April 2014


A Perspective on Catalytic Strategies for Deoxygenation in Biomass Pyrolysis
journal, August 2016


Acetone Hydrodeoxygenation over Bifunctional Metallic–Acidic Molybdenum Carbide Catalysts
journal, January 2016


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


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


Zeolite-catalysed C–C bond forming reactions for biomass conversion to fuels and chemicals
journal, January 2016


Catalytic hydrodeoxygenation
journal, June 2000


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


Catalytic Upgrading of Biomass-Derived Methyl Ketones to Liquid Transportation Fuel Precursors by an Organocatalytic Approach
journal, February 2015


Structure and site evolution of molybdenum carbide catalysts upon exposure to oxygen
journal, June 2015


Production of advanced biofuels: Co-processing of upgraded pyrolysis oil in standard refinery units
journal, April 2010


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


Catalytic hydroprocessing of biomass fast pyrolysis bio-oil to produce hydrocarbon products
journal, October 2009


Molybdenum incorporated mesoporous silica catalyst for production of biofuels and value-added chemicals via catalytic fast pyrolysis
journal, January 2015


Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds
journal, April 2013


Application of Molecular Sieves in Transformations of Biomass and Biomass-Derived Feedstocks
journal, January 2013


Production of Fuels and Chemicals from Biomass: Condensation Reactions and Beyond
journal, July 2016


Renewable fuels and chemicals by thermal processing of biomass
journal, March 2003


Hydrodeoxygenation of pyrolysis oil fractions: process understanding and quality assessment through co-processing in refinery units
journal, January 2011


Investigation into the shape selectivity of zeolite catalysts for biomass conversion
journal, April 2011


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


Catalytic deoxygenation on transition metal carbide catalysts
journal, January 2016


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


Design and operation of a pilot-scale catalytic biomass pyrolysis unit
journal, January 2015


Ketonization Reactions of Carboxylic Acids and Esters over Ceria−Zirconia as Biomass-Upgrading Processes
journal, July 2010

  • Gaertner, Christian A.; Serrano-Ruiz, Juan Carlos; Braden, Drew J.
  • Industrial & Engineering Chemistry Research, Vol. 49, Issue 13
  • https://doi.org/10.1021/ie1004338

The effect of zeolite ZSM-5 catalyst deactivation during the upgrading of biomass-derived pyrolysis vapours
journal, June 1995


CC Bond Formation Reactions for Biomass-Derived Molecules
journal, August 2010


Bio-oil Stabilization by Hydrogenation over Reduced Metal Catalysts at Low Temperatures
journal, August 2016


    Works referencing / citing this record:

    Valorization of aqueous waste streams from thermochemical biorefineries
    journal, January 2019


    Valorization of aqueous waste streams from thermochemical biorefineries
    journal, January 2019


    Hybridization of ZSM‐5 with Spinel Oxides for Biomass Vapour Upgrading
    journal, January 2020


    Separation of BTX chemicals from biomass pyrolysis oils via continuous flash distillation
    journal, April 2019


    Structure of carbon black continuously produced from biomass pyrolysis oil
    journal, January 2018