Accepted Manuscript

Title: Biodiesel production from waste cooking oils through

esterification: Catalyst screening, chemical equilibrium and
reaction kinetics

Author: Kolja Neumann Kathrin Werth Alejandro Martı́n

Andrzej Górak

PII: S0263-8762(15)00459-1
DOI: http://dx.doi.org/doi:10.1016/j.cherd.2015.11.008
Reference: CHERD 2091

To appear in:

Received date: 22-6-2015

Revised date: 12-11-2015
Accepted date: 18-11-2015

Please cite this article as: Neumann, K., Werth, K., Martín, A., Górak, A.,Biodiesel
production from waste cooking oils through esterification: Catalyst screening, chemical
equilibrium and reaction kinetics, Chemical Engineering Research and Design (2015),
http://dx.doi.org/10.1016/j.cherd.2015.11.008

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 Biodiesel production from waste cooking oils

through esterification: Catalyst screening, chemical

equilibrium and reaction kinetics

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Kolja Neumann a,*, Kathrin Werth a, Alejandro Martín a, Andrzej Górak a,f

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a
TU Dortmund University, Department of Biochemical and Chemical Engineering,

Laboratory of Fluid Separations, Emil-Figge-Straße 70, 44227 Dortmund, Germany

b
an
Lodz University of Technology, Faculty of Process and Environmental Engineering,

Department of Environmental Engineering, Wólczañska 213, 90-924 Lódz, Poland

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* Corresponding author. Tel.: +49 231 755 2357; Fax: +49 231 755 3035.

E-mail addresses: kolja.neumann@bci.tu-dortmund.de, kathrin.werth@bci.tu-dortmund.de,

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andrzej.gorak@bci.tu-dortmund.de
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Page 1 of 38
KEYWORDS

Process intensification; free fatty acids; homogeneous catalysis; heterogeneous catalysis;

biofuels; esterification

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HIGHLIGHTS

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 Acid catalysed esterification enables biodiesel production from waste cooking oils.

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 Sulphuric acid identified as promising homogeneous catalyst for investigated system.

 Chemical equilibrium determined experimentally and modelled between 348 and 393 K.
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 Reaction kinetics determined based on experimental reaction data.
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ABSTRACT
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Fatty esters provide new building-blocks for sustainable chemical and biochemical processes

or can be used as biofuels. For a greener and more economic production of these esters waste
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cooking oils are a promising feedstock, but a pre-treatment step is required. In this step the

high content of free fatty acids is reduced by an acid catalysed esterification. To further
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enhance the overall process efficiency, reactive distillation is favourable for the pre-treatment.

In order to enable a comprehensive analysis of an industrial production process, a step-by-step

procedure considering lab-scale experiments and determination of important model

parameters is provided. In this study the reaction kinetics of the esterification of oleic acid

with ethanol forming the ester ethyl oleate is determined. Prior, a suitable catalyst matching

the operating window of a reactive distillation process is identified in an experimental

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Page 2 of 38
screening.

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 1 INTRODUCTION

The application of renewable feedstocks and their efficient processing are crucial in the

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development of sustainable processes. Fatty esters, which are formed in the transesterification

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of vegetable oils, provide new building-blocks for sustainable chemical and biochemical

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processes. However, nowadays fatty esters are mainly used as biodiesel, which is a promising

alternative fuel based on renewable resources (Demirbas 2008; Sims et al. 2008; Martinez-

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Hernandez et al. 2014). Biodiesel offers various environmental benefits like a drastic

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reduction of carbon dioxide emissions compared to fossil fuels (van Gerpen 2005); it is

biodegradable and non-toxic. Furthermore, the combustion properties are similar to petroleum
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based diesel, and the integration into the existing infrastructure of fossil fuels is easy (Lotero

et al. 2005; Sadhukhan und Ng 2011).

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In common industrial biodiesel production processes the transesterification of vegetable oils

is performed batch-wise using short-chain alcohols, mostly methanol, and homogeneous

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alkaline catalysts (Ahn et al. 1995; Kiss 2014; Santacesaria et al. 2012). Nevertheless, there
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are several disadvantages of the alkaline catalysed transesterification. Oil feedstocks with a

high purity are required; especially containing a low amount of free fatty acids to avoid losses
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of raw material by saponification, which occurs in the presence of the alkaline catalyst and

water that is inevitably in the mixture. Furthermore, the soap formation would lead to

difficulties in the following purification steps of biodiesel and glycerine (Freedman et al.

1984). To avoid saponification and to overcome the aforementioned limitations meso- and

macro-porous heterogeneous catalysts are investigated as an alternative process concept

(Davison et al. 2013; Kapil et al. 2011).

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An economic production of biodiesel is challenging, because of the high raw material costs

for the refined virgin vegetable oils, which account for up to 75 % of the total production

costs (Lim und Teong 2010; Phan und Phan 2008). Therefore, the use of cheaper low-quality

oils, such as waste cooking oil, non-refined non-edible oil (e.g. Jatropha curcas oil, castor oil)

or animal fat, have a great potential to reduce the production costs. The raw material costs for

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waste cooking oils could be about one third of the price of virgin vegetable oils (Phan und

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Phan 2008). Additionally, competition with the food procurement in developing countries is

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avoided by applying non-edible feedstocks to produce a new generation of biodiesel, also

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known as second generation biodiesel (Carriquiry et al. 2011). But the main drawback of the

low-quality oils is the high content of free fatty acids and water that prevent the direct
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application in the conventional biodiesel production process. Non-refined Jatropha curcas oil

contains around 14 wt% of free fatty acids (Kumar Tiwari et al. 2007), whereas waste cooking
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oils could contain up to 34 wt% (Liu et al. 2010). Using a non-refined oil feedstock in the

transesterification an decreased ester yield was observed by Feedman et al. (1984). Under the
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alkaline conditions in the transesterification and in the presence of water, the free fatty acids

tend to hydrolyse. Furthermore, neutralisation reaction of the alkaline catalyst and the free
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fatty acids would lead to losses of catalyst and free fatty acids (Kumar Tiwari et al. 2007). In
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order to avoid this undesired side reactions and material losses a pre-treatment of the low-

quality oil is necessary prior to the transesterification, in which the amount of free fatty acids
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is reduced below 3 wt% (Meher et al. 2006).

In the pre-treatment the free fatty acid content of the low quality oil is reduced by an acid

catalysed esterification of the free fatty acids with an alcohol. Though the acid catalysed

esterification is more time consuming than, for example, a neutralisation, it results in a higher

recovery of biodiesel due to lower losses of feedstock (Bhosle und Subramanian 2005). In

state of the art processes the equilibrium limited esterification reaction is carried out in a

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Page 5 of 38
batch reactor using an excess of alcohol to shift the equilibrium towards the products. To

fulfil the product specifications of less than 3 wt% of free fatty acids in the reaction product, a

high amount of catalyst and alcohol is necessary to reach the desired conversion in a

reasonable reaction time that could result in costly processes. Furthermore, the reaction rate of

the esterification, and thus the time for one batch cycle, is dependent on the initial content of

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free fatty acids (Marchetti et al. 2007). For high initial contents of free fatty acid the product

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specifications might not be fulfilled in the conventional pre-esterification step anymore,

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because a high amount of water is formed, which limits the conversion. In this case high

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pressure esterification, the so called hydrotreating, is an option (Bezergianni et al. 2010),

though it might lead to higher operating costs compared to the low pressure process.
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Generally several approaches of process intensification to improve the esterification of fatty

acids can be found in literature such as the use of simulated moving beds (Kapil et al. 2010)
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or cavitational reactors (Kelkar et al. 2008). Qiu et al. (2010) and Kiss (2014) published a

comprehensive review about several process intensification technology investigated in the

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field of biodiesel production.

A further opportunity to intensify the esterification of free fatty acids is the application of
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reactive distillation. Reactive distillation integrates reaction and separation into one apparatus,
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thus, leading to increased conversion by overcoming equilibrium limitations (Harmsen 2007;

Górak und Stankiewicz 2011). Furthermore, reactive distillation would enable a continuous
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process and might be more flexible regarding fluctuating feedstock composition. Reactive

distillation could lead to reduced capital costs and energy consumption, which may increase

the profitability of the biodiesel production process. To enhance the reaction rates

homogeneous and heterogeneous catalysts could be applied in the reactive section of the

distillation column to achieve the required conversion. Homogeneous catalysts are suitable for

most reactive distillation processes, since the reaction rate can easily be adjusted by the

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amount of catalyst used, which enables more flexible processes. However, using

heterogeneous catalysts is advantageous because no separation of catalyst from the product is

necessary (Keller 2014). In the biodiesel production process the acid catalysed esterification

of the low-quality oils would be followed by an alkaline catalysed transesterification;

therefore, the application of a heterogeneous catalyst in the reactive distillation is favourable,

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since no additional separation step is necessary. Both catalyst concepts have already been

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discussed in literature for the esterification of fatty acids. The homogeneous catalysed

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esterification of myristic acid with isopropanol was investigated by Bock et al. (1997) in a

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column setup with alcohol recovery system. Steinigeweg and Gmeling (2003) showed the

feasibility of heterogeneously catalysed reactive distillation for the esterification of decanoic

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acid with methanol, obtaining almost full acid conversion. Bhatia et al. (2006) reported the

production of isopropyl palmitate in a reactive distillation column using a custom-made zinc

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acetate catalyst.

Though, the feasibility of reactive distillation for the esterification of short-chain fatty acids
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has already been shown in literature, the investigation of the esterification of fatty acids with a

chain length of 18 carbon atoms like oleic acid or linoleic acid is rare. Since these long-chain
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fatty acids are the main components in most vegetable and low-quality oils, we investigate the
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esterification of oleic acid with ethanol to form ethyl oleate and water in order to determine

the potential of reactive distillation for the pre-treatment of waste cooking oils. There are
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limited studies available that deal with the transformation of a lab-scale process into a process

design activity for the integration of process intensification technologies into large scale

processes. Therefore, we develop a step-by-step procedure to enable a model-based process

design of an industrial process and its economic and ecologic evaluation, incorporating the

determination of all essential experimental data for the model development. For the design of

reactive distillation processes knowledge about the reaction kinetics is crucial. In a first step

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heterogeneous and homogeneous catalysts are screened to identify a suitable catalyst to

integrate the esterification into a reactive distillation column. For the best-suited catalyst a

systematic experimental investigation of the chemical reaction equilibrium and the reaction

rate is performed to determine the reaction kinetics. The effects of the main process variables,

such as reaction temperature, amount of catalyst and ethanol to oleic acid ratio, on the

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reaction rate are investigated. Based on these results the chemical equilibrium constant and

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the reaction kinetics are determined. The kinetic parameters will be used in following studies

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to enable a model-based analysis and design of reactive distillation and an evaluation of the

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biodiesel production process based on waste cooking oils.

2 REACTION SYSTEM
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In this study the esterification of oleic acid with ethanol is investigated. Oleic acid is chosen,

because it represents one of the mostly present fatty acids in non-edible and waste cooking
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oils (Atabani et al., 2013; Issariyakul et al., 2007). The use of ethanol, instead of methanol

like in most common processes, provides an interesting opportunity to further increase the
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ecological benefits of the process, since it can be produced from renewable resources by
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fermentation. Scheme 1 shows the reaction equation of the esterification of oleic acid (OAc)

with ethanol (EtOH) to produce the desired product ethyl oleate (EtO). The reaction is
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equilibrium-limited and water is formed as a by-product. Most often acidic catalysts are used

to enhance the reaction rate. The boiling temperatures of the pure components are listed in

Table 1. The reaction mixture shows non-ideal thermodynamic behaviour with a

homogeneous light-boiling azeotrope being formed between ethanol and water (see Table 2).

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 Scheme 1. Esterification of oleic acid with ethanol to form ethyl oleate and water.

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Table 1: Molecular formula and pure-component boiling points Tboil at atmospheric pressure.

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Component Molecular formula Tboil / K Reference
Ethanol C2H6O 351.55 (Stull 1947)

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Oleic acid C18H34O2 633.15 (Stull 1947)
Ethyl oleate C20H38O2 608.36 (García Santander, Carlos M. et al. 2012)
Water H2O 373.17 an(NIST 2015)
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Table 2: Azeotropic data for ethanol and water at
atmospheric pressure (Lide 2009).

Binary system (i - j) Taz / K xi / mol mol-1

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Ethanol - water 351.25 0.897

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3 MATERIALS AND METHODS

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3.1 CATALYSTS

Ethanol and oleic acid react in the liquid phase without the use of a catalyst, but very low

reaction rates are reported (Pinnarat und Savage 2010). Since relatively fast reaction rates are

required to carry out the esterification of oleic acid with ethanol in a reactive distillation

column, catalysts have to be used in order to enhance the reaction rates. For other

esterification reactions, which have already been realized in reactive distillation processes,

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Page 9 of 38
several acidic homogeneous and heterogeneous catalysts are reported in literature (Brehelin et

al. 2007; Buchaly et al. 2012; Calvar et al. 2007). To identify a suitable catalyst for this

reaction system an experimental screening of a homogeneous and a heterogeneous catalyst is

performed.

3.1.1 Homogeneous catalyst

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Sulphuric acid is the most common homogenous catalyst used for esterification (Berrios et al.

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2007), further investigated acids can be found in the review of Lotero et al. (2005). Since

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sulphuric acid shows high reaction rates and good economics, it is chosen to represent the

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homogeneous catalyst in this study.

3.1.2 Heterogeneous catalyst

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Steinigeweg and Gmehling (2003) used the strong acidic ion-exchange resin Amberlyst® 15

to investigate conversion of short-chain fatty acids with methanol in reactive distillation.

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Several ion-exchange resins were used as catalyst for esterification of long-chain fatty acids
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with alcohols in batch reactors (Marchetti et al. 2007; Park et al. 2008); (Özbay et al. 2008)

(Park et al. 2010). Again, the review of Lotero et al. (2005) provides a good overview of the
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available literature. Amberlyst® 15 is chosen for the comparison with sulfuric acid in this

study, since this catalyst has already been successfully tested for different reactive distillation
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applications (Steinigeweg und Gmehling 2003). Due to the presence of water in the reaction

system, which might lead to catalyst deactivation, the modified water-resistant Amberlyst® 15
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hydrogen form wet is used.

3.2 CHEMICALS

Oleic acid pure Ph. Eur. was purchased from the Company AppliChem with a purity of

65-88 %. The impurities are other fatty acids such as myristic acid (C14:0, max. 5 %),

palmitic acid (C16:1 max. 16 %), palmitoleic acid (C16:1 max. 8 %) and stearic acid (C18,

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Page 10 of 38
max. 6 %). Ethanol was purchased by VWR Prolabor with a purity of ≥ 99.8 %. Sulphuric

acid with a purity of ≥ 98 % was supplied by Merck KGaA. Amberlyst® 15, hydrogen form

wet, was delivered by Sigma Aldrich. Ethyl dodecanoate, the internal standard for the GC

analysis, was purchased by Alfa Aesar with a purity of ≥ 98 %.

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3.3 EXPERIMENTAL SETUP

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The chosen reactor allows the investigation of the whole range of expected reaction

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conditions in the reactive distillation column according to the changing boiling temperature

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along the column height. To ensure that the reaction takes place in the liquid phase, the

pressure in the experiments has to be adjusted in order to prevent an increased evaporation of

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the light boilers, here ethanol and water, yielding in erroneous results. Therefore, the

experimental investigations are performed at atmospheric and elevated pressure using two
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different batch reactors (see Figure 1).
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Figure 1: Experimental setup. Left: conventional continuous stirred batch reactor; right: high-pressure
continuous stirred batch reactor.

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The first series of experiments are performed in a 250 ml three-necked stirred glass flask

placed in a tempered oil-bath, heated by a thermostatic bath, to maintain a constant reaction

temperature. Reaction mixture and oil bath are agitated by a magnetic stirrer at approximately

360 rpm. A thermometer is installed through the first neck of the flask to measure the

temperature in the reaction mixture. At the second neck in the middle a water-cooled total

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condenser is placed to prevent a loss of volatile components. The third neck is equipped with

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a septum to serve as sampling point and to insert the catalyst to start the reaction.

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Esterification of oleic acid with ethanol at 10 bars is performed in a high-pressure reactor,

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from the Company Parr. At this operating pressure the evaporation of the volatile components

is minimized in the investigated temperature range. The high-pressure reactor consists of a

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300 ml stainless steel vessel with a flange with a seal in between. Several valves are provided

at the flange to have an access to the reaction mixture. One valve incorporates an inlet for the
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helium supply, which provides the desired operating pressure. Helium is used since it acts as

an inert and does not take part in the reaction. Once pressurized, two valves are used to feed
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chemicals and to withdraw samples, respectively. Additionally to insert the homogeneous

catalyst, a stainless-steel cannula was installed at the top flange. Furthermore, a manometer to
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observe the pressure and a PT-100 thermocouple to measure the temperature in the reactor are
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installed. The heating system consisted of a thermostatic bath which is controlled by the

measured temperature and the programmed set-point. To ensure a good mixing a magnetic stir
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bar is used.

3.4 EXPERIMENTAL PROCEDURE

To run an experiment at ambient pressure with the homogeneous catalyst sulphuric acid, oleic

acid is added to the flask and heated up to the reaction temperature. The second reactant

ethanol is mixed with the sulphuric acid separately to avoid a start of the reaction before

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reaching the required temperature. After reaching this temperature, ethanol and catalyst

mixture are filled into the flask and the time measurement is started. In order to obtain reliable

data to determine reaction kinetics a sufficient number of samples during the kinetic regime

are required. Subsequently, the intervals between sample times have to be large enough to

evaluate the reaction rate at the beginning of the experiment. The time intervals between two

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samplings are increased with progress of the reaction since those are intended to verify the

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setting of the chemical equilibrium. Each sample is withdrawn from the reactor using a

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syringe and had a volume of 2 ml. The sulphuric acid in the samples is neutralized by adding

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diluted alkaline solution, and the samples are stored subcooled in order to stop the reaction.

The experimental procedure to determine reaction kinetics at elevated pressures is similar to

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the procedure described above. At the beginning reagents are preheated separately and are

mixed afterwards to start the reaction. Oleic acid is preheated directly in the reactor while
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sulphuric acid and ethanol are mixed, preheated and stored in a cannula, which is connected

to one valve at the top flange. To start the reaction an overpressure is applied to the cannula,
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thus the mixture of ethanol and sulphuric acid enters the reactor. A suction line connected to

the sampling port is used to take samples from the reaction mixture during the experiments.
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Prior to take each sample, the suction line was flushed by discarding approximately 1 mL of
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liquid from the line.

The experimental procedure using Amberlyst® 15 as heterogeneous catalysts only differs

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slightly form the procedure using sulphuric acid. In the experiments with Amberlyst® 15,

oleic acid and ethanol are mixed in the reactor and heated up, because the non-catalytic

reaction is considered to be negligible. After reaching the reaction temperature a sample is

taken to verify the assumption that the acid index in the mixture at room temperature do not

change after reaching the reaction temperature. To start the reaction the heterogeneous

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catalyst was added and this point was defined at time 0. Samples are taken over the whole

reaction time to observe the progress of the reaction.

3.5 ANALYTICAL METHODS

Different offline analytical methods are applied in order to analyse the reaction mixture

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compositions. A gas chromatograph from Shimadzu (type GC-14B), equipped with a flame-

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ionization detector with a temperature of 543.15 K, is used to analyse the content of ethyl

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oleate and ethanol. A non-polar column HP5 from the company Agilent with a length of 30

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m, an inner diameter of 0.32 mm and film thickness of 0.25 μm is applied, and helium is used

as carrier gas at a pressure of 50 kPa. Single component calibration curves are established
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with an overall accuracy of 2.02 % using ethyl dodecanoate as internal standard to calculate

the mass fractions in the samples. Each sample is analysed three times, and the average mass
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fractions are used for evaluation. All data are recorded and evaluated using the software

LabSolutions®. The developed method takes in total 38 minutes and starts at a temperature of
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333.15 K. With a sampling rate of 100 ms the sample is injected into the column with a

volume of 1 µL and a temperature of 543.15 K. After starting GC analysis the temperature is

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increased to 393.15 K with a heating rate of 10 K/min followed by a further increase to

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503.15 with a heating rate of 7 K/min. This temperature is maintained for 5 minutes and with

a heating rate of 7 K/min the temperature is increased up to 534.15 K. After reaching the
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543.15K the heating rate is changed to 9 K/min and the column is heated till the final

temperature of 573.15 K is reached which is maintained constant for additional 2 minutes.

Typical retention times were 1.5 min for Ethanol, 24.1 min for oleic acid and 24.4 min for

ethyl oleate.

The mass fraction of oleic acid is determined by acid-base titration. The ASTM D 664/D 974

and EN 14104 are standardised methods to determine the acid index, and a detailed

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description can be found in literature (Knothe 2006). In the present study the procedure of the

EN 14104 is applied incorporating the titration of the samples with 0.055 molar alcoholic

potassium hydroxide solution and phenolphthalein as indicator. The mass fraction of fatty

acid is calculated according to Eq. 3.1 with VKOH as the volume of potassium solution

added by titration, cKOH as the molar concentration of the potassium solution and msample as the

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weight of the sample analysed.

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(3.1)

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Following this procedure the conversion of oleic acid XOAc is determined by calculating the

relative difference between the initial mass fraction of fatty acid (t0 = 0 min) and the
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mass fraction of a sample taken at a certain reaction time according to the following
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equation:
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(3.2)
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The water content is determined likewise by titration using a compact volumetric Karl Fischer

titrator (type V30) from the company Mettler Toledo. Each sample is analysed by triplicate to

determine the standard deviation of measurement.

3.6 DESIGN OF EXPERIMENTS

At the beginning preliminary experiments are performed to identify a suitable homogenous or

heterogeneous catalyst. Subsequently a first series of experiments is performed to determine

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the required operating conditions. To assess, whether the esterification reaction of the chosen

chemical reaction system is appropriate for the application of reactive distillation, decisive

parameters influencing the reaction rate and conversion are investigated. For esterification of

long-chain fatty acids the following parameters are identified; reaction temperature, molar

ratio of alcohol to fatty acid and mass fraction of catalyst (Hassan and Vinjamur, 2013;

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Lucena et al., 2011). The chosen parameters and their ranges are listed in Table 3. In this

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-1 -1
study catalyst mass fractions ωcat of 0.005 gcatalyst goleic acid to 0.045 gcatalyst goleic acid ; and

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ethanol to oleic acid ratios χEtOH/OAc between 1:1 and 6:1 are evaluated.

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Table 3: Investigated reaction operating parameters in the first series of experiments.

Conditions
ωcat / gcatalyst goleic acid
-1
1
0.015
2
0.015
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0.015
4
0.005
5
0.015
6
0.045
Treac / K 347 347 347 347 347 347
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χEtOH/OAc / mol mol-1 1:1 3:1 6:1 3:1 3:1 3:1
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Once the operating conditions are set in the first series of experiments (see Section 4), in a

second series of experiments the experimental data to determine the thermodynamic

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equilibrium and the reaction kinetics are generated. Reaction temperatures between 348.15 K
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and 393.15 K, which are in a relevant range for the application of the esterification in a

reactive distillation column, are chosen. The upper temperature limit was set to 393.15 K to
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minimize etherification of ethanol, which is enhanced at elevated temperatures above

413.15 K (Kiviranta-Pääkkönen et al. 1998; Varisli et al. 2007).

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 4 EXPERIMENTAL RESULTS AND DISCUSSION

4.1 CATALYSTSCREENING

A suitable catalyst for the application in reactive distillation has to satisfy different criteria,

such as fast reaction kinetics in the expected temperature range and being commercially

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available and low priced. The experimental results for the homogenous catalyst sulphuric acid

and the heterogeneous catalyst Amberlyst® 15 are presented in the following. The

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experiments are performed at a temperature of 347 K according to the experimental procedure

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described in section 3. Different mass fractions of the homogenous (ωcat = 0.015 gcatalyst goleic
-1
acid ) and the heterogeneous catalyst (ωcat = 0.285 gcatalyst goleic acid-1) are added to the reaction
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mixture, since preliminary experiments revealed a big difference in the activity of the

homogenous and the heterogeneous catalyst. Furthermore, the molar ratio of ethanol to oleic
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acid was increased in the heterogeneously catalysed experiments to enhance the reaction rate.

Figure 2 shows that for the homogenous catalyst sulphuric acid a fast reaction rate is observed
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and the equilibrium conversion is reached after less than 120 min reaction time for the applied

reaction conditions. The heterogeneous catalyst Amberlyst® 15 also shows a catalytic activity
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for the investigated esterification reaction. Nevertheless, the reaction rate is significantly
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lower compared to the homogeneously catalysed esterification. Thus, sulphuric acid is

identified as suitable catalyst for the application in a reactive distillation column to achieve
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considerably high conversion in the respective residence time.

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Page 17 of 38
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Figure 2: Conversion of oleic acid at 347 K. Cycles: heterogeneous catalyst Amberlyst® 15 and
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stoichiometric ratio χEtOH/OAc = 25:1; triangles: homogeneous catalyst sulphuric acid and stoichiometric
ratio χEtOH/OAc = 6:1.
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4.2 INFLUENCE OF THE AMOUNT OF CATALYST AND THE REACTANT RATIO

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Several experimental runs are performed to analyse the influence of important operational
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parameters on the reaction rate, namely the amount of catalyst and the molar ratio of the

reactants. For these fast pre-screenings an investigation of the conversion of oleic acid is
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sufficient, though resulting in larger errors for increasing amounts of catalyst, which also has
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to be neutralized. A detailed analysis of all reactants is performed for experiments used for the

determination of the reaction kinetics. Since the influence of the temperature on the reaction

rate was investigated in detail for the determination of the reaction kinetics, the reaction

temperature during the pre-screening is kept constant at 347 K.

There is a certain trade-off between fast reaction kinetics and an economic operation of the

reactive distillation process. High excesses of alcohol and large amounts of catalyst will lead

to very fast reaction rates. In contrast to these requirements an economic process requires low

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Page 18 of 38
catalyst amounts because the catalyst has to be neutralized in a subsequent process step.

Additionally, high amounts of sulphuric acid lead to corrosion, and thus to high investment

costs. Furthermore, the stoichiometric ratio of alcohol to acid should be low to reduce the

amount of alcohol, which is directly linked with the separation and raw material costs.

The influence of the amount of the catalyst sulphuric acid on the conversion of oleic acid is

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shown in Figure 3. In the diagram the conversions are normalised to the conversion of oleic

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acid of the experimental run with ωcat = 0.015 gcatalyst goleic acid-1.

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Figure 3: Comparison of the normed conversion of oleic acid for different amounts of sulfuric acid
(ωcat: 0.005, 0.015 and 0.045 gcatalyst goleic acid-1) after certain reaction times at a temperature of 347 K
and a stoichiometric ratio χEtOH/OAc of 3:1. The conversions are related to the conversion of oleic acid of
Ac

the experimental run with ωcat = 0.015 gcatalyst goleic acid-1.

As expected high catalyst amounts result in faster reaction rates. Taking the error bars into

account, the conversion of fatty acid after 60 min with a catalyst amount of

ωcat = 0.015 gcatalyst goleic acid-1 is comparable to ωcat = 0.045 gcatalyst goleic acid-1. In comparison, a
-1
catalyst amount of ωcat = 0.005 gcatalyst goleic acid leads to a much lower conversion of oleic

20
Page 19 of 38
acid. Due to the limited residence times in a column, the reaction rate for the lowest amount

of sulphuric acid is too slow to ensure a high conversion of oleic acid in a reactive distillation

process. According to these results a catalyst content of ωcat = 0.015 gcatalyst goleic acid-1 is chosen

to investigate the influence of the stoichiometric ratio and later for the determination of the

reaction kinetics.

t
In Figure 4 the results for the investigation of different oleic acid to ethanol ratios are

ip
displayed, whereby the conversion is normalised to the conversion of oleic acid of the

cr
experimental run with a stoichiometric ratio χEtOH/OAc of 3:1. Very low conversion of oleic

us
acid for the stoichiometric ratio χEtOH/OAc of 1:1 is observed and sufficient conversion for

χEtOH/OAc of 3:1. The conversion rate after 15 minutes is remarkably close for the
an
stoichiometric ratios of 3:1 and 6:1. The higher conversion after 120 minutes can be explained

by the different thermodynamic equilibrium compositions.

M
ed
pt
ce
Ac

Figure 4: Comparison of the normed conversion after certain reaction times at a temperature of 347 K,
a catalyst amount of ωcat = 0.015 gcatalyst goleic acid-1 and different stoichiometric ratios (χEtOH/OAc = 1:1,
3:1 and 6:1). The conversions are related to the conversion of the experimental run with χEtOH/OAc
of 3:1.

21
Page 20 of 38
According to these experimental findings the catalyst mass fraction and the molar ratio of

reactants were set to ωcat = 0.015 g g-1 and χEtOH/OAc = 3:1 for the determination of the reaction

kinetics described in the following chapters.

t
ip
5 CHEMICAL EQUILIBRIUM CONSTANT

cr
The conversion of oleic acid and ethanol in the esterification is limited by the chemical

equilibrium. Equilibrium conditions are reached when the composition of the reaction mixture

us
does not change any more in course of time. Several expressions are used to describe reaction

an
equilibria, for example, the equilibrium ratios Kx or Kc basing on molar fractions or

concentrations, respectively, or the chemical equilibrium constant Ka basing on activities.

M
Generally the chemical equilibrium ratios, Kx(Treac, xi) and Kc(Treac, ci), change with

temperature and composition of the reaction mixture, whereas the chemical equilibrium
ed

constant Ka(Treac) only depends on temperature but not on composition (Sandler 2006). For

homogenously catalysed esterification reactions Richert et al. (2015) found out that Kx
pt

strongly dependents on the amount of alcohol in the reaction mixture, while Ka remains
ce

constant. Considering the esterification in a reactive distillation column, where the

composition profile changes significantly along the column height, the application of the
Ac

chemical equilibrium constant Ka is favoured to describe the reaction kinetics. The chemical

equilibrium constant Ka can be calculated according to Eq. (5.1) as the ratio of the activities

aieq of the reactants and products in the equilibrium.

(5.1)

22
Page 21 of 38
The activity ai of a component i, is defined as the product of the activity coefficient and the

molar fraction of component i, which are determined experimentally (Eq. (5.2)). In the

present study the activity coefficients are calculated by the group contribution method

UNIFAC using Aspen Properties®.

t
ip
(5.2)

cr
To describe the temperature dependency of the chemical equilibrium constant the van’t Hoff

us
equation (Eq. (5.3)) is applied (Sandler 2006). With the integrated form of the van’t Hoff

equation (Eq. (5.4)) the chemical equilibrium constants at different reaction temperatures
an
Ka(Treac) can be calculated basing on the enthalpy of reaction and the ideal gas
M
constant R. The integration boundaries are the reference temperature Tref and a certain reaction

temperature Treac.
ed

(5.3)
pt

(5.4)
ce
Ac

In order to determine the temperature dependency of chemical equilibrium constant, the

equilibrium composition is measured experimentally in a temperature range of 348.15 K to

393.15 K, which is a relevant range for the reactive distillation process. To ensure that the

chemical equilibrium is reached and to determine the chemical equilibrium constant, only

measurements after long reaction times are taken into account. To obtain the unknown

parameter in Eq. (5.4), e.g. , a linear least square regression of the experimentally

23
Page 22 of 38
determined values to the van’t Hoff equation is performed. The value for the chemical

equilibrium constant obtained at the highest reaction temperature, Tref = 393.15 K, is used as

the reference value Ka(Tref). The logarithm of the measured Ka values is plotted against the

reciprocal value of the corresponding reaction temperature to obtain the van’t Hoff plot (see

Figure 5). The plot shows that the chemical equilibrium constant increases with increasing

t
temperature, thus the esterification is favoured by higher reaction temperatures. The shown

ip
absolute error bars are calculated according to error propagation based on the error of the

cr
molar fractions; the error of the activity coefficients cannot be determined. The solid line is

us
calculated by linear least square regression of the van’t Hoff equation taking just the grey

indicated experimental values into account. The resulting expression is as follows in Eq. (5.5).
an
All black coloured Ka values in Figure 5 are experimentally determined and were not used for

regression but for validation. These values show a comparable trend to the values calculated
M
by Eq. (5.5).
ed

(5.5)
pt

The determined enthalpy of reaction = 61.69 ± 3.52 kJ mol-1 reveals an endothermic

ce

reaction. For the esterification of comparable reaction systems, also consisting of a fatty acid

and an alcohol, reaction enthalpy values higher than 50 kJ mol-1 are reported (Moya-León et
Ac

al. 2006). Hence the calculated value is in good agreement with literature data.

24
Page 23 of 38
 t
ip
cr
us
Figure 5: Van’t Hoff plot for the chemical equilibrium constant Ka. Circles: experimental results for
an
the esterification of oleic acid and ethanol between 348.15 K and 393.15 K (grey: used for linear least
square regression, black: used for validation); solid line: result of the linear least square regression.
M
6 REACTION KINETICS
ed

For the modelling of a reactive distillation process not only the knowledge about the chemical

equilibrium but also about the reaction rate, especially the initial reaction rate, is necessary to
pt

describe a reaction in the column. Thus, the kinetic model approach used for the esterification
ce

of oleic acid with ethanol is presented in the following, and consequently a model validation

is performed based on the experimental results.

Ac

6.1 KINETIC MODEL APPROACH

Generally, the reaction rate ri describes the variation of the concentration ci of a component i

with time (see Eq. (6.1)). The reaction rate is proportional to the stoichiometric coefficient υi

of component i. For homogeneously catalysed reactions the reaction rate is dependent on the

25
Page 24 of 38
amount of catalyst applied ωcat (Baerns 2006), as shown in the experimental investigation (see

Section 4). Furthermore, the reaction rate is dependent on the reaction temperature Treac.

(6.1)

For the investigated esterification the variation of the concentration ci of a component i with

t
ip
time is given by the empirical approach of a second-order reaction (see Eq. (6.2)). Wherein kf

cr
is the forward reaction rate constant and kb is the backward reaction rate constant, which are

both dependent on the temperature.

us
(6.2)
an
For the continuously stirred tank reactor a constant reaction volume is assumed, thus the total
M
concentration ctot of the liquid mixture is constant. According to this Eq. (6.2) is rearranged
ed

and integrated into Eq. (6.1):

(6.3)
pt
ce

To account for the strongly non-ideal thermodynamic phase behaviour of the reaction system,

activities should be used to describe the composition of the liquid phase. Therefore, the
Ac

reaction rate constants are substituted by the following expression (Berry et al. 1980):

(6.4)

This theory assumes that the reaction rate constant k is dependent on the activity coefficients

γj of the reactants i and the activity coefficient of the transition state γ#. Since the formation of

26
Page 25 of 38
reaction products in the homogeneously catalysed esterification reaction is assumed to be

ideal the activity coefficient for the transition state γ# is set equal to one. Considering Eq. (6.4)

and Eq. (5.2) the reaction rate of the investigated esterification of oleic acid with ethanol can

be described as follows:

(6.5)

t
ip
cr
With the definition of the chemical equilibrium constant the following relation between the

forward and backward reaction rate constant is given:

us
(6.6)
an
By integrating this relation (Eq. (6.6)) into the expression of the reaction rate (Eq. (6.5)) the
M
number of adjustable parameters can be reduced to one, since the value of the equilibrium
ed

constant can be directly calculated based on the experimental data (see Eq. (6.7)). The

forward reaction rate constant kf’ was fitted to the experimental kinetic data by a non-linear
pt

regression. The regression was performed in the simulation environment Aspen Custom

Modeler® by use of a non-linear least square algorithm.

ce

(6.7)
Ac

To describe the temperature dependency of the forward reaction rate constant an Arrhenius

approach is applied (Eq. (6.8). The Arrhenius approach describes the forward reaction rate

constant as a function of the pre-exponential factor k0, the activation energy EA and the ideal

gas constant R.

27
Page 26 of 38
 (6.8)

Figure 6 presents the Arrhenius plot for a temperature range of 348.15 K to 393.15 K. To

determine the unknown parameters k0 and EA a least square regression of the fitted reaction

rate constants were performed. The pre-exponential factor is determined as

t
ip
k0 = 4.72·102 m3 mol-1 s-1and the activation energy is EA = 36.62 kJ mol-1.

cr
us
an
M
ed
pt
ce

Figure 6: Arrhenius plot for the reaction rate constant kf. Rhombus: fitted to experimental results for
the esterification of oleic acid and ethanol between 348.15 K and 393.15 K (grey: used for linear least
square regression, black: used for validation); solid line: result of the linear least square regression.
Ac

6.2 MODEL VALIDATION

To verify the accuracy of the determined kinetic parameters the simulated temporal

concentration courses of the reaction are compared with experimental data. In Figure 7 the

experimentally determined temporal course of the mass fraction of ethyl oleat for the reaction

temperatures of 348.15 K and 378.15 K are compared with the simulated results. It can be

28
Page 27 of 38
shown that the experimental data well agree with the applied activity-based kinetic approach

of second order. The simulated molar fractions of all components in comparison to the

experimental values for the kinetic experiments between 348.15 K and 393.15 K can be found

in Figure 8.

t
ip
cr
us
an
M
ed

Figure 7: Experimentally determined and simulated temporal course of the mass fraction of ethyl
oleate in dependence of the reaction temperatures. Cycles: experimental data at 348.15 K, black line:
pt

simulated data at 348.15 K; triangles: experimental data at 378.15 K, grey line: simulated data at
378.15 K.
ce
Ac

29
Page 28 of 38
 t
ip
cr
us
Figure 8: Experimentally determined and simulated molar fractions of all components for reaction
an
temperatures between 348.15 K and 393.15 K, dashed lines: +/-30 % accuracy.
M
7 CONCLUSION
ed

In order to enable a comprehensive computer-aided process analysis of an industrial biodiesel

production process based on waste cooking oils, a step-by-step procedure considering lab-
pt

scale experiments and determination of important model parameters is provided. In the first

series of experiments a catalyst screening is performed to identify a suitable catalyst for a

ce

reactive distillation process. It is found that the homogenous catalyst sulphuric acid

outperform the heterogeneous catalyst Amberlyst® 15. To develop a reliable kinetic model the
Ac

influence of the amount of sulphuric acid, the reactant ratio and the reaction temperature on

the reaction rate and the chemical equilibrium are investigated experimentally. The results are

used to fit the parameters of the kinetic model, which considers an activity based approach of

second order. The developed kinetic model is validated against own experimental data and it

is shown that the simulated data are in good agreement with the experimental results. Hence,

the kinetic model can be used in the following works incorporating the development of a

30
Page 29 of 38
reactive distillation model, to enable process analysis and design of a biodiesel production

process using waste cooking oils or other low-quality oils as raw material.

ACKNOWLEDGEMENTS

t
The research leading to these results has received funding from the Ministry of Innovation,

ip
Science and Research of North Rhine-Westphalia in the frame of CLIB-Graduate Cluster

cr
Industrial Biotechnology

us
We gratefully acknowledge the valuable scientific support of Katrin Kissing.

NOMENCLATURE an
Latin letters
M
ai Activity of component i (mol mol-1)

c Molar concentration (mol m-3)

ed

EA Activation energy (kJ mol-1)

Enthalpy of reaction (kJ mol-1)

pt

k Reaction rate constant (m3 mol-1 s-1)

ce

k0 Pre-exponential factor (m3 mol-1 s-1)

K Equilibrium ratio/constant
Ac

m mass (kg)

ri Reaction rate of component i (mol m-3 s-1)

R Ideal gas constant (J mol-1 K-1)

t Time (min)

T Temperature (K)

V Volume (m-3)

xi Molar fraction of component i (mol mol-1)

31
Page 30 of 38
Xi Conversion of component i (%)

Greek letters

γi Activity coefficient of component i

υi Stoichiometric coefficient of component i

χEtOH/OAc Molar ratio of ethanol and oleic acid (mol mol-1)

t
ωcat Mass fraction of catalyst (g g-1)

ip
cr
Subscripts

a Activity-based

us
az Azeotrope

b Backward

boil Boiling point

an
c Concentration-based
M
f Forward

i Component i
ed

j Reactant j

reac Reaction
pt

ref Reference value

ce

tot Total

x Molar-based
Ac

# Transition state

Abbreviations

AI Acid index

CO2 Carbon dioxide

DOE Design of experiments

EtOH Ethanol

KOH Potassium hydroxide

32
Page 31 of 38
OAc Oleic acid

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