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

Title: Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn)

Abstract

Here, the impetus to explore biomass derived chemicals arises from a desire to enable renewable and sustainable commodity chemicals. To this end, we report catalytic production of propene, a building-block molecule, from 1-propanol. We found that zeolite catalysts are quite versatile and can produce propene at or below 230 C with high selectivity. Increasing the reaction temperature above 230 C shifted product selectivity towards C4+ hydrocarbons. Cu-ZSM-5 was found to exhibit a broader temperature window for high propene selectivity and could function at higher 1-propanol space velocities than H-ZSM-5. A series of experiments with 1-propan(ol-D) showed deuterium incorporation in the hydrocarbon product stream including propene suggesting that hydrocarbon pool type pathway might be operational concurrent with dehydration to produce C4+ hydrocarbons. Diffuse reflectance infra-red spectroscopy of 1-propanol and 1-propan(ol-D) over Cu-ZSM-5 in combination with deuterium labeling experiments suggest that deuterium incorporation occurs in two steps. Incorporation of deuterium occurs post dehydration via exchange with the partially deuterated catalyst surface.

Authors:
 [1];  [2];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Carbon Fiber Technology Facility (CFTF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1350920
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 56; Journal Issue: 1; Journal ID: ISSN 0888-5885
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lepore, Andrew W., Li, Zhenglong, Davison, Brian H., Foo, Guo -Shiou, Wu, Zili, and Narula, Chaitanya Kumar. Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn). United States: N. p., 2017. Web. https://doi.org/10.1021/acs.iecr.7b00592.
Lepore, Andrew W., Li, Zhenglong, Davison, Brian H., Foo, Guo -Shiou, Wu, Zili, & Narula, Chaitanya Kumar. Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn). United States. https://doi.org/10.1021/acs.iecr.7b00592
Lepore, Andrew W., Li, Zhenglong, Davison, Brian H., Foo, Guo -Shiou, Wu, Zili, and Narula, Chaitanya Kumar. Mon . "Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn)". United States. https://doi.org/10.1021/acs.iecr.7b00592. https://www.osti.gov/servlets/purl/1350920.
@article{osti_1350920,
title = {Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn)},
author = {Lepore, Andrew W. and Li, Zhenglong and Davison, Brian H. and Foo, Guo -Shiou and Wu, Zili and Narula, Chaitanya Kumar},
abstractNote = {Here, the impetus to explore biomass derived chemicals arises from a desire to enable renewable and sustainable commodity chemicals. To this end, we report catalytic production of propene, a building-block molecule, from 1-propanol. We found that zeolite catalysts are quite versatile and can produce propene at or below 230 C with high selectivity. Increasing the reaction temperature above 230 C shifted product selectivity towards C4+ hydrocarbons. Cu-ZSM-5 was found to exhibit a broader temperature window for high propene selectivity and could function at higher 1-propanol space velocities than H-ZSM-5. A series of experiments with 1-propan(ol-D) showed deuterium incorporation in the hydrocarbon product stream including propene suggesting that hydrocarbon pool type pathway might be operational concurrent with dehydration to produce C4+ hydrocarbons. Diffuse reflectance infra-red spectroscopy of 1-propanol and 1-propan(ol-D) over Cu-ZSM-5 in combination with deuterium labeling experiments suggest that deuterium incorporation occurs in two steps. Incorporation of deuterium occurs post dehydration via exchange with the partially deuterated catalyst surface.},
doi = {10.1021/acs.iecr.7b00592},
journal = {Industrial and Engineering Chemistry Research},
number = 1,
volume = 56,
place = {United States},
year = {2017},
month = {4}
}

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

Save / Share:

Works referenced in this record:

Ethylene from ethanol over zeolite catalysts
journal, January 1987


Catalytic Transformations of Ethanol for Biorefineries
journal, January 2014

  • Gallo, Jean M. R.; Bueno, José M. C.; Schuchardt, Ulf
  • Journal of the Brazilian Chemical Society
  • DOI: 10.5935/0103-5053.20140272

Hydrolysis of lignocellulosic materials for ethanol production: a review
journal, May 2002


Production of isopropanol by metabolically engineered Escherichia coli
journal, November 2007

  • Jojima, Toru; Inui, Masayuki; Yukawa, Hideaki
  • Applied Microbiology and Biotechnology, Vol. 77, Issue 6, p. 1219-1224
  • DOI: 10.1007/s00253-007-1246-8

Simultaneous production of isopropanol, butanol, ethanol and 2,3-butanediol by Clostridium acetobutylicum ATCC 824 engineered strains
journal, January 2012


Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 2: Gasification systems
journal, December 2009


A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas
journal, September 2009


One-step hydrogenolysis of glycerol to biopropanols over Pt–H4SiW12O40/ZrO2 catalysts
journal, January 2012

  • Zhu, Shanhui; Zhu, Yulei; Hao, Shunli
  • Green Chemistry, Vol. 14, Issue 9
  • DOI: 10.1039/c2gc35564g

Mechanistic Investigation of Isopropanol Conversion on Alumina Catalysts: Location of Active Sites for Alkene/Ether Production
journal, June 2015


Dehydration of butanol to butene over solid acid catalysts in high water environments
journal, February 2009


Theoretical study of the adsorption of C1–C4 primary alcohols in H-ZSM-5
journal, January 2010

  • Nguyen, Cuong M.; Reyniers, Marie-Françoise; Marin, Guy B.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 32
  • DOI: 10.1039/c000503g

Catalytic consequences of acid strength in the conversion of methanol to dimethyl ether
journal, February 2011


Catalytic Conversion of Bio-ethanol to Ethylene over La-Modified HZSM-5 Catalysts in a Bioreactor
journal, June 2009


Mechanistic studies of the catalytic dehydration of isobutyl alcohol on NaH-ZSM-5
journal, January 1990

  • Williams, Carol; Makarova, Marina A.; Malysheva, Ludmila V.
  • Journal of the Chemical Society, Faraday Transactions, Vol. 86, Issue 20
  • DOI: 10.1039/ft9908603473

Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites
journal, September 2014

  • Jones, Andrew J.; Iglesia, Enrique
  • Angewandte Chemie International Edition, Vol. 53, Issue 45
  • DOI: 10.1002/anie.201406823

Propylene from Renewable Resources: Catalytic Conversion of Glycerol into Propylene
journal, February 2014


Zeolite acidity dependence on structure and chemical environment. Correlations with catalysis
journal, April 1987


Acidity Differences between Inorganic Solids Induced by Their Framework Structure. A Combined Quantum Mechanics/Molecular Mechanics ab Initio Study on Zeolites
journal, February 1998

  • Brändle, Martin; Sauer, Joachim
  • Journal of the American Chemical Society, Vol. 120, Issue 7
  • DOI: 10.1021/ja9729037

Characterization of Acidic OH Groups in Zeolites of Different Types:  An Interpretation of NH 3 -TPD Results in the Light of Confinement Effects
journal, April 2002

  • Hunger, Bernd; Heuchel, Matthias; Clark, Louis A.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 15
  • DOI: 10.1021/jp012688n

An Examination of Confinement Effects in High-Silica Zeolites
journal, February 2001

  • Yang, L.; Trafford, K.; Kresnawahjuesa, O.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 10
  • DOI: 10.1021/jp002964i

Structure and Reactivity of Zn-Modified ZSM-5 Zeolites: The Importance of Clustered Cationic Zn Complexes
journal, December 2011

  • Almutairi, Sami M. T.; Mezari, Brahim; Magusin, Pieter C. M. M.
  • ACS Catalysis, Vol. 2, Issue 1
  • DOI: 10.1021/cs200441e

Radioisotope tracer study of co-reactions of methanol with ethanol using 11C-labelled methanol over alumina, H-ZSM-5 and Cu-ZSM-5
journal, August 2007


A [Cu 2 O] 2+ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol
journal, October 2009

  • Woertink, Julia S.; Smeets, Pieter J.; Groothaert, Marijke H.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 45
  • DOI: 10.1073/pnas.0910461106

Heterobimetallic Zeolite, InV-ZSM-5, Enables Efficient Conversion of Biomass Derived Ethanol to Renewable Hydrocarbons
journal, November 2015

  • Narula, Chaitanya K.; Li, Zhenglong; Casbeer, Erik M.
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep16039

Heterometal Incorporation in Metal-Exchanged Zeolites Enables Low-Temperature Catalytic Activity of NO x Reduction
journal, October 2012

  • Yang, Xiaofan; Wu, Zili; Moses-Debusk, Melanie
  • The Journal of Physical Chemistry C, Vol. 116, Issue 44
  • DOI: 10.1021/jp3056043

Selective catalytic reduction of NO with NH3 over HZSM-5-supported Fe–Cu nanocomposite catalysts: The Fe–Cu bimetallic effect
journal, April 2014


The promotional role of Ce in Cu/ZSM-5 and in situ surface reaction for selective catalytic reduction of NO x with NH 3
journal, January 2015

  • Lai, Shuangshuang; Meng, Dongmei; Zhan, Wangcheng
  • RSC Advances, Vol. 5, Issue 110
  • DOI: 10.1039/C5RA12505G

An infrared spectroscopy study of simple alcohols adsorbed on H-ZSM-5
journal, June 1987


Methods for NH3 titration of Brønsted acid sites in Cu-zeolites that catalyze the selective catalytic reduction of NOx with NH3
journal, April 2014


Activation Energies for the Reaction of Ethoxy Species to Ethene over Zeolites
journal, November 2010

  • Kondo, Junko N.; Nishioka, Daisuke; Yamazaki, Hiroshi
  • The Journal of Physical Chemistry C, Vol. 114, Issue 47
  • DOI: 10.1021/jp107082t

Formation and Decomposition of Surface Ethoxy Species on Acidic Zeolite Y
journal, August 2005


HC-SCR reaction pathways on ion exchanged ZSM-5 catalysts
journal, January 2009


Infrared study of adsorption of methanol, deuterated methanol and ethylene on the surface of ZSM-5 type zeolite
journal, March 1982


I.r. study of the transformations of olefins, alcohols and ethers on zeolites
journal, July 1982


Infrared study on the mechanism of olefins and alcohols conversions over H-ZSM-5 zeolite
journal, January 1984


    Works referencing / citing this record:

    A comprehensive metabolic map for production of bio-based chemicals
    journal, January 2019