Calcium Phosphate Catalysts for Ethanol Coupling to Butanol and Butadiene

Prillaman, J. Tyler; Miyake, Naomi; Davis, Robert J.

doi:10.1007/s10562-020-03342-5

Title: Calcium Phosphate Catalysts for Ethanol Coupling to Butanol and Butadiene

Journal Article · Fri Aug 07 00:00:00 EDT 2020 · Catalysis Letters

DOI:https://doi.org/10.1007/s10562-020-03342-5· OSTI ID:1656838

Prillaman, J. Tyler ^[1]; Miyake, Naomi ^[1];

^[1]

University of Virginia, Charlottesville, VA (United States)

The catalytic conversion of ethanol to butanol and butadiene at 633 K and atmospheric pressure (7 vol% ethanol) was studied over calcium phosphate materials pretreated over a wide temperature range. For calcium phosphate pretreated at or below 923 K, the resulting solid had an apatite structure identified by X-ray diffraction and strong acid sites probed by triethylamine (TEA) adsorption microcalorimetry. The low temperature pretreated materials were not effective at ethanol coupling reactions but instead were highly selective to acid-catalyzed products ethene and diethyl ether. Pretreatment of calcium phosphate at 973 K transformed the apatite structure to β-tricalcium phosphate, which exposed both acid and base sites evaluated by TEA and CO₂ adsorption microcalorimetry. In conclusion, high temperature pretreated calcium phosphate catalysts formed the coupling products butanol and butadiene during ethanol reaction. The butadiene selectivity was improved by supporting calcium phosphate on zirconia.

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Research Organization:: Univ. of Virginia, Charlottesville, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-95ER14549

OSTI ID:: 1656838

Journal Information:: Catalysis Letters, Vol. 151, Issue 3; ISSN 1011-372X

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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References (38)

Recent Advances in Catalytic Conversion of Ethanol to Chemicals Sun, Junming; Wang, Yong ACS Catalysis, Vol. 4, Issue 4 https://doi.org/10.1021/cs4011343	journal	March 2014
Production of Butadiene from Alcohol Toussaint, W. J.; Dunn, J. T.; Jachson, D. R. Industrial & Engineering Chemistry, Vol. 39, Issue 2 https://doi.org/10.1021/ie50446a010	journal	February 1947
Direct Synthesis of n -Butanol from Ethanol over Nonstoichiometric Hydroxyapatite Tsuchida, Takashi; Sakuma, Shuji; Takeguchi, Tatsuya Industrial & Engineering Chemistry Research, Vol. 45, Issue 25 https://doi.org/10.1021/ie0606082	journal	December 2006
Multiproduct Steady-State Isotopic Transient Kinetic Analysis of the Ethanol Coupling Reaction over Hydroxyapatite and Magnesia Hanspal, Sabra; Young, Zachary D.; Shou, Heng ACS Catalysis, Vol. 5, Issue 3 https://doi.org/10.1021/cs502023g	journal	February 2015
Influence of Preparation Factors on Ca/P Ratio and Surface Basicity of Hydroxyapatite Catalyst Tsuchida, Takashi; Kubo, Jun; Yoshioka, Tetsuya Journal of the Japan Petroleum Institute, Vol. 52, Issue 2 https://doi.org/10.1627/jpi.52.51	journal	January 2009
Influence of Magnesium Substitution on the Basic Properties of Hydroxyapatites Diallo-Garcia, Sarah; Laurencin, Danielle; Krafft, Jean-Marc The Journal of Physical Chemistry C, Vol. 115, Issue 49 https://doi.org/10.1021/jp209316k	journal	November 2011
Effect of the SiO2 support on the catalytic performance of Ag/ZrO2/SiO2 catalysts for the single-bed production of butadiene from ethanol Dagle, Vanessa Lebarbier; Flake, Matthew D.; Lemmon, Teresa L. Applied Catalysis B: Environmental, Vol. 236 https://doi.org/10.1016/j.apcatb.2018.05.055	journal	November 2018
DRIFTS of Probe Molecules Adsorbed on Magnesia, Zirconia, and Hydroxyapatite Catalysts Hill, Ian M.; Hanspal, Sabra; Young, Zachary D. The Journal of Physical Chemistry C, Vol. 119, Issue 17 https://doi.org/10.1021/jp509889j	journal	April 2015
Influence of surface acid and base sites on the Guerbet coupling of ethanol to butanol over metal phosphate catalysts Hanspal, Sabra; Young, Zachary D.; Prillaman, J. Tyler Journal of Catalysis, Vol. 352 https://doi.org/10.1016/j.jcat.2017.04.036	journal	August 2017
Zeolite Structural Confinement Effects Enhance One-Pot Catalytic Conversion of Ethanol to Butadiene Dai, Weili; Zhang, Shanshan; Yu, Zhiyang ACS Catalysis, Vol. 7, Issue 5 https://doi.org/10.1021/acscatal.7b00433	journal	April 2017
Ethanol catalytic condensation over Mg–Al mixed oxides derived from hydrotalcites León, Marta; Díaz, Eva; Ordóñez, Salvador Catalysis Today, Vol. 164, Issue 1 https://doi.org/10.1016/j.cattod.2010.10.003	journal	April 2011
Investigations into the conversion of ethanol into 1,3-butadiene Jones, Matthew D.; Keir, Callum G.; Iulio, Carlo Di Catalysis Science & Technology, Vol. 1, Issue 2 https://doi.org/10.1039/c0cy00081g	journal	January 2011
Butadiene from Ethanol. Reaction Mechanism Jones, H. E.; Stahly, E. E.; Corson, B. B. Journal of the American Chemical Society, Vol. 71, Issue 5 https://doi.org/10.1021/ja01173a084	journal	May 1949
An analysis of the chemical, physical and reactivity features of MgO–SiO ₂ catalysts for butadiene synthesis with the Lebedev process Ochoa, Juliana Velasquez; Bandinelli, Claudia; Vozniuk, Olena Green Chemistry, Vol. 18, Issue 6 https://doi.org/10.1039/C5GC02194D	journal	January 2016
Synthesis of Biogasoline from Ethanol over Hydroxyapatite Catalyst Tsuchida, Takashi; Yoshioka, Tetsuya; Sakuma, Shuji Industrial & Engineering Chemistry Research, Vol. 47, Issue 5 https://doi.org/10.1021/ie0711731	journal	March 2008
One-step catalytic conversion of ethanol to butadiene in the fixed bed. II BINARY- AND TERNARY-OXIDE CATALYSTS Bhattacharyya, S. K.; Ganguly, N. D. Journal of Applied Chemistry, Vol. 12, Issue 3 https://doi.org/10.1002/jctb.5010120302	journal	March 1962
Selective synthesis of 1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts Ogo, Shuhei; Onda, Ayumu; Yanagisawa, Kazumichi Applied Catalysis A: General, Vol. 402, Issue 1-2 https://doi.org/10.1016/j.apcata.2011.06.006	journal	July 2011
Deoxygenation of Certain Aldehydes and Ketones: Preparation of Butadiene and Styrene ¹ Quattlebaum, W. M.; Toussaint, W. J.; Dunn, J. T. Journal of the American Chemical Society, Vol. 69, Issue 3 https://doi.org/10.1021/ja01195a040	journal	March 1947
Reaction of ethanol over hydroxyapatite affected by Ca/P ratio of catalyst Tsuchida, T.; Kubo, J.; Yoshioka, T. Journal of Catalysis, Vol. 259, Issue 2 https://doi.org/10.1016/j.jcat.2008.08.005	journal	October 2008
Butadiene Formation from Ethanol over Silica-Magnesia Catalysts Niiyama, Hiroo; Morii, Saburo; Echigoya, Etsuro Bulletin of the Chemical Society of Japan, Vol. 45, Issue 3 https://doi.org/10.1246/bcsj.45.655	journal	March 1972
Catalytic study of the conversion of ethanol into 1,3-butadiene Makshina, E. V.; Janssens, W.; Sels, B. F. Catalysis Today, Vol. 198, Issue 1 https://doi.org/10.1016/j.cattod.2012.05.031	journal	December 2012
Ethanol conversion into butadiene over Zr-containing molecular sieves doped with silver Sushkevich, Vitaly L.; Ivanova, Irina I.; Taarning, Esben Green Chemistry, Vol. 17, Issue 4 https://doi.org/10.1039/C4GC02202E	journal	January 2015
From Sugars to Wheels: The Conversion of Ethanol to 1,3-Butadiene over Metal-Promoted Magnesia-Silicate Catalysts Shylesh, Sankaranarayanapillai; Gokhale, Amit A.; Scown, Corinne D. ChemSusChem, Vol. 9, Issue 12 https://doi.org/10.1002/cssc.201600195	journal	May 2016
Identification of Surface Basic Sites and Acid–Base Pairs of Hydroxyapatite Diallo-Garcia, Sarah; Osman, Manel Ben; Krafft, Jean-Marc The Journal of Physical Chemistry C, Vol. 118, Issue 24 https://doi.org/10.1021/jp500469x	journal	June 2014
Transformation of ethanol into 1,3-butadiene over magnesium oxide/silica catalysts Kvisle, S.; Aguero, A.; Sneeden, R. P. A. Applied Catalysis, Vol. 43, Issue 1 https://doi.org/10.1016/S0166-9834(00)80905-7	journal	January 1988
Effect of Preparation Method and CuO Promotion in the Conversion of Ethanol into 1,3-Butadiene over SiO ₂ -MgO Catalysts Angelici, Carlo; Velthoen, Marjolein E. Z.; Weckhuysen, Bert M. ChemSusChem, Vol. 7, Issue 9 https://doi.org/10.1002/cssc.201402361	journal	July 2014
Review of old chemistry and new catalytic advances in the on-purpose synthesis of butadiene Makshina, Ekaterina V.; Dusselier, Michiel; Janssens, Wout Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C4CS00105B	journal	January 2014
Influence of acid–base properties on the Lebedev ethanol-to-butadiene process catalyzed by SiO ₂ –MgO materials Angelici, Carlo; Velthoen, Marjolein E. Z.; Weckhuysen, Bert M. Catalysis Science & Technology, Vol. 5, Issue 5 https://doi.org/10.1039/C5CY00200A	journal	January 2015
Chemocatalytic Conversion of Ethanol into Butadiene and Other Bulk Chemicals Angelici, Carlo; Weckhuysen, Bert M.; Bruijnincx, Pieter C. A. ChemSusChem, Vol. 6, Issue 9 https://doi.org/10.1002/cssc.201300214	journal	May 2013
Design of a Metal-Promoted Oxide Catalyst for the Selective Synthesis of Butadiene from Ethanol Sushkevich, Vitaly L.; Ivanova, Irina I.; Ordomsky, Vitaly V. ChemSusChem, Vol. 7, Issue 9 https://doi.org/10.1002/cssc.201402346	journal	August 2014
Control of calcium accessibility over hydroxyapatite by post-precipitation steps: influence on the catalytic reactivity toward alcohols Ben Osman, Manel; Diallo Garcia, Sarah; Krafft, Jean-Marc Physical Chemistry Chemical Physics, Vol. 18, Issue 40 https://doi.org/10.1039/C6CP05294K	journal	January 2016
Mechanistic study of ethanol conversion into butadiene over silver promoted zirconia catalysts Sushkevich, Vitaly L.; Ivanova, Irina I. Applied Catalysis B: Environmental, Vol. 215 https://doi.org/10.1016/j.apcatb.2017.05.060	journal	October 2017
Heterogeneous Catalysts for the Guerbet Coupling of Alcohols Kozlowski, Joseph T.; Davis, Robert J. ACS Catalysis, Vol. 3, Issue 7 https://doi.org/10.1021/cs400292f	journal	June 2013
Aldol Condensation of Acetaldehyde over Titania, Hydroxyapatite, and Magnesia Young, Zachary D.; Hanspal, Sabra; Davis, Robert J. ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00264	journal	April 2016
Nature of deficiency in nonstoichiometric hydroxyapatites. I. Catalytic activity of calcium and strontium hydroxyapatites Joris, S. J.; Amberg, C. H. The Journal of Physical Chemistry, Vol. 75, Issue 20 https://doi.org/10.1021/j100689a024	journal	September 1971
Role of Magnesium Silicates in Wet-Kneaded Silica–Magnesia Catalysts for the Lebedev Ethanol-to-Butadiene Process Chung, Sang-Ho; Angelici, Carlo; Hinterding, Stijn O. M. ACS Catalysis, Vol. 6, Issue 6 https://doi.org/10.1021/acscatal.5b02972	journal	May 2016
Reactivity of ethanol over hydroxyapatite-based Ca-enriched catalysts with various carbonate contents Silvester, Lishil; Lamonier, Jean-François; Faye, Jérémy Catalysis Science & Technology, Vol. 5, Issue 5 https://doi.org/10.1039/C5CY00327J	journal	January 2015
Mechanism and Kinetics of Ethanol Coupling to Butanol over Hydroxyapatite Ho, Christopher R.; Shylesh, Sankaranarayanapillai; Bell, Alexis T. ACS Catalysis, Vol. 6, Issue 2 https://doi.org/10.1021/acscatal.5b02672	journal	January 2016

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Title: Calcium Phosphate Catalysts for Ethanol Coupling to Butanol and Butadiene

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