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Estimation of kinetic parameters and diffusion coefficients for the transesterification of triolein with methanol on a solid ZnAl2O4 catalyst.

Identifieur interne : 000213 ( Main/Exploration ); précédent : 000212; suivant : 000214

Estimation of kinetic parameters and diffusion coefficients for the transesterification of triolein with methanol on a solid ZnAl2O4 catalyst.

Auteurs : Florent Allain [France] ; Jean-François Portha [France] ; Emilien Girot [France] ; Laurent Falk [France] ; Aurélie Dandeu [France] ; Vincent Coupard [France]

Source :

RBID : Hal:hal-01291766

English descriptors

Abstract

The transesterification of vegetable oils by methanol implies a set of three parallel–series reversible reactions. Over a heterogeneous catalyst, reactions are limited by molecular diffusion, resulting in the use of a large excess of methanol to achieve a high conversion. This excess is detrimental to process efficiency because it involves large energy requirement for downstream separation. In order to identify the coupled physico-chemical phenomena and to optimize the process, a pilot unit was developed to perform transesterification of triglycerides with methanol over a solid ZnAl2O4 catalyst in a tubular fixed bed reactor under high pressure and temperature. The effects of different parameters such as particle diameter, temperature, residence time and molar feed ratio of methanol to triglyceride on fatty acid methyl ester (FAME) yield and triglyceride (TG) conversion were studied. A pseudo-homogeneous reactor model has been developed to identify rate laws and kinetic parameters by exploiting the experimental data in stationary regime. A set of kinetic constants was also determined for the given catalyst considering two kinetic models: an Eley–Rideal model with the reaction between TG and methanol as the rate determining step and a classical second order model taking into account thermodynamic equilibrium without adsorption. A heterogeneous model has also been established to determine molecular diffusion coefficients for each species in the mixture, through the use of experimental results in the transient regime. These molecular diffusion coefficients are dependent on the mixture viscosity and temperature. As a result, it was determined that diffusion of triglycerides and the first reaction kinetic rates are limiting the global conversion of the system.

Url:
DOI: 10.1016/j.cej.2015.07.075


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<country>France</country>
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<settlement type="city">Nancy</settlement>
<settlement type="city">Metz</settlement>
<region type="region" nuts="2">Grand Est</region>
<region type="old region" nuts="2">Lorraine (région)</region>
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<orgName type="university">Université de Lorraine</orgName>
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<author>
<name sortKey="Falk, Laurent" sort="Falk, Laurent" uniqKey="Falk L" first="Laurent" last="Falk">Laurent Falk</name>
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<idno type="IdRef">153068876</idno>
<idno type="RNSR">201320573K</idno>
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<orgName>Laboratoire Réactions et Génie des Procédés</orgName>
<orgName type="acronym">LRGP</orgName>
<date type="start">2013-01-01</date>
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<addrLine>Université de Lorraine - ENSIC, 1 rue de Grandville BP 20451, 54001 Nancy Cedex</addrLine>
<country key="FR"></country>
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<orgName>Université de Lorraine</orgName>
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<date type="start">2012-01-01</date>
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<address>
<addrLine>34 cours Léopold - CS 25233 - 54052 Nancy cedex</addrLine>
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<ref type="url">http://www.univ-lorraine.fr/</ref>
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<orgName>Centre National de la Recherche Scientifique</orgName>
<orgName type="acronym">CNRS</orgName>
<date type="start">1939-10-19</date>
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<country>France</country>
<placeName>
<settlement type="city">Nancy</settlement>
<settlement type="city">Metz</settlement>
<region type="region" nuts="2">Grand Est</region>
<region type="old region" nuts="2">Lorraine (région)</region>
</placeName>
<orgName type="university">Université de Lorraine</orgName>
<placeName>
<settlement type="city">Nancy</settlement>
<region type="region" nuts="2">Grand Est</region>
<region type="region" nuts="2">Lorraine (région)</region>
</placeName>
<orgName type="laboratoire" n="5">Laboratoire réactions et génie des procédés</orgName>
<orgName type="university">Université de Lorraine</orgName>
<orgName type="institution">Centre national de la recherche scientifique</orgName>
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</author>
<author>
<name sortKey="Dandeu, Aurelie" sort="Dandeu, Aurelie" uniqKey="Dandeu A" first="Aurélie" last="Dandeu">Aurélie Dandeu</name>
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<orgName>IFP Energies Nouvelles</orgName>
<orgName type="acronym">IFPEN</orgName>
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<country>France</country>
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<author>
<name sortKey="Coupard, Vincent" sort="Coupard, Vincent" uniqKey="Coupard V" first="Vincent" last="Coupard">Vincent Coupard</name>
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<orgName>IFP Energies Nouvelles</orgName>
<orgName type="acronym">IFPEN</orgName>
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<orgName>IFP Energies Nouvelles</orgName>
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<address>
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</tutelles>
</hal:affiliation>
<country>France</country>
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<idno type="DOI">10.1016/j.cej.2015.07.075</idno>
<series>
<title level="j">Chemical Engineering Journal</title>
<idno type="ISSN">1385-8947</idno>
<imprint>
<date type="datePub">2015</date>
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<keywords scheme="mix" xml:lang="en">
<term>Biodiesel</term>
<term>Diffusion coefficients</term>
<term>Kinetics</term>
<term>Reactor modeling</term>
<term>Transesterification</term>
</keywords>
</textClass>
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<front>
<div type="abstract" xml:lang="en">The transesterification of vegetable oils by methanol implies a set of three parallel–series reversible reactions. Over a heterogeneous catalyst, reactions are limited by molecular diffusion, resulting in the use of a large excess of methanol to achieve a high conversion. This excess is detrimental to process efficiency because it involves large energy requirement for downstream separation. In order to identify the coupled physico-chemical phenomena and to optimize the process, a pilot unit was developed to perform transesterification of triglycerides with methanol over a solid ZnAl2O4 catalyst in a tubular fixed bed reactor under high pressure and temperature. The effects of different parameters such as particle diameter, temperature, residence time and molar feed ratio of methanol to triglyceride on fatty acid methyl ester (FAME) yield and triglyceride (TG) conversion were studied. A pseudo-homogeneous reactor model has been developed to identify rate laws and kinetic parameters by exploiting the experimental data in stationary regime. A set of kinetic constants was also determined for the given catalyst considering two kinetic models: an Eley–Rideal model with the reaction between TG and methanol as the rate determining step and a classical second order model taking into account thermodynamic equilibrium without adsorption. A heterogeneous model has also been established to determine molecular diffusion coefficients for each species in the mixture, through the use of experimental results in the transient regime. These molecular diffusion coefficients are dependent on the mixture viscosity and temperature. As a result, it was determined that diffusion of triglycerides and the first reaction kinetic rates are limiting the global conversion of the system.</div>
</front>
</TEI>
<affiliations>
<list>
<country>
<li>France</li>
</country>
<region>
<li>Grand Est</li>
<li>Lorraine (région)</li>
</region>
<settlement>
<li>Metz</li>
<li>Nancy</li>
</settlement>
<orgName>
<li>Centre national de la recherche scientifique</li>
<li>Laboratoire réactions et génie des procédés</li>
<li>Université de Lorraine</li>
</orgName>
</list>
<tree>
<country name="France">
<region name="Grand Est">
<name sortKey="Allain, Florent" sort="Allain, Florent" uniqKey="Allain F" first="Florent" last="Allain">Florent Allain</name>
</region>
<name sortKey="Coupard, Vincent" sort="Coupard, Vincent" uniqKey="Coupard V" first="Vincent" last="Coupard">Vincent Coupard</name>
<name sortKey="Dandeu, Aurelie" sort="Dandeu, Aurelie" uniqKey="Dandeu A" first="Aurélie" last="Dandeu">Aurélie Dandeu</name>
<name sortKey="Falk, Laurent" sort="Falk, Laurent" uniqKey="Falk L" first="Laurent" last="Falk">Laurent Falk</name>
<name sortKey="Girot, Emilien" sort="Girot, Emilien" uniqKey="Girot E" first="Emilien" last="Girot">Emilien Girot</name>
<name sortKey="Portha, Jean Francois" sort="Portha, Jean Francois" uniqKey="Portha J" first="Jean-François" last="Portha">Jean-François Portha</name>
</country>
</tree>
</affiliations>
</record>

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