Condensed-Phase Ethanol Conversion to Higher Alcohols

Tyler L. Jordison, Carl T. Lira, Dennis J. Miller

Research output: Contribution to journalArticle

  • 11 Citations

Abstract

Higher alcohols (C4+) can be formed from ethanol via condensation pathways collectively known as Guerbet reactions. Most prior Guerbet reaction studies involve vapor-phase reactions, with n-butanol yields typically no higher than 30% of theoretical. We report here condensed-phase Guerbet reactions of ethanol over Ni/γ-Al2O3 catalysts modified by La2O3. Higher alcohol selectivities in excess of 80% at 230 °C and autogenous pressures are obtained in batch autoclave reactions. At these conditions, which are near the critical temperature of ethanol, the liquid phase is significantly expanded, byproduct gases (CH4 and CO2) are significantly dissolved in the liquid phase, and the vapor phase contains significant quantities of alcohols. To accurately compute ethanol conversion and product yields, both composition and quantity of each phase present at reaction conditions must be determined. To do this, the SR-Polar equation of state is combined with chromatographic analysis of liquid-phase samples taken during reaction to model the phase equilibrium in the reactor at reaction conditions. Composition, density, and total number of moles of the vapor and liquid phases in the reactor are determined from the model and analysis, and they are used to calculate more accurate values of conversion and product yield than those calculated by liquid-phase samples alone.

LanguageEnglish (US)
Pages10991-11000
Number of pages10
JournalIndustrial and Engineering Chemistry Research
Volume54
Issue number44
DOIs
StatePublished - Nov 11 2015

Profile

Alcohols
Ethanol
Liquids
Vapors
Chromatographic analysis
1-Butanol
Autoclaves
Carbon Monoxide
Chemical analysis
Butenes
Equations of state
Phase equilibria
Byproducts
Condensation
Gases
Catalysts
Temperature

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)
  • Industrial and Manufacturing Engineering

Cite this

Condensed-Phase Ethanol Conversion to Higher Alcohols. / Jordison, Tyler L.; Lira, Carl T.; Miller, Dennis J.

In: Industrial and Engineering Chemistry Research, Vol. 54, No. 44, 11.11.2015, p. 10991-11000.

Research output: Contribution to journalArticle

@article{97dd5f67107b4757a42626b3c146517a,
title = "Condensed-Phase Ethanol Conversion to Higher Alcohols",
abstract = "Higher alcohols (C4+) can be formed from ethanol via condensation pathways collectively known as Guerbet reactions. Most prior Guerbet reaction studies involve vapor-phase reactions, with n-butanol yields typically no higher than 30{\%} of theoretical. We report here condensed-phase Guerbet reactions of ethanol over Ni/γ-Al2O3 catalysts modified by La2O3. Higher alcohol selectivities in excess of 80{\%} at 230 °C and autogenous pressures are obtained in batch autoclave reactions. At these conditions, which are near the critical temperature of ethanol, the liquid phase is significantly expanded, byproduct gases (CH4 and CO2) are significantly dissolved in the liquid phase, and the vapor phase contains significant quantities of alcohols. To accurately compute ethanol conversion and product yields, both composition and quantity of each phase present at reaction conditions must be determined. To do this, the SR-Polar equation of state is combined with chromatographic analysis of liquid-phase samples taken during reaction to model the phase equilibrium in the reactor at reaction conditions. Composition, density, and total number of moles of the vapor and liquid phases in the reactor are determined from the model and analysis, and they are used to calculate more accurate values of conversion and product yield than those calculated by liquid-phase samples alone.",
author = "Jordison, {Tyler L.} and Lira, {Carl T.} and Miller, {Dennis J.}",
year = "2015",
month = "11",
day = "11",
doi = "10.1021/acs.iecr.5b02409",
language = "English (US)",
volume = "54",
pages = "10991--11000",
journal = "Industrial & Engineering Chemistry Product Research and Development",
issn = "0888-5885",
publisher = "American Chemical Society",
number = "44",

}

TY - JOUR

T1 - Condensed-Phase Ethanol Conversion to Higher Alcohols

AU - Jordison,Tyler L.

AU - Lira,Carl T.

AU - Miller,Dennis J.

PY - 2015/11/11

Y1 - 2015/11/11

N2 - Higher alcohols (C4+) can be formed from ethanol via condensation pathways collectively known as Guerbet reactions. Most prior Guerbet reaction studies involve vapor-phase reactions, with n-butanol yields typically no higher than 30% of theoretical. We report here condensed-phase Guerbet reactions of ethanol over Ni/γ-Al2O3 catalysts modified by La2O3. Higher alcohol selectivities in excess of 80% at 230 °C and autogenous pressures are obtained in batch autoclave reactions. At these conditions, which are near the critical temperature of ethanol, the liquid phase is significantly expanded, byproduct gases (CH4 and CO2) are significantly dissolved in the liquid phase, and the vapor phase contains significant quantities of alcohols. To accurately compute ethanol conversion and product yields, both composition and quantity of each phase present at reaction conditions must be determined. To do this, the SR-Polar equation of state is combined with chromatographic analysis of liquid-phase samples taken during reaction to model the phase equilibrium in the reactor at reaction conditions. Composition, density, and total number of moles of the vapor and liquid phases in the reactor are determined from the model and analysis, and they are used to calculate more accurate values of conversion and product yield than those calculated by liquid-phase samples alone.

AB - Higher alcohols (C4+) can be formed from ethanol via condensation pathways collectively known as Guerbet reactions. Most prior Guerbet reaction studies involve vapor-phase reactions, with n-butanol yields typically no higher than 30% of theoretical. We report here condensed-phase Guerbet reactions of ethanol over Ni/γ-Al2O3 catalysts modified by La2O3. Higher alcohol selectivities in excess of 80% at 230 °C and autogenous pressures are obtained in batch autoclave reactions. At these conditions, which are near the critical temperature of ethanol, the liquid phase is significantly expanded, byproduct gases (CH4 and CO2) are significantly dissolved in the liquid phase, and the vapor phase contains significant quantities of alcohols. To accurately compute ethanol conversion and product yields, both composition and quantity of each phase present at reaction conditions must be determined. To do this, the SR-Polar equation of state is combined with chromatographic analysis of liquid-phase samples taken during reaction to model the phase equilibrium in the reactor at reaction conditions. Composition, density, and total number of moles of the vapor and liquid phases in the reactor are determined from the model and analysis, and they are used to calculate more accurate values of conversion and product yield than those calculated by liquid-phase samples alone.

UR - http://www.scopus.com/inward/record.url?scp=84946926029&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84946926029&partnerID=8YFLogxK

U2 - 10.1021/acs.iecr.5b02409

DO - 10.1021/acs.iecr.5b02409

M3 - Article

VL - 54

SP - 10991

EP - 11000

JO - Industrial & Engineering Chemistry Product Research and Development

T2 - Industrial & Engineering Chemistry Product Research and Development

JF - Industrial & Engineering Chemistry Product Research and Development

SN - 0888-5885

IS - 44

ER -