Selective synthesis of 1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts

Shuhei Ogo; Ayumu Onda; Kazumichi Yanagisawa

doi:10.1016/j.apcata.2011.06.006

Selective synthesis of 1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts

Shuhei Ogo, Ayumu Onda^*, Kazumichi Yanagisawa

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

157 Citations (Scopus)

Abstract

We previously reported the ability of strontium hydroxyapatite to catalyze the conversion of ethanol into 1-butanol with higher selectivity than that reported for calcium hydroxyapatite catalysts. In the present study, we investigated the catalytic conversions of ethanol over substituted hydroxyapatites, such as Sr₁₀(PO₄)₆(OH) ₂, Ca₁₀(VO₄)₆(OH)₂, Sr₁₀(VO₄)₆(OH)₂, and Ca ₁₀(PO₄)₆(OH)₂, and their solid solutions, such as Ca_{10 - z}Sr_z(PO₄) ₆(OH)₂, Ca₁₀(PO₄) _{6 - x}(VO₄)_{6 - x}(OH)₂, and Sr ₁₀(PO₄)_{6 - x}(VO₄) _{6 - x}(OH)₂, were investigated. The strontium phosphate hydroxyapatite [Sr₁₀(PO₄)₆(OH)₂: Sr-P] exhibited the highest 1-butanol selectivity among the tested catalysts in the region of the ethanol conversions between 1 and 24%. The reaction mechanism of 1-butanol formation over the Sr-P hydroxyapatite catalyst includes the dehydrogenation of ethanol into acetaldehyde, the aldol condensation of acetaldehyde into crotonaldehyde, and the hydrogenations of crotonaldehyde, 2-buten-1-ol, and/or butyraldehyde into 1-butanol. The Sr-P hydroxyapatite catalyst showed high selectivity into crotonaldehyde in the aldol condensation of acetaldehyde and inhibited the coking in the hydrogen transfer reaction of 2-buten-1-ol into 1-butanol, which might be reasons why the Sr-P hydroxyapatite catalyst showed the high 1-butanol selectivity in the catalytic conversion of ethanol.

Original language	English
Pages (from-to)	188-195
Number of pages	8
Journal	Applied Catalysis A: General
Volume	402
Issue number	1-2
DOIs	https://doi.org/10.1016/j.apcata.2011.06.006
Publication status	Published - 2011 Jul 31
Externally published	Yes

Keywords

1-Butanol
Ethanol
Strontium phosphate hydroxyapatite

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology

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10.1016/j.apcata.2011.06.006

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@article{2fa3192c8e0a407782b43f8c7b60df1f,

title = "Selective synthesis of 1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts",

abstract = "We previously reported the ability of strontium hydroxyapatite to catalyze the conversion of ethanol into 1-butanol with higher selectivity than that reported for calcium hydroxyapatite catalysts. In the present study, we investigated the catalytic conversions of ethanol over substituted hydroxyapatites, such as Sr10(PO4)6(OH) 2, Ca10(VO4)6(OH)2, Sr10(VO4)6(OH)2, and Ca 10(PO4)6(OH)2, and their solid solutions, such as Ca10 - zSrz(PO4) 6(OH)2, Ca10(PO4) 6 - x(VO4)6 - x(OH)2, and Sr 10(PO4)6 - x(VO4) 6 - x(OH)2, were investigated. The strontium phosphate hydroxyapatite [Sr10(PO4)6(OH)2: Sr-P] exhibited the highest 1-butanol selectivity among the tested catalysts in the region of the ethanol conversions between 1 and 24%. The reaction mechanism of 1-butanol formation over the Sr-P hydroxyapatite catalyst includes the dehydrogenation of ethanol into acetaldehyde, the aldol condensation of acetaldehyde into crotonaldehyde, and the hydrogenations of crotonaldehyde, 2-buten-1-ol, and/or butyraldehyde into 1-butanol. The Sr-P hydroxyapatite catalyst showed high selectivity into crotonaldehyde in the aldol condensation of acetaldehyde and inhibited the coking in the hydrogen transfer reaction of 2-buten-1-ol into 1-butanol, which might be reasons why the Sr-P hydroxyapatite catalyst showed the high 1-butanol selectivity in the catalytic conversion of ethanol.",

keywords = "1-Butanol, Ethanol, Strontium phosphate hydroxyapatite",

author = "Shuhei Ogo and Ayumu Onda and Kazumichi Yanagisawa",

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doi = "10.1016/j.apcata.2011.06.006",

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T1 - Selective synthesis of 1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts

AU - Ogo, Shuhei

AU - Onda, Ayumu

AU - Yanagisawa, Kazumichi

PY - 2011/7/31

Y1 - 2011/7/31

N2 - We previously reported the ability of strontium hydroxyapatite to catalyze the conversion of ethanol into 1-butanol with higher selectivity than that reported for calcium hydroxyapatite catalysts. In the present study, we investigated the catalytic conversions of ethanol over substituted hydroxyapatites, such as Sr10(PO4)6(OH) 2, Ca10(VO4)6(OH)2, Sr10(VO4)6(OH)2, and Ca 10(PO4)6(OH)2, and their solid solutions, such as Ca10 - zSrz(PO4) 6(OH)2, Ca10(PO4) 6 - x(VO4)6 - x(OH)2, and Sr 10(PO4)6 - x(VO4) 6 - x(OH)2, were investigated. The strontium phosphate hydroxyapatite [Sr10(PO4)6(OH)2: Sr-P] exhibited the highest 1-butanol selectivity among the tested catalysts in the region of the ethanol conversions between 1 and 24%. The reaction mechanism of 1-butanol formation over the Sr-P hydroxyapatite catalyst includes the dehydrogenation of ethanol into acetaldehyde, the aldol condensation of acetaldehyde into crotonaldehyde, and the hydrogenations of crotonaldehyde, 2-buten-1-ol, and/or butyraldehyde into 1-butanol. The Sr-P hydroxyapatite catalyst showed high selectivity into crotonaldehyde in the aldol condensation of acetaldehyde and inhibited the coking in the hydrogen transfer reaction of 2-buten-1-ol into 1-butanol, which might be reasons why the Sr-P hydroxyapatite catalyst showed the high 1-butanol selectivity in the catalytic conversion of ethanol.

AB - We previously reported the ability of strontium hydroxyapatite to catalyze the conversion of ethanol into 1-butanol with higher selectivity than that reported for calcium hydroxyapatite catalysts. In the present study, we investigated the catalytic conversions of ethanol over substituted hydroxyapatites, such as Sr10(PO4)6(OH) 2, Ca10(VO4)6(OH)2, Sr10(VO4)6(OH)2, and Ca 10(PO4)6(OH)2, and their solid solutions, such as Ca10 - zSrz(PO4) 6(OH)2, Ca10(PO4) 6 - x(VO4)6 - x(OH)2, and Sr 10(PO4)6 - x(VO4) 6 - x(OH)2, were investigated. The strontium phosphate hydroxyapatite [Sr10(PO4)6(OH)2: Sr-P] exhibited the highest 1-butanol selectivity among the tested catalysts in the region of the ethanol conversions between 1 and 24%. The reaction mechanism of 1-butanol formation over the Sr-P hydroxyapatite catalyst includes the dehydrogenation of ethanol into acetaldehyde, the aldol condensation of acetaldehyde into crotonaldehyde, and the hydrogenations of crotonaldehyde, 2-buten-1-ol, and/or butyraldehyde into 1-butanol. The Sr-P hydroxyapatite catalyst showed high selectivity into crotonaldehyde in the aldol condensation of acetaldehyde and inhibited the coking in the hydrogen transfer reaction of 2-buten-1-ol into 1-butanol, which might be reasons why the Sr-P hydroxyapatite catalyst showed the high 1-butanol selectivity in the catalytic conversion of ethanol.

KW - 1-Butanol

KW - Ethanol

KW - Strontium phosphate hydroxyapatite

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VL - 402

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JO - Applied Catalysis A: General

JF - Applied Catalysis A: General

IS - 1-2

ER -

Selective synthesis of 1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts

Abstract

Keywords

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