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Title: Effect of the SiO2 support on the catalytic performance of Ag/ZrO2/SiO2 catalysts for the single-bed production of butadiene from ethanol

Abstract

A ternary Ag/ZrO2/SiO2 catalyst system was studied for single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO2 loading, and choice of SiO2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO2/SiO2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325°C, 1 atm, and 0.23 h–1). Several classes of silica—silica gels, fumed silicas, mesoporous silicas)—were evaluated as catalyst supports, and SBA-16 was found to be the most promising choice. The SiO2 support was found to significantly influence both conversion and selectivity. A higher SiO2 catalyst surface area facilitates increased Ag dispersion which leads to greater conversion due to the accelerated initial ethanol dehydrogenation reaction step. By independently varying Ag and ZrO2 loading, Ag was found to be the main component that affects ethanol conversion. ZrO2 loading and thus Lewis acid sites concentration was found to have little impact on the ethanol conversion. Butadiene selectivity depends on the concentration of Lewis acid site, which in turn differs depending on the choice of SiO2 support material. We observed a direct relationship between butadiene selectivity and concentration of Lewis acidmore » sites. Butadiene selectivity decreases as the concentration of Lewis acid sites increases, which corresponds to an increase in ethanol dehydration to ethylene and diethyl ether. Additionally, adding H2 to the feed had little effect on conversion while improving catalytic stability; however, selectivity to butadiene decreased. Lastly, catalyst regenerability was successfully demonstrated for several cycles.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1439097
Alternate Identifier(s):
OSTI ID: 1591653
Report Number(s):
PNNL-SA-128543
Journal ID: ISSN 0926-3373; PII: S0926337318304855
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis B: Environmental
Additional Journal Information:
Journal Volume: 236; Journal Issue: C; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ethanol; Butadiene; Biomass; Single-Step; SiO2Ag/ZrO2/SiO2acidity; Regeneration

Citation Formats

Dagle, Vanessa Lebarbier, Flake, Matthew D., Lemmon, Teresa L., Lopez, Johnny Saavedra, Kovarik, Libor, and Dagle, Robert A. Effect of the SiO2 support on the catalytic performance of Ag/ZrO2/SiO2 catalysts for the single-bed production of butadiene from ethanol. United States: N. p., 2018. Web. doi:10.1016/j.apcatb.2018.05.055.
Dagle, Vanessa Lebarbier, Flake, Matthew D., Lemmon, Teresa L., Lopez, Johnny Saavedra, Kovarik, Libor, & Dagle, Robert A. Effect of the SiO2 support on the catalytic performance of Ag/ZrO2/SiO2 catalysts for the single-bed production of butadiene from ethanol. United States. https://doi.org/10.1016/j.apcatb.2018.05.055
Dagle, Vanessa Lebarbier, Flake, Matthew D., Lemmon, Teresa L., Lopez, Johnny Saavedra, Kovarik, Libor, and Dagle, Robert A. Sat . "Effect of the SiO2 support on the catalytic performance of Ag/ZrO2/SiO2 catalysts for the single-bed production of butadiene from ethanol". United States. https://doi.org/10.1016/j.apcatb.2018.05.055. https://www.osti.gov/servlets/purl/1439097.
@article{osti_1439097,
title = {Effect of the SiO2 support on the catalytic performance of Ag/ZrO2/SiO2 catalysts for the single-bed production of butadiene from ethanol},
author = {Dagle, Vanessa Lebarbier and Flake, Matthew D. and Lemmon, Teresa L. and Lopez, Johnny Saavedra and Kovarik, Libor and Dagle, Robert A.},
abstractNote = {A ternary Ag/ZrO2/SiO2 catalyst system was studied for single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO2 loading, and choice of SiO2 support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO2/SiO2-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325°C, 1 atm, and 0.23 h–1). Several classes of silica—silica gels, fumed silicas, mesoporous silicas)—were evaluated as catalyst supports, and SBA-16 was found to be the most promising choice. The SiO2 support was found to significantly influence both conversion and selectivity. A higher SiO2 catalyst surface area facilitates increased Ag dispersion which leads to greater conversion due to the accelerated initial ethanol dehydrogenation reaction step. By independently varying Ag and ZrO2 loading, Ag was found to be the main component that affects ethanol conversion. ZrO2 loading and thus Lewis acid sites concentration was found to have little impact on the ethanol conversion. Butadiene selectivity depends on the concentration of Lewis acid site, which in turn differs depending on the choice of SiO2 support material. We observed a direct relationship between butadiene selectivity and concentration of Lewis acid sites. Butadiene selectivity decreases as the concentration of Lewis acid sites increases, which corresponds to an increase in ethanol dehydration to ethylene and diethyl ether. Additionally, adding H2 to the feed had little effect on conversion while improving catalytic stability; however, selectivity to butadiene decreased. Lastly, catalyst regenerability was successfully demonstrated for several cycles.},
doi = {10.1016/j.apcatb.2018.05.055},
journal = {Applied Catalysis B: Environmental},
number = C,
volume = 236,
place = {United States},
year = {2018},
month = {5}
}

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Cited by: 6 works
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Figures / Tables:

Table 1 Table 1: Effect of H2 addition to the feed on the catalytic performance over 4Ag/4ZrO2/SiO2-646, 1Ir/4ZrO2/SiO2-646 and 2Ir/4ZrO2/SiO2-646.

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Works referenced in this record:

Review of old chemistry and new catalytic advances in the on-purpose synthesis of butadiene
journal, January 2014

  • Makshina, Ekaterina V.; Dusselier, Michiel; Janssens, Wout
  • Chem. Soc. Rev., Vol. 43, Issue 22
  • DOI: 10.1039/C4CS00105B

Butadiene production process overview
journal, March 2007


Catalytic transformation of ethanol into 1,3-butadiene
journal, September 2014


Recent Advances in Catalytic Conversion of Ethanol to Chemicals
journal, March 2014


Sustainability assessment of novel chemical processes at early stage: application to biobased processes
journal, January 2012

  • Patel, Akshay D.; Meesters, Koen; den Uil, Herman
  • Energy & Environmental Science, Vol. 5, Issue 9
  • DOI: 10.1039/c2ee21581k

Early-Stage Comparative Sustainability Assessment of New Bio-based Processes
journal, September 2013

  • Patel, Akshay D.; Meesters, Koen; den Uil, Herman
  • ChemSusChem, Vol. 6, Issue 9
  • DOI: 10.1002/cssc.201300168

Chemocatalytic Conversion of Ethanol into Butadiene and Other Bulk Chemicals
journal, May 2013

  • Angelici, Carlo; Weckhuysen, Bert M.; Bruijnincx, Pieter C. A.
  • ChemSusChem, Vol. 6, Issue 9
  • DOI: 10.1002/cssc.201300214

One-step catalytic conversion of ethanol to butadiene in the fixed bed. II BINARY- AND TERNARY-OXIDE CATALYSTS
journal, March 1962


With Open Arms: Open Sites of ZrBEA Zeolite Facilitate Selective Synthesis of Butadiene from Ethanol
journal, July 2015

  • Sushkevich, Vitaly L.; Palagin, Dennis; Ivanova, Irina I.
  • ACS Catalysis, Vol. 5, Issue 8
  • DOI: 10.1021/acscatal.5b01024

Ag-Promoted ZrBEA Zeolites Obtained by Post-Synthetic Modification for Conversion of Ethanol to Butadiene
journal, July 2016


Bimetallic Zn and Hf on Silica Catalysts for the Conversion of Ethanol to 1,3-Butadiene
journal, May 2015


Ethanol conversion into butadiene over Zr-containing molecular sieves doped with silver
journal, January 2015

  • Sushkevich, Vitaly L.; Ivanova, Irina I.; Taarning, Esben
  • Green Chemistry, Vol. 17, Issue 4
  • DOI: 10.1039/C4GC02202E

Design of a Metal-Promoted Oxide Catalyst for the Selective Synthesis of Butadiene from Ethanol
journal, August 2014

  • Sushkevich, Vitaly L.; Ivanova, Irina I.; Ordomsky, Vitaly V.
  • ChemSusChem, Vol. 7, Issue 9
  • DOI: 10.1002/cssc.201402346

Conversion of Oxygen Derivatives of Hydrocarbons into Butadiene.
journal, February 1945


Butadiene from Ethanol. Reaction Mechanism
journal, May 1949

  • Jones, H. E.; Stahly, E. E.; Corson, B. B.
  • Journal of the American Chemical Society, Vol. 71, Issue 5
  • DOI: 10.1021/ja01173a084

Ternary Ag/MgO-SiO 2 Catalysts for the Conversion of Ethanol into Butadiene
journal, March 2015

  • Janssens, Wout; Makshina, Ekaterina V.; Vanelderen, Pieter
  • ChemSusChem, Vol. 8, Issue 6
  • DOI: 10.1002/cssc.201500081

Mechanistic study of ethanol conversion into butadiene over silver promoted zirconia catalysts
journal, October 2017


Mechanistic Study of Ethanol Dehydrogenation over Silica-Supported Silver
journal, May 2013

  • Sushkevich, Vitaly L.; Ivanova, Irina I.; Taarning, Esben
  • ChemCatChem, Vol. 5, Issue 8
  • DOI: 10.1002/cctc.201300033

Meerwein–Ponndorf–Verley–Oppenauer reaction of crotonaldehyde with ethanol over Zr-containing catalysts
journal, July 2014


Zeolite Structural Confinement Effects Enhance One-Pot Catalytic Conversion of Ethanol to Butadiene
journal, April 2017


Steam reforming of hydrocarbons from biomass-derived syngas over MgAl2O4-supported transition metals and bimetallic IrNi catalysts
journal, May 2016


Highly active and stable MgAl2O4-supported Rh and Ir catalysts for methane steam reforming: A combined experimental and theoretical study
journal, July 2014


Comparative Investigation of Benzene Steam Reforming over Spinel Supported Rh and Ir Catalysts
journal, April 2013

  • Mei, Donghai; Lebarbier, Vanessa M.; Rousseau, Roger
  • ACS Catalysis, Vol. 3, Issue 6
  • DOI: 10.1021/cs4000427

Investigations into the conversion of ethanol into 1,3-butadiene
journal, January 2011

  • Jones, Matthew D.; Keir, Callum G.; Iulio, Carlo Di
  • Catalysis Science & Technology, Vol. 1, Issue 2
  • DOI: 10.1039/c0cy00081g

Study of acetaldehyde condensation chemistry over magnesia and zirconia supported on silica
journal, December 2010

  • Ordomsky, V. V.; Sushkevich, V. L.; Ivanova, I. I.
  • Journal of Molecular Catalysis A: Chemical, Vol. 333, Issue 1-2
  • DOI: 10.1016/j.molcata.2010.10.001

Ethylene and diethyl-ether production by dehydration reaction of ethanol over different heteropolyacid catalysts
journal, September 2007

  • Varisli, Dilek; Dogu, Timur; Dogu, Gulsen
  • Chemical Engineering Science, Vol. 62, Issue 18-20
  • DOI: 10.1016/j.ces.2007.01.017

Catalytic dehydration of ethanol over hierarchical ZSM-5 zeolites: studies of their acidity and porosity properties
journal, January 2016

  • Tarach, Karolina A.; Tekla, Justyna; Makowski, Wacław
  • Catalysis Science & Technology, Vol. 6, Issue 10
  • DOI: 10.1039/C5CY01866H

Works referencing / citing this record:

Catalytic Investigation of Ag Nanostructures Loaded on Porous Hematite Cubes: Infiltrated versus Exteriors
journal, May 2019

  • Manivannan, Shanmugam; Kim, Mun‐Seok; Yim, Taeeun
  • ChemistrySelect, Vol. 4, Issue 17
  • DOI: 10.1002/slct.201900326

Catalytic conversion of ethanol into butadiene over high performance LiZnHf-MFI zeolite nanosheets
journal, January 2019

  • Wang, Chan; Zheng, Mingyuan; Li, Xinsheng
  • Green Chemistry, Vol. 21, Issue 5
  • DOI: 10.1039/c8gc03983f

Catalytic activation of ethylene C–H bonds on uniform d 8 Ir( i ) and Ni( ii ) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts
journal, January 2019

  • Jaegers, Nicholas R.; Khivantsev, Konstantin; Kovarik, Libor
  • Catalysis Science & Technology, Vol. 9, Issue 23
  • DOI: 10.1039/c9cy01442j

The Role of the Oxygen Vacancies in the Synthesis of 1, 3‐Butadiene from Ethanol
journal, October 2019

  • Chagas, Luciano H.; Zonetti, Priscila C.; Matheus, Caio R. V.
  • ChemCatChem, Vol. 11, Issue 22
  • DOI: 10.1002/cctc.201901243

Effect of ZnO on acid–base properties and catalytic performances of ZnO/ZrO 2 –SiO 2 catalysts in 1,3-butadiene production from ethanol–water mixture
journal, January 2019

  • Larina, Olga V.; Kyriienko, Pavlo I.; Balakin, Dmytro Yu.
  • Catalysis Science & Technology, Vol. 9, Issue 15
  • DOI: 10.1039/c9cy00991d