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Fuel 140 (2015) 724–730

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Fuel
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Determination of the kinetics of biodiesel saponification in alcoholic


hydroxide solutions
Valentine C. Eze, Adam P. Harvey, Anh N. Phan ⇑
School of Chemical Engineering & Advanced Materials (CEAM), Newcastle University, NE1 7RU, UK

h i g h l i g h t s

 Quantitatively investigated kinetics of fatty acid alkyl esters saponification in alcoholic hydroxides.
 FAME saponification occurred 5–7 times more rapidly in ethanol than in methanol.
 Found actual saponification rate constants for the methanol–KOH and ethanol–KOH.
 Found activation energies for the FAME saponification in the alcoholic hydroxides.
 Provided useful data in understanding/modelling base-catalysed transesterification reactions.

a r t i c l e i n f o a b s t r a c t

Article history: The research focused mainly on kinetics of the side reactions occurring during homogeneous base-
Received 8 July 2013 catalysed transesterification processes, which were not studied previously. The rates of fatty acid methyl
Received in revised form 18 September esters (FAME) saponification with sodium and potassium hydroxides were investigated in methanol and
2014
ethanol (commonly used in biodiesel production) at temperatures of 40, 50 and 60 °C. The effect of water
Accepted 1 October 2014
Available online 18 October 2014
on the rate of FAME saponification in the alcoholic hydroxide solutions was also studied (at 60 °C). The
apparent rate constants of FAME saponification were strongly influenced by the types of alcohol, but little
affected by variation of the metal hydroxides. The apparent rate constants for FAME saponification using
Keywords:
Kinetics
the ethanol hydroxides were 5–7 times higher than for methanol hydroxides. This was due to the lower
Transesterification acidity of ethanol, leading to a higher concentration of hydroxide ions in the ethanol–hydroxide solu-
FAME Saponification tions. The rate constant of the FAME saponification increased with temperature. For example, it was
Rate constants 1.31 L mol1 min1 at 40 °C, but 3.08 and 5.63 L mol1 min1 at 50 and 60 °C in the methanol–NaOH solu-
Hydroxide-alkoxide equillibrium tion. Arrhenius activation energies for the FAME saponification in the alcoholic hydroxides were in the
range of 60.3–64.0 kJ mol1. It was found that the FAME saponification rate in ethanol–hydroxides was
3.5 times higher than that in methanol–hydroxides in the presence of water. This indicates that use of
methanol should be preferred over ethanol in alkali-catalysed transesterification, as the amount of soap
produced by saponification of triglycerides and alkyl esters will be lower.
Crown Copyright Ó 2014 Published by Elsevier Ltd. All rights reserved.

1. Introduction MG þ ROH $ AE þ GL ð3Þ


Overall reaction:
Transesterification of triglycerides with alcohols with/without
catalyst is one method for producing biodiesel, a renewable alter- TG þ 3ROH $ 3AE þ GL ð4Þ
native to diesel. It proceeds via three reversible stepwise reactions
(TG: triglyceride; DG: diglyceride; MG: monoglyceride; GL:
[1,2] as follows
glycerol; ROH: alcohol; AE: alkyl esters).
TA þ ROH $ AE þ DG ð1Þ In alkali-catalysed homogeneous transesterifications, hydrox-
ides and methoxides of sodium and potassium are commonly used.
DG þ ROH $ AE þ MG ð2Þ In a hydroxide-catalysed transesterification process, alongside
three main transesterification steps (Eqs. (1)–(3)), there can also
be saponification of the oil (TG) and the alkyl esters (AE) (Eqs. (6)
⇑ Corresponding author. Tel.: +44 0191 208 5212. and (7)) to form soap. This occurs alongside the main reactions
E-mail address: anh.phan@ncl.ac.uk (A.N. Phan). due to the existence of the hydroxide-alkoxide equilibrium (Eq.

http://dx.doi.org/10.1016/j.fuel.2014.10.001
0016-2361/Crown Copyright Ó 2014 Published by Elsevier Ltd. All rights reserved.
V.C. Eze et al. / Fuel 140 (2015) 724–730 725

(5)). This equilibrium shifts towards the formation of hydroxide CH3 CH2 OH + KOH ↔ CH3 CH2 OK + H2 O
when the water content is increased. The formation of soap leads
to emulsification, which renders the downstream separation of
glycerol very difficult. The deleterious effect of water means that Fig. 2. Ethanol–KOH reaction.
in practice transesterification is limited to very dry (<0.5 wt% mois-
ture) vegetable oils. The depletion of metal hydroxide in a saponification mixture
containing alcohol where carboxylic acid esters were saponified
K eq using 0.1–0.5 M NaOH prepared in approximately 9:1 (v/v) of CH2-
ROH þ OH $ RO þ H2 O ð5Þ
Cl2/methanol was reported [7]. The presence of sodium methoxide
formed by the reaction of NaOH with methanol lead to the transe-
TG þ 3OH ! 3Soap þ GL ð6Þ sterification of the original esters to form ‘‘methyl ester’’ [7]. How-
ever, the authors explained these results due to ‘‘hydroxide ions
assisted’’ bimolecular collisions of methanol and the original
AE þ OH ! Soap þ ROH ð7Þ esters.
Saponification of alkyl esters can occur in aqueous hydroxide Furthermore, the magnitudes of activation energies for alkyl
solutions [3], mixtures of water and soluble organic solvents, such esters saponification indicate that the differences in the desolva-
as dimethyl sulphoxide (DMSO) [4], ethanol [5,6] and mixtures of tion energies of the OH in aqueous/protic and aprotic solvents
protic solvents, e.g. methanol and dichloromethane [7]. It has been was not entirely responsible for the higher rates of alkyl esters
reported that saponification of carboxylic acid esters in hydroxide saponification in dipolar aprotic co-solvents. For instance, the
solutions is a bimolecular reaction, which is first order for ester and Arrhenius activation energies of 41.40–63.18 kJ mol1 [3,5,6,11]
hydroxide ions [3,8]. Hydroxide ions attack the carbonyl to form a for alkyl esters saponification in aqueous/protic medium were
tetrahedral intermediate, which then decomposes to the products too small to account for the desolvation energy of 423.4 kJ mol1
(Fig. 1a). However, recent studies [7,9] found that the reactions [9] required for the desolvation of OH in the aqueous medium.
did not occur via simple bimolecular collisions, but rather required The values of the activation energies for alky esters saponification
a molecule of water to form the tetrahedral intermediate. This indi- suggest that the direct collision of desolvated OH ions is
cates that a water molecule stabilises the transition-state complex implausible.
through hydrogen bonding (Fig. 1b). Such hydrogen bonding could Although extensive research on the kinetics of alkaline hydroly-
also be provided by other protic solvents such as simple alcohols. sis of esters has been done, no study has been carried out on the
The rate of saponification of alkyl esters was strongly depen- kinetics of fatty acid alkyl esters saponification in alcohol hydrox-
dent on steric and electronic interactions of the esters and metal ides. Such investigation is essential to understanding the compet-
hydroxides with the solvent [7]. Such interactions determine the itive saponification of biodiesel produced during alkali-catalysed
rate of saponification in various solvent environments. For homogeneous transesterification. As methanol and ethanol are
instance, the hydroxide anions are highly solvated because of the commonly used for the biodiesel production, kinetic studies of
electronic charge in a predominantly aqueous and protic solvent saponification of fatty acid alkyl esters (biodiesel) in these alco-
environment. The solvation of the OH anions reduces the rate of holic media provide fundamental in choosing alcohol and/or oper-
direct collisions between the anions and the alkyl ester molecules ating conditions to achieve high yield and quality product. In this
in the solution [10]. This phenomenon was used to explain the study, the kinetics of fatty acid methyl esters (FAME) saponifica-
higher rate of saponification of esters in 0.5 M KOH prepared in tion in both methanol–hydroxide and ethanol–hydroxide solutions
80–90% (v/v) DMSO in water than that of 0.5 M KOH prepared in of NaOH and KOH at a temperature range of 40–60 °C were inves-
80–90% (v/v) ethanol in water [4]. 63.5% of the ester was saponified tigated. These conditions are similar to those used in commercial
in a 0.5 M KOH solution prepared in 83.5% (v/v) aqueous DMSO, homogeneously catalysed biodiesel processes. The effect of water
whereas only 9.2% was saponified in a 0.5 M KOH prepared in on the rate of the FAME saponification in the alcoholic NaOH and
83.5% (v/v) aqueous ethanol after 3 min at the same conditions. KOH solutions was also studied.
However, the differences in the rates of saponification of the esters
in 0.5 M KOH prepared in 83.5% (v/v) aqueous DMSO and 0.5 M
KOH prepared in 83.5% (v/v) aqueous ethanol were not entirely 2. Materials and methods
due to the reduction in the desolvation energy of the OH in the
aqueous DMSO solution. The authors did not take into account 2.1. Materials
the reactions of the KOH with ethanol to form potassium ethoxide
(Fig. 2), which reduces the amount of KOH in the solutions and Refined RSO (Henry Colbeck, UK) used in production of the
consequently lowering the rate of saponification. FAME contained approximately 98.7 wt% triglycerides, 0.03 wt%

(a) OH

R C OR' +
-
OH R C OR' R C O- + R'OH
-
O O O

(b) OR' OR'


R C -
O H C H R C O- + R'OH + H2O
+ R O
O - O
O O O
H H H H

Fig. 1. Saponification of alkyl esters (a) reaction mechanism for alkyl esters saponification; (b) bimolecular collision by solvated hydroxide ions to form H-bond stabilised
tetrahedral intermediate.
726 V.C. Eze et al. / Fuel 140 (2015) 724–730

moisture and 0.05 wt% free fatty acids. The measured oil’s viscosity 0.25 mm diameter BPX70 CP wax capillary column. The oven tem-
and density at 60 °C were 25.5 mPas and 890 kg/m3 [12]. perature was set at 210 °C (isothermal) while the injector and FID
Fatty acid methyl esters (97.85 wt% purity), known as FAME, detector temperatures were set at 250 and 260 °C, respectively.
were obtained via a continuous alkaline catalysed transesterifica- The amounts of FAME in the samples were quantified using the
tion process at a molar ratio of methanol to rapeseed oil of 6:1, British standard for quantification of FAME content (BS EN
reaction temperature of 60 °C as described in previous studied 14103: 2003). Errors in FAME analysis were ±1.3%. The FAME
[12]. FAME consisted mainly of esters of oleic acid (63.2%), linoleic saponification experiments at 60 °C using methanol–KOH were
acid (19.8%), linolenic acid (8.6%) and less than 10 wt% of others repeated three times for reproducibility (errors less than ±1.6%).
(palmitic acid: 5.3%, stearic acid: 1.7% and icosenoic acid: 1.4%). Conversion of the FAME (±0.012) to soap was calculated as follows:
Sodium hydroxide (97% purity), potassium hydroxide (90%
purity), methanol (99.8% purity), hydrochloric acid (36.5–38.0% Wo  Wt
FAME conversion to soap ðXÞ: X ¼ ð8Þ
purity), potassium hydrogen phthalate (99.5% purity) and other Wo
analytical standard chemicals such as methyl heptadecanoate
(wt: weight fraction of FAME in the sample; wo: weight fraction of
(99.0% purity), methyl oleate (99.0% purity) were purchased from
FAME at zero saponification).
Sigma–Aldrich. Ethanol (99.99% purity) was obtained from Fisher
Scientific.
3. Results and discussion
2.2. Experimental methods
3.1. Effect of alcohols and alkali on the rates of the FAME
FAME was dried in oven for 12 h at 105 °C to remove all water. saponification
The dried FAME was then saponified with 0.5 M NaOH (or KOH) in
alcoholic solutions using a 100 ml three-neck jacketed glass reac- Fatty acid alkyl esters saponification is an undesired reaction
tor connecting to a water condenser and a thermocouple for mon- during alkali-catalysed transesterification, as it hinders the separa-
itoring reaction temperature as shown in Fig. 3. tion process, reduces yield and reduces the quality of the raw bio-
Approximately 75 ml of 0.5 M alcoholic hydroxide solution was diesel product. As presented in Table 1, KOH has a stronger effect
heated in the reactor to the desired temperature of 40, 50 or 60 °C on the saponification of FAME than NaOH in methanol solution.
by circulating hot water inside the jacket. As soon as the desired For instance, at 60 °C reaction temperature, the FAME conversion
temperature reached, 6 g of pre-heated FAME was transferred into was 0.06 for KOH, but was only 0.03 for NaOH after 2 min. The
the reactor and mixed vigorously using a magnetic stirrer. The ratio finding in this study was similar to others [14], who reported that
of FAME and hydroxide alcohol solution (w/v) in this study was saponification was much faster for KOH than for NaOH. The differ-
adapted from the saponification procedure of fats and oils [13]. ence became smaller when the reaction time was above 30 min.
The same procedure was also used to obtain the weight percentage Generally, the effect of temperature and reaction time on the
of FAME in alcohol solution in absence of hydroxide – without saponification of FAME was similar for both metal hydroxides.
saponification (Wo). Increasing the reaction temperature increased the rate of conver-
About 0.5 ml of the reaction sample was collected using a sion of FAME into soap, e.g. the conversion was 0.14 at 40 °C but
1000 lm micropipette at various time intervals for 60 min. The 0.34 at 60 °C for methanol–NaOH at 30 min reaction time.
sample was transferred into a pre-weighed 2 ml vial containing Because of the similarity of KOH and NaOH as shown in the
0.5 ml HCl (0.5 M) to quench the reaction immediately. All the Table 1, the following discussion only focuses on the effect of the
samples were stored in a freezer for further analysis. alcoholic hydroxides of the potassium solutions. As shown in
Fig. 4, the conversion of the FAME to soap at the reaction times
of 0–30 min was 4 times faster for ethanol–hydroxide solutions
2.3. Analysis
than for methanol–hydroxide solutions for all tested reaction tem-
peratures. For example, the FAME conversion was 0.1 for metha-
FAME content in the sample collected during the experiments
nol–KOH, but 0.43 for ethanol–KOH at 50 °C and 10 min reaction
were analysed using a 5890 Hewlett Packard Series II gas chroma-
time (Fig. 4(b)). At 60 °C, the conversion was 0.36 for methanol–
tography (GC) equipped with a 30 m length, 0.25 lm thickness and
KOH but was 0.86 for ethanol–KOH after 30 min reaction time
(Fig. 4(c)). This agreed well with other findings which the amount
of soap formation in both ester-rich phase and glycerine-rich phase
was 3.5 times higher when using ethanol than when using metha-
nol for alkaline catalysed transesterification [14]. Menegheti et al.
[17] obtained higher fatty acid alkyl esters conversion and lower
Condenser soap formation when using methanol than ethanol. The higher
rates of saponification in the ethanol–hydroxide systems accounts
for the lower ester contents in the ethanolysis.
Sampling port The higher conversions of the FAME to soap obtained for etha-
nol–KOH in the Fig. 4 can be explained by the existence of more
hydroxide ions (OH) in the ethanol–KOH than in the methanol–
3-neck glass KOH due to the stronger acidity of methanol than ethanol (4.4 times
jacketed reactor
higher), which will be discussed later in detail (Section 3.3). As a
result, the formation of methoxide ions (CH3O) is more favourable
in a methanol–KOH system, resulting in less free hydroxide ions
(OH) for the FAME saponification, than that of ethoxide ions
Magnetic stirrer
(C2H5O) in an ethanol–KOH system. Therefore, the higher rates
of FAME saponification in the ethanol–KOH solution was as a result
of higher amount of available hydroxide ions concentration in the
Fig. 3. Experimental set-up for FAME saponification. solution. This study provided a full explanation about the reduction
V.C. Eze et al. / Fuel 140 (2015) 724–730 727

Table 1
Effect of sodium hydroxide and potassium hydroxide in methanol on the conversion of FAME into soap at temperatures of 40 °C, 50 °C and 60 °C.

Temperature, °C Conversion of FAME into soap (X)


0.5 M NaOH solution prepared in 99.8% methanol 0.5 M KOH solution prepared in 99.8% methanol
Reaction time (min) 60 °C 50 °C 40 °C 60 °C 50 °C 40 °C
0 0.00 0.00 0.00 0.00 0.00 0.00
0.5 0.01 0.00 0.00 0.01 0.01 0.00
2 0.03 0.04 0.02 0.06 0.04 0.01
5 0.10 0.04 0.04 0.14 0.06 0.05
10 0.16 0.12 0.07 0.20 0.14 0.08
20 0.26 0.19 0.11 0.30 0.20 0.10
30 0.34 0.26 0.14 0.36 0.27 0.16
40 0.40 0.30 0.17 0.42 0.32 0.19
50 0.47 0.34 0.20 0.50 0.38 0.22
60 0.53 0.38 0.23 0.53 0.40 0.24

1.0 1.0
(a) 40oC Methanol solution (b) 50oC Methanol solution
Ethanol solution Ethanol solution
0.8 0.8
Soap formation

Soap formation
0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Reaction time (mins) Reaction time (mins)

1.0
(c) 60oC Methanol solution
Ethanol solution
0.8
Soap formation

0.6

0.4

0.2

0.0
0 10 20 30 40 50 60
Reaction time (mins)

Fig. 4. FAME saponification in 0.5 M alcohol–KOH solutions at a molar ratio of FAME to KOH of 1:1.85 and reaction temperatures of (a) 40 °C, (b) 50 °C and (c) 60 °C.

of fatty acid alkyl esters in alkali-catalysed biodiesel production be restricted to short chain alcohols. The longer chain (higher
with methanol [12,15,16] and with ethanol [14,17] at greater molecular weight) alcohols such as propanol and butanol contain
reaction times, particularly at high catalyst concentrations. even more mole fractions of hydroxide ions in the alcoholic
Previously this has been either explained qualitatively hydroxide solution, which accelerate saponification reactions of
[12,14,16,17] or wrongly attributed to increased reverse transeste- the biodiesel. Therefore, in order to minimise saponification reac-
rification [15]. tions, methanol must be chosen in homogeneous alkali-catalysed
Menegheti et al. [17] and Mendow et al. [14] also observed that transesterification. In addition, fatty acid methyl esters have lower
more soap formation and consequently less yield of fatty acid alkyl viscosity than other alkyl esters produced from ethanol and longer
esters was obtained in the ethanolysis of sunflower oil than the chain alcohols [18].
methanolysis. An explanation for the increase in saponification
rate was due to higher solubility of the hydroxide catalyst in the 3.2. Kinetics of fatty acid methyl esters (FAME) saponification in the
oil-ethyl esters phase than in the oil-methyl esters phase [14]. alcoholic bases
However, the results in this study indicate that the higher rate of
saponification in ethanol than that in methanol is due to higher Kinetic studies of the fatty acid alkyl esters saponification in
amount of hydroxide ions (OH). This suggests that the choice of association with biodiesel production have not been reported in
alcohol for homogeneous alkali-catalysed biodiesel process must literature. The aim of this section is to explain quantitatively the
728 V.C. Eze et al. / Fuel 140 (2015) 724–730

reduction in fatty acid alkyl esters in homogeneously alkali- R0 OH þ  OH


R0 O þ H2 O ð4Þ
catalysed biodiesel production at various reaction times and
The amount of hydroxide ions available for the saponification of
catalyst concentrations.
FAME is a fraction of the original hydroxide dissolved in the alco-
The saponification rate of FAME in an alcoholic hydroxide solu-
hol. Caldin and Long [19] reported that the hydroxide ion fraction
tion was analysed based on bimolecular collisions of the metal
available in the 0.5 M ethanol–sodium hydroxide at 25 °C was
hydroxide and FAME, with FAME as the limiting reactant [3,8,9].
0.037. This hydroxide ion fraction was assumed to be same for
The saponification rate of FAME in alcoholic hydroxide solution
the 0.5 M ethanol–potassium hydroxide at the same condition. In
can be written as:
this study, the hydroxide ion fraction of 0.037 was used to estimate
dX ME the actual rate constants for the FAME saponification in the etha-
¼ kbdt ð9Þ nol–hydroxides. The actual rate constants of the FAME saponifica-
ð1  X ME ÞðhB  X ME Þ
tion in the methanol–hydroxides were calculated based on the
Integrating Eq. (9): relative acidity of ethanol and methanol, e.g. methanol was 4.4
  times more acidic than ethanol at 26 °C [21]. The estimated rela-
1 ðhB  X ME Þ 0
 ln ¼ kbt ¼ k t ð10Þ tive apparent saponification rate constants of ethanol–hydroxides
ðhB  1Þ½MEo hB ð1  X ME Þ
to methanol–hydroxides were 5.396, 5.423 and 6.938 at 40, 50
Eq. (10) could be simplified as: and 60 °C, respectively. These corresponded to 0.0069, 0.0068
0 and 0.0053, mole fractions hydroxide ions in the methanol–
A  lnB ¼ k t hydroxide solutions at 40, 50 and 60 °C. Table 3 shows the actual
where k = kb is the apparent saponification rate constant (L mol1 rate constants of the FAME saponification in the alcoholic hydrox-
min1), k is actual saponification rate constant (L mol1 min1), b ide solutions using these hydroxide ions fractions.
is mole fraction of unreacted metal hydroxide in the alcoholic The actual FAME saponification rate constants (k) were inde-
hydroxide solutions, ME is Fatty acid methyl esters, [ME]o is initial pendent of both alcohol and metal hydroxide but depended on
concentration of FAME, (mol/L), XME is conversion of FAME to soap, temperatures as shown in Table 3. The Arrhenius activation ener-
hB is the ratio of the initial concentration of alcoholic hydroxide gies of the FAME saponification ranged from 60 to 64 kJ mol1,
solutions to FAME. within the range reported in the literature for alkyl esters saponi-
The apparent rate constants for the saponification of FAME at fication [3,5,6].
temperatures of 40, 50 and 60 °C were determined using Eq. (10) The actual saponification rate constants for the ethyl acetate,
and the experimental data obtained from Table 1 and Fig. 4. The ethyl propanoate and ethyl laurate esters in the Table 4 were cal-
correlation coefficients (R2) of all the plots used to estimate the rate culated using the data from Caldin and Long [19] for sodium
constants were more than 0.99. There was a linear relationship hydroxide–ethoxide–water solution and the apparent rate con-
between the saponification rate constants and temperature for all stant for the saponification in 85 wt% aqueous ethanol [5,6]. As
the tested temperatures. As shown in Table 2, the apparent rate listed in Table 4, the alkyl ester saponification rate constants are
constants (k0 ) increased approximately a factor of 2 for every strongly dependent upon the carboxylic acid chain length. The
10 °C increase in the temperature, e.g. it increased from saponification rates constants at 50 °C (55 °C) were 8.07 L mol1
0.0536 L mol1 min1 at 40 °C to 0.114 L mol1 min1 at 50 °C and min1 for acetic acid ester, 4.10 L mol1 min1 for propanoic acid
0.2152 L mol1 min1 at 60 °C for the ethanol–potassium hydrox- ester and 3.17 L mol1 min1 for lauric acid ester.
ide solution. This indicates that the saponification of the fatty acid
alkyl esters is an endothermic reaction. The difference in the appar- 3.4. Effect of water in the alcoholic hydroxide solutions on FAME
ent FAME saponification rate constants between NaOH and KOH saponification
was small, e.g. the apparent rate constant was 0.105 L mol1 min1
for the ethanol–NaOH and 0.114 L mol1 min1 for ethanol–KOH at Anhydrous ethanol (99.99% purity) and methanol (99.8% purity)
50 °C reaction temperature (8% difference), but significant between were used in order to determine the effect of alkaline catalysts on
methanol and ethanol. The apparent rate constant for FAME sapon- the saponification of FAME during transesterification, and to eval-
ification was 5–7 times higher for the ethanol–hydroxide than for uate the effect of water on the saponification. The results for the
the methanol–hydroxide. This was due to more hydroxide ions FAME saponification at a reaction temperature of 60 °C using alco-
available in the ethanol–hydroxide solution than in the metha- holic hydroxide solutions containing 0–10% (v/v) of water in the
nol–hydroxide solution as explained above. alcohols, are presented in the Figs. 5 and 6.
Figs. 5 and 6 clearly show that water accelerates the rates of
3.3. The hydroxide–alkoxide equilibrium for the alcoholic solutions of FAME saponification. For instance, at 2 min reaction time, the
the NaOH and KOH FAME conversions to soap in the methanol–hydroxides increased
rapidly from 0.03 to 0.10, 0.17 and then to 0.21 for the metha-
When a metal hydroxide is dissolved in an alcoholic solution, nol–NaOH; and from 0.06 to 0.13, 0.19 and to 0.26 for the metha-
there exists an equilibrium between hydroxide and ethoxide ions nol–KOH when the water content rose from 0% to 2, 4 and 10 vol%
as shown below: (Fig. 5). The rapid increase in the FAME conversion to soap in the

Table 2 Table 3
Apparent rate constants (k0 ) for the methyl esters saponification in 0.5 M alcoholic Actual rate constants (k) and activation energy (Ea) for the saponification of FAME in
hydroxide solutions at various temperatures (L mol1 min1). 0.5 M alcoholic hydroxide solutions at various temperatures (L mol1 min1).

Solution k0 (L mol1 min1) Solution k (L mol1 min1) Activation energy (kJ mol1)
40 °C 50 °C 60 °C 40 °C 50 °C 60 °C
Methanol–NaOH 0.0090 0.0208 0.0300 Methanol–NaOH 1.313 3.078 5.626 61.73
Methanol–KOH [20] 0.0099 0.0195 0.0316 Methanol–KOH [20] 1.444 2.921 5.926 61.16
Ethanol–NaOH 0.0484 0.1050 0.2120 Ethanol–NaOH 1.308 2.838 5.723 64.01
Ethanol–KOH 0.0536 0.1140 0.2152 Ethanol–KOH 1.449 3.081 5.816 60.26
V.C. Eze et al. / Fuel 140 (2015) 724–730 729

Table 4
Comparison of the kinetic parameters for the FAME saponification with that reported in the literature for other alkyl esters.

Alkyl esters and the saponification media k (L mol1 min1) Ea (kJ mol1) References
40 °C 50 °C
Ethyl acetate and 0.05 M NaOH in aqueous ethanol 3.88 8.07 61.50 Smith and Levenson [6]
Ethyl propanoate and 0.05 M NaOH in aqueous ethanol 1.98 4.10 61.50 Smith and Levenson [6]
Ethyl laurate and 0.05 M NaOH in aqueous ethanol 1.57 @ 45 °C 3.17 @ 55 °C 63.18 Levenson and Smith [5]
FAME and 0.5 M methanol–KOH 1.44 2.92 61.16 Eze et al. [20]
FAME and 0.5 M methanol–NaOH 1.31 3.08 61.73 This study
FAME and 0.5 M ethanol–NaOH 1.31 2.84 64.01 This study
FAME and 0.5 M ethanol–KOH 1.45 3.08 60.26 This study

presence of water is due to the reaction of the water with alkoxide 1.0
ions in the hydroxide–alkoxide equilibrium (Eq. (4)), producing
more hydroxide ions, by Le Chatelier’s principle. The rate of the
FAME saponification in methanol–hydroxide (Fig. 5) was again 0.8
below that of the ethanol–hydroxide shown in Fig. 6, because

FAME conversion to soap


methanol has a higher acidity than ethanol [21], resulting in fewer
hydroxide ions being available for saponification. As shown in
0.6
Table 5, the apparent rate constants of the FAME saponification
increased with increasing water content, e.g. from 0.03 to
0.399 L mol1 min1 for methanol–NaOH and from 0.212 to
1.494 L mol1 min1 for the ethanol–NaOH, when the water con- 0.4
tent rose from 0 to 10 vol%. This corresponds to an increase in Ethanol-NaOH solution
the apparent rate constants by factors of 3.7% and 12.7% per unit 0% (v/v)
increase in the vol% water in the alcohol for the methanol–NaOH 0.2 2% (v/v)
and ethanol–NaOH, respectively. The deleterious effects of water 4% (v/v)
on alkali-catalysed homogeneous transesterification can be fully 10% (v/v)

inferred from this study. The increased hydroxide ions concentra-


0.0
tion in the presence of water leads to the saponification of both 0 5 10 15 20 25 30 35
glycerides and fatty acid alkyl esters (biodiesel). Soap formation Time (mins)
due to the saponification of glyceride and biodiesel reduces the
biodiesel yield, and causes emulsification, which adversely affects 1.0
glycerol separation unit operations in the downstream processing
[22,23]. To minimise such reactions, anhydrous reactants must
be used for the reactions. Some studies suggest that reactants that
0.8
contain some moisture (less than 0.3 wt%) can be used in the base-
FAME conversion to soap

catalysed homogeneous transesterification [24], such process


achieves less biodiesel conversions due to the increased triglycer-
ide and biodiesel saponification in the presence of water. 0.6
The actual rate constants (k) for the FAME saponification were
expected to be similar at the fixed reaction temperature of 60 °C.
The increases in the apparent rate constants (k0 ) when increased 0.4 Ethanol-KOH solution
water content in Table 5 are plainly due to the increase in the mole

0% (v/v)
1.0 0.2 2% (v/v)
4% (v/v)
10% (v/v)

0.8
FAME conversion to soap

0.0
0 5 10 15 20 25 30 35
Time (mins)
0.6
Fig. 6. Effect of water level on FAME saponification in 0.5 M solutions of ethanol–
NaOH and ethanol–KOH at a molar ratio of FAME to hydroxide of 1:1.85, 60 °C.
0.4

fractions (b) of the hydroxides (k0 = kb). The actual rate constants
0% (v/v)
0.2 2% (v/v)
for the fatty acids alkyl esters saponification at the various water
4% (v/v) contents, calculated using the hydroxide–alkoxide equilibrium in
10% (v/v) the Eq. (4), were consistent with the values in the Table 3. For
0.0 instance, the actual rate constants for the FAME saponification
0 10 20 30 40 50 60 70
were 5.808 L mol1 min1 at 2% (v/v) water, 5.942 L mol1 min1
Time (mins) at 4% (v/v) water and 5.598 L mol1 min1 at 10% (v/v) water, for
Fig. 5. Effect of water level on FAME saponification in 0.5 M solutions of methanol–
the saponification of FAME in 0.5 M NaOH–methanol solutions
NaOH at a molar ratio FAME to hydroxide of 1:1.85, 60 °C. containing various levels of water.
730 V.C. Eze et al. / Fuel 140 (2015) 724–730

Table 5
Apparent rate constants (k0 ) for fatty acid alkyl saponification at 60 °C using alcoholic hydroxide solutions with various vol% water concentrations in the alcohols (L mol1 min1).

Alkyl esters in alcoholic solutions k0 (L mol1 min1)


0% (v/v) 2% (v/v) 4% (v/v) 10% (v/v)
FAME in 0.5 M NaOH–methanol 0.0300 0.116 0.198 0.399
FAME in 0.5 M KOH–methanol [20] 0.0316 0.104 0.175 0.344
FAME in 0.5 M NaOH–ethanol 0.2120 0.517 0.768 1.494
FAME in 0.5 M KOH–ethanol 0.2152 0.464 0.647 1.340
Ethyl laurate in 0.05 M NaOH–ethanol [5] – – – 1.122a
a
Calculated for 12 vol% water and 55 °C reaction temperature.

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