Fuel 256 (2019) 115831

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A novel inspection of mechanisms in conversion of refined palm oil to T

biodiesel with alkaline catalyst
D. Nguyen Thoaia,b, I. Chanakaewsomboona, K. Prasertsita, S. Photaworna, C. Tonguraia,
⁎

a
Department of Chemical Engineering, Faculty of Engineering, Prince of Songkla University, Songkhla 90112, Thailand
b
Department of Chemical Engineering, Faculty of Chemistry, Quy Nhon University, Binh Dinh 820000, Viet Nam

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: The aim of this work was to investigate the two-phase system in alkaline catalyzed methanol transesterification.
Mechanism An alkoxide-methanol solution was gradually added dropwise to 50 °C refined palm oil (RPO), and the solution
Biodiesel was imaged periodically using an LCD digital microscope until the alcohol phase was in large excess. Vice versa,
Methanolysis RPO was dropwise added to an alkoxide-methanol solution. A concave glass slide was used as a microreactor and
Transesterification
the methanolysis was also observed with a microscope and photographed at desired time points. Varying the
Alkaline catalyst
Liquid-liquid reaction
alkoxide concentration in transesterification of refined palm oil and methanol was investigated experimentally.
After 10 min of reaction, the solution settled to ester and glycerol phases; each phase was weighted and soap,
alkoxide and glycerol contents were determined. The results show that transesterification takes place in a two-
phase system and the reaction takes place in the film zone of liquid triglyceride. The concentration of alkoxide is
a key factor determining the rate of reaction. The 0.133 M ratio of catalyst to oil gives a final ester content of
97.31%. Novel mechanisms in transesterification are also proposed.

1. Introduction reactions in transesterification can be written as follows [2]:

catalyst
“Biodiesel production is a deceptively simple process, and there are TG + 3ROH G+ 3E (1)
a lot of things the authors do not know about the biodiesel process” said This reaction occurs in three major steps:
by Prof. Jon Van Gerpen, a well-known researcher of biodiesel pro- (2)
TG + ROH DG + E
duction, in the Collective Biofuels Conference 2012 [1]. These state-
ments inspired us to clarify factors that affect the reactions. The overall DG + ROH MG + E (3)

⁎
Corresponding author.
E-mail address: chakrit.tong@gmail.com (C. Tongurai).

https://doi.org/10.1016/j.fuel.2019.115831
Received 13 December 2018; Received in revised form 7 June 2019; Accepted 17 July 2019
Available online 02 August 2019
0016-2361/ © 2019 Published by Elsevier Ltd.
D.N. Thoai, et al.
MG + ROH G+ E (4)
Here TG, DG, MG, G, E, and ROH are triglyceride, diglyceride,
monoglyceride, glycerol, alkyl ester, and alcohol, respectively.
The mechanism of alkaline-catalyzed methanolysis of triglyceride is
shown in detail in Eqs. (5)–(8). An alkoxide is created from the alkali
metal alkoxides or the reaction between alkaline and alcohol. Firstly, the
nucleophilic alkoxide pairs with the carbonyl group of triglyceride to
form a primary tetrahedral intermediate. Then, an alcohol reacts with
this intermediate to regenerate the alkoxide and a secondary tetrahedral
intermediate, which transforms to an alkyl ester and diglyceride [3]. The
regenerated active alkoxide (Eq. (7)) is now able to attack another car-
bonyl group of the glycerides to create a new catalytic cycle. Finally,
diglycerides and monoglycerides are converted by similar catalytic cycles
and transformed to two types of final products: glycerols and a mixture of
alkyl esters.
here BOR is alkali metal alkoxide; R is alkyl group of an alcohol; and R1,
R2, and R3 are long-chain hydrocarbons.
Free fatty acids (FFA) and water in the oil and alcohol phases also
play very important roles in soap formation. Free fatty acids react with
an alkaline catalyst and turn into soap and water or alcohol as follows:
FFA + KOH Soap + Water (9)
FFA + KOCH3 Soap + CH3 OH (10)
Water can hydrolyse ester in a reverse esterification, giving FFA and
alcohol as follows:
Ester + Water FFA + Alcohol (11)
The FFA is neutralized with alkaline catalyst in an irreversible re-
action and turns to soap.
Alkoxide catalyst also reacts with fatty acid methyl esters (FAME) to
form soap and dimethyl ether as follows:
FAME + KOCH3 Soap + CH3 OCH3 (12)
There are a number of kinetic studies of transesterification based on
assuming a single liquid phase [4–8]. On the other hand, a few of these
models were concerned with liquid-liquid reactions or two-phase re-
actions, such as those by Slinn [9], Tubino et al. [10], and Uemura et al.
[11]. However, the progression of the two-phase reactions is not elu-
cidated.
This study aimed to explore the intrinsic kinetics of alkaline-trans-
esterification via microscope visualization. The rate-determining
2
Fuel 256 (2019) 115831
catalyst concentration was investigated. Finally, a conceptual kinetic
model of the liquid-liquid reaction is proposed.
2. Materials and methods
In this work, an LCD digital microscope was used to investigate me-
thanolysis with alkaline catalysts, and trials were started from excess oil or
from excess alcohol for transesterification. Methanol and potassium
methoxide drops were gradually added to an oil pool, to observe the ki-
netics with excess oil. This trial attempted to explore the effects of mis-
cibility of methanol with oil, and whether the reaction is homogeneous or
liquid-liquid type. In contrast, when oil drops were gradually added to
alcohol and catalyst pool, the oil was expected to change to nearly pure
ester and dissolve in the alcohol. The trial was continued until no more
phase changes were seen. The microscopy images were taken periodically.
(5)
(6)
(7)
(8)
Observations of methanolysis on a concave glass slide microreactor
at room temperature were also done to determine the reaction zone.
The pictures reveal the situation clearly.
2.1. Stability of phase morphology with liquid-liquid reaction
2.1.1. Methanolysis with excess oil
The experimental setup is shown in Fig. 1. The reaction was carried
out in a 1 L three-neck flask, with magnetic stirring, using a 50 mm
Teflon-coated magnetic bar, and at 500 rpm. The reaction temperature
was in the range 50–52 °C sensed with a thermocouple and regulated by
a temperature controller. A reflux condenser was used to maintain at-
mospheric pressure. Firstly, two hundred grams of refined palm oil
(RPO) with acidity below 0.5 mg KOH/g sample was loaded into the
flask and was heated to the desired temperature. A catalyst solution
containing methanol (45 g), KOCH3 (1.5 g), and phenolphthalein (5
drops of 1% phenolphthalein in methanol 22.6 g) were slowly fed to the
reactor by a peristaltic pump until 6:1 methanol:oil molar ratio. In
order to avoid a lot of soap from excess alkaline catalyst, after that only
methanol was fed to the flask and the experiment was ended when the
methanol:oil molar ratio reached 42:1. Ten μL samples were taken at
desired time points to determine the molar methanol to oil ratio. The
sample was immediately dropped on a microscope glass slide, covered
with a cover glass, and photographed using a microscope, LCD 307.
D.N. Thoai, et al.
Fig. 1. The experimental setup for investigating stability of phase morphology
with liquid-liquid reaction.
2.1.2. Methanolysis with excess methanol
These experiments were similar to the previous ones, except that a
catalyst solution (24.19 g methanol, 0.81 g KOCH3, and 5 drops phe-
nolphthalein indicator) was loaded in the three-neck flask and heated to
the desired temperature, before continually adding RPO (641 g) into
the reactor using a peristaltic pump. The experiment was ended when
the methanol:oil molar ratio reached 1:1.
2.2. Reaction zone study
A concave glass slide was used as a microreactor. A small pool of
RPO (approx. 10 μL) at room temperature was put on the concave glass
slide and centered under the LCD 307 microscope. A very fine drop of
methanol-alkoxide-phenolphthalein solution (1 μL) was dropped into
the pool of RPO. A photo was taken every 5 s. A reversed trial was done
by putting a fine drop of RPO (1 μL) to the center of the concave slide,
then a small amount of methanol-alkoxide-phenolphthalein solution
(approx. 10 μL) was dropped in and photos were taken every 5 s. These
trials were repeated several times.
2.3. The concentration effect of potassium methoxide on methanolysis of
refined palm oil
The transesterification of refined palm oil was carried out in a
500 mL three-neck flask. The flask was equipped with a magnetic
stirrer, a thermometer, a reflux condenser, and a sample outlet.
Potassium methoxide catalyst (32%wt in methanol) was varied in
0.37–1.81%wt of oil.
All experiments were performed at the selected conditions: reaction
temperature (50 °C), methanol:oil molar ratio (6:1) and speed of mag-
netic stirrer at 500 rpm. The mixing effect from the different stirrer
speeds 500, 600 and 750 rpm had been already investigated and these
gave similar results. Bambase et al. [12] also showed no effect from
mixing intensity at 400 or 600 rpm. The experiment began as follows.
Three hundred grams of RPO was poured into the flask and heated to
the desired reaction temperature. A potassium methoxide catalyst so-
lution was prepared and added into the reactor. The reaction was kept
at the designated conditions. After 10 min of reaction, the reaction
mixture was poured into a separation funnel and let stand for 2 h. The
glycerol phase (lower phase) was separated from the ester phase by
decanting. The remaining catalyst and soap content were determined
for each phase. The ester phase was washed using warm water (50 °C)
to remove impurities, including methanol, remaining catalyst, soap,
and glycerol. The washed ester was heated to remove residual water.
3
Fuel 256 (2019) 115831
2.4. Analytical methods
The water contents in refined palm oil and methanol were measured
by the Karl Fischer method (ISO 12937). FFA content was tested by
titration (Method AOAC 940.28). Catalyst and soap contents were
measured by titration (modified AOCS Official Method Cc 17–79). Ester
content was analyzed following the chemical method [13].
3. Results and discussion
3.1. The microscope images of methanolysis process
Representative photographs of methanolysis with excess oil and
excess methanol are shown in Table 1. All the pictures show two
phases, at any ratio of oil and methanol. The pink color of phe-
nolphthalein in a drop indicates methanol phase in which the meth-
oxide catalyst prefers to stay. These results are identical to the trials of
Csernica and Hsu [14], the partition coefficient of potassium catalyst
(CK+,MeOH/CK+ ,SBO) > 29.67 for molar ratio MeOH:SBO (soy bean
oil) > 6:1. The microscope images show that the disperse phase is
methanol drops in the continuous triglyceride phase from MeOH:RPO
molar ratio of 1:1 until 27:1. At the molar ratios of 27:1 to 30:1 the
continuous phase was ambiguous. At molar ratio 30:1 phase inversion
had taken place, so the continuous phase was methanol-glycerol as the
amount of oil was less than that of catalyst solution. White spherical
drops of ester phase became the disperse phase until the end of ex-
periments at molar ratio 42:1. These phenomena match the binary
phase diagram of soybean oil and methanol presented by Csernica and
Hsu [14]. The binary phase diagram shows methanol-rich phase and
triglyceride-rich phase.
3.2. The microscope images of reaction zone
With a drop of methanol-alkoxide solution in refined palm oil
(Table 2), the pink color faded within 600 s. The droplet sizes became
gradually smaller from the initial 62 to 56, 46 and 41 μm diameter
within 60, 240 and 600 s, respectively. The fading and reduction in
diameter indicate the diffusion of methanol-alkoxide solution outwards
from the drop. A thin layer appeared after 90 s and later on became
light brown. The light brown phase was assumed to be glycerol. In the
reversed tests, a refined palm oil drop had a pink spot in the center after
240 s and seemed to disappear within 600 s. The diameter of droplet
changed slightly from the initial 83 to 90 μm after 600 s. This matches
the binary phase diagram investigated by Csernica and Hsu [14]. The
solubility of triglyceride in methanol-rich phase is approximately 10
times less than of methanol in triglyceride-rich phase. This supports the
diffusion of methanol-alkoxide solution into the drop, as the pink al-
kaline drop phase occupied the lowest part of the concave slide. The
authors assumed the small amount of generated glycerol was dissolved
in the comparatively large methanol-alkoxide solution phase. When
triglyceride was converted to ester, it became more polar and easily
dissolved in the methanol solution. Please note that equal volumes of
triglyceride and methanol have different numbers of moles. From the
microscope images, the plausible reaction zone should be in the tri-
glyceride phase where the methanol and alkaline catalyst diffuse into.
3.3. The effect of potassium methoxide on methanolysis of refined palm oil
This trial aimed to explore the role of alkaline catalyst on the re-
action rate and as a reactant in neutralization with FFA and saponifi-
cation to ester. The molar amount of potassium methoxide was varied
from less than the molar contents of both FFA and water in both oil and
methanol (99.8% purity) to content higher than commercial level (1%
wt of oil), as shown in Table 3. Remaining catalyst and soap contents
were measured from both phases (ester and glycerol). From Table 4, the
results show low conversion or low ester content when using a low
D.N. Thoai, et al. Fuel 256 (2019) 115831

Table 1
Photographs of methanolysis with initial excess oil or with excess alcohol and alkaline.
Alcohol and alkaline to initially excess Oil Oil to initially excess alcohol and alkaline

MeOH/Oil Molar Photograph with 100× magnification Dispersed Phase Oil/MeOH Molar Photograph with 100× magnification Dispersed Phase
ratio ratio

10 drops Single phase 10 drops Single phase

1:1 Methanol-glycerol- 1:42 Oil-ester

catalyst

3:1 Methanol-glycerol- 1:36 Oil-ester

catalyst

6:1 Methanol-glycerol- 1:30 Oil-ester

catalyst

18:1 Methanol-glycerol- 1:24 Methanol-glycerol-

catalyst catalyst

24:1 Methanol-glycerol- 1:21 Methanol-glycerol-

catalyst catalyst

27:1 Methanol-glycerol- 1:18 Methanol-glycerol-

catalyst catalyst

30:1 Oil-ester 1:6 Methanol-glycerol-

catalyst

42:1 Oil-ester 1:1 Methanol-glycerol-

catalyst

amount of catalyst, and very low contents of remaining catalyst. The
molar amounts of soap and remaining catalyst approximately equal the
molar alkaline input. These results present the loss of alkaline catalyst
as a reactant with FFA and water. The excess molar amount of alkaline
over water and FFA (Runs #1, 2 and 3) is necessary to attain the
standard requirement of ester content (> 96.5%).
Bambase et al. [12] studied the kinetics of hydroxide-catalyzed
methanolysis of crude sunflower oil (SFO) and reported the effect of
catalyst loading of NaOH:SFO set at 0.055, 0.110, or 0.219 relative to
the molar ratio of catalyst/oil. The catalyst loading at 0.055 M ratio
resulted in a slow reaction and the conversion was terminated at 60%
because the available catalyst had been saponified. In comparison with
Bambase’s work, our trial run #3 at catalyst loading of 0.133 gave
triglyceride conversion (97.31%) higher than the 0.110 ratio case of
Bambase (95.51%). The remaining catalyst of run #4 was 0.004 from
the initial 0.021 mol, yielding a low triglyceride conversion of 85.06%
with saponification of available catalyst, as in Bambase’s work.
The catalyst/MeOH ratios initially and at the end of reaction, in the
glycerol phase, are shown in Table 4. In the two-phase system, the
methanol phase is assumed to be stagnant and methanol and catalyst
diffuse into the triglyceride phase [11]. At a high catalyst loading (Runs
#1–3), our trials showed the maximum difference in the catalyst/MeOH
ratio from the initial 16% (Run #1). At a low catalyst loading, this ratio
change looks large, but the maximum difference is 0.004 mol/mol (Run
#6) and is below the 0.005 mol/mol of Run #1. Another explanation is
that some glycerol droplets were generated in the main body of

4
D.N. Thoai, et al. Fuel 256 (2019) 115831

Table 2 triglyceride phase, where available alkaline catalysts were saponified to

Photographs of methanolysis with excess oil or excess alcohol and alkaline for soap, and this depleted the catalyst concentration in the glycerol phase.
up to 600 s (Photographs taken with 40× magnification). The concentration of alkaline catalyst in triglyceride phase was very
Time (s) Alcohol and alkaline to excess oil Oil to excess alcohol and alkaline low and in most cases it was in the glycerol phase, similar to the
findings of Mendow (0.175 gMeONa/kgbiodiesel and 44.58 gMeONa/
5 kgglycerol) [15].

4. Proposed novel mechanism of alkaline transesterification

10 From the photography results (Table 1), the authors believe that the
methanolysis via alkaline catalyst is a liquid-liquid reaction. The me-
thanol drops or oil drops do not dissolve in the continuous phase even
at the beginning of the reaction when the disperse phase is very small in
proportion to the continuous phase. The depletion of methanol and
30 alkaline catalyst from the droplet of methanol (Table 2) and the growth
of triglyceride droplets in methanol solution indicate mass transfer into
the triglyceride phase. Also, Csernica et al. [14] showed the much
higher solubility of methanol in triglyceride-rich phase than of trigly-
ceride in methanol-rich phase. So, a model with a two-phase system
60 should appropriate as in Uemura et al. [13], who proposed mass
transfer of oil into methanol droplets. Therefore, a model of mass
transfer of methanol to oil is proposed in this paper.
Bambase et al. reported the conversion SFO at 82.7% after 2 min of
reaction time, so this reaction is relatively rapid [12]. Assuming fast
90 transesterification that turns methanol drops to glycerol-methanol
phase would make it difficult for the methanol to get into the oil phase.
The initial reaction starts from small droplets of alcohol or oil; the
smaller volume of liquid becomes the droplet phase. Let us introduce a
model with small alcohol droplets here. Usually, the authors mix the
120 alkaline catalyst to alcohol prior to adding it to the oil. Then, this al-
cohol solution is mixed into the oil, and due to the low solubility of
alcohol and catalyst mix, it immediately forms small droplets. Some
alcohol and companion catalyst diffuse to the triglyceride film. The fast
alkaline catalyzed transesterification turns triglyceride to diglyceride,
240
monoglyceride, and ester, while leaving glycerol moving back to al-
cohol droplets, because glycerol has very low solubility in oil. In con-
trast, ester goes to the oil phase, while most of the diglyceride or
monoglyceride is distributed at the interfaces of the droplets, having
emulsifier capacity. The initial state of reaction and interface behavior
360
for the liquid-phase reaction are shown in Fig. 2.
Soap from the acid-base reaction of free fatty acid and alkaline
catalyst may be present at the interface of a droplet, and all of these
compounds, namely soap, diglyceride, monoglyceride, and glycerol,
become a barrier to the transfer of alcohol and catalyst to oil. The mass
600
transfer resistance becomes an important factor affecting the overall
reaction rate, and is in turn affected by both the emulsifier substance
and the thickness of glycerol layer.
From the viewpoint of the alcohol droplet, the generated glycerol
tends to move inwards towards the center and an alcohol and catalyst
countercurrent moves outwards. If more glycerol is present in the outer
shell, then the rate of alcohol and catalyst transfer to the droplet surface

Table 3
Conditions and phase separation in methanolysis of refined palm oil.
Run# RPO MeOH KOCH3 FFA + H2O Phase Separation Ester content

Glycerol phase Ester phase

g mol g mol g mol %wt g g %wt

1 300 0.354 67.92 2.123 5.43 0.078 0.019 50.18 317.09 98.13
2 300 0.354 67.92 2.123 4.35 0.062 0.020 49.73 315.4 97.72
3 300 0.354 67.92 2.123 3.26 0.047 0.020 48.50 317.2 97.31
4 300 0.354 67.92 2.123 2.26 0.021 0.021 43.19 321.18 85.03
5 300 0.354 67.92 2.123 1.50 0.016 0.021 39.16 324.97 79.31
6 300 0.354 67.92 2.123 1.13 0.011 0.021 31.79 333.93 70.30

5
D.N. Thoai, et al. Fuel 256 (2019) 115831

Table 4
Conversion by methanolysis of refined palm oil.
Run# Ester content Remaining Catalyst Soap Glycerol Phase Analysis Catalyst/MeOH ratio Generated glycerol

Glycerol content MeOH content Glycerol Phase Initial

%wt mol mol g mol g mol mol/mol mol/mol g

1 98.13 0.027 0.045 29.56 0.321 20.62 0.644 0.043 0.037 31.84
2 97.72 0.017 0.042 30.02 0.326 19.70 0.616 0.027 0.029 33.61
3 97.31 0.012 0.033 30.02 0.326 18.48 0.577 0.020 0.022 31.69
4 85.03 0.004 0.017 24.48 0.266 18.71 0.585 0.007 0.010 29.88
5 79.31 0.00131 0.014 22.49 0.244 16.67 0.521 0.003 0.008 27.90
6 70.30 0.00050 0.010 16.18 0.176 15.61 0.488 0.001 0.005 24.52

Remark: All factors were statistically significant (P < 0.05).

is lower. Mixing may cause coalescence of droplets or break large We also assume that the step in which the alkoxide bonds with
droplets into smaller ones. However, coalescence dominates over dro- carbon of the carbonyl group and creates a primary tetrahedral inter-
plet breakage because of the high rigidity of a glycerol and alcohol mediate (Eq. (6)) is the rate determining step. Therefore, the con-
droplets. centration of alkoxide is key to this reaction and from our trial more
Mass transfer limited reaction rates are always referred to in bio- than 27 mol of methanol accompany 1 mol of alkoxide (Run# 1). There
diesel context, but most have considered the rate at which oil can get to is alcohol in excess compared to catalyst and the authors can neglect the
the reaction zone in the alcohol/catalyst droplets and the rate at which concentration of alcohol in the rate equation. When the reaction takes
esters can get away [2,6,16,17]. The authors propose the alternative place in the liquid triglyceride film, we propose this general rate.
point of view that the actual mass transfer limit to rate of reaction
1
comes from alcohol and catalyst transfer into the liquid film reaction rTGlf = 1 SA
CCi CTGlf
zone near the droplet surface. +
kAaf a kAlf a (13)
1 SA
4.1. Proposed model for liquid-liquid transesterification here kAaf a
and kAlf a
are alcohol film resistance and liquid film re-
sistance, respectively.
Based on the fluid-fluid reaction kinetics by Levenspiel [18], models
of gas to liquid and diffusional resistances are applied to this case, as
4.2. Liquid-liquid transesterification model in the initial stages
the alcohol drops stand for the gas phase and triglyceride for the liquid
phase. A very simple model is proposed here (Fig. 2). There is no soap
If the alcohol film resistance is assumed to be zero, the reaction rate
and emulsifier shell, and the alkaline catalyst does not react with any
of triglyceride in liquid film should be,
substance. We start with the fact that alcohol is slightly soluble in tri-
glyceride (8 vol%) but the solubility of triglyceride in alcohol is poorer 1
rTGlf = CCi CTGlf
(< 1 vol%). So, we assume the reaction will take place only in the li- SA
kAlf a (14)
quid film as the reaction zone. Firstly, assuming the alcohol drop is
nearly 100% pure alcohol, there is no alcohol film resistance and the The concentration of alkoxide catalyst in liquid film can be de-
bulk concentration of alcohol (CAb) equals the interface liquid film termined by mass transfer alone or by mass transfer and reaction.
concentration of alcohol (CAf). Let SA be the solubility factor of alcohol Usually a catalyst is not consumed, but the alkoxide catalyst can react
in liquid triglyceride, so the concentration of alcohol in the liquid phase with ester to form soap, so alkoxide can be also considered a reactant
(CAi) satisfies CAf = SACAi. Alcohol and catalyst diffuse into the trigly- [16] and a deactivating catalyst should be applied. Here, we propose a
ceride liquid film and alkoxide reacts with triglyceride to form an in- simple rate equation and consider the alkoxide concentration constant
termediate, after which the intermediate reacts with alcohol and gives only affected by mass transfer. So, the initial stages of reaction are of
an alkoxide back, resulting in FAME and diglyceride. This transester- second order while Darnoko and Cheryan [5] found a pseudo-second-
ification reaction is fast and glycerol is the final product of transester- order model.
ification. Generated FAME in the liquid film diffuses back into the bulk
triglyceride as the triglyceride counter diffuses to the liquid film. Thus,
the liquid film has more polarity than in the initial stages, and the SA 4.3. Liquid-liquid transesterification model in the intermediate stages
continuously decreases. The produced glycerol, which is polar, goes to
alcohol drops and forms glycerol shells. In this stage triglyceride is far more than 70 mol% converted. As
The authors assume that alkaline is a companion to alcohol, so the glycerol comes back to the alcohol drop and forms a glycerol shell, the
solubility factor of alcohol can represent the solubility of alkaline cat- situation conceptually matches two-film theory. The resistance in gly-
alyst (CCf = SACCi). cerol film plays an important role in lowering the concentration of al-
The general rate expression for mass transfer and reaction is cohol and alkoxide catalyst at the interface of glycerol film (alcohol
film) and liquid film of FAME and triglyceride. As a result, the con-
rTGlf =
1 dNTG
; moles triglyceride disappeared/(volume of liquid centrations of alcohol and catalyst at the interface (CAf and CCf) are
Vlf dt
lowered, and the solubility factor of alcohol (SA) is lower than in the
film) (time)
initial stages. The concentration of triglyceride is drastically lower and
rTGlf = the rate of reaction of triglyceride based on a unit volume of
it becomes a minor component in the liquid film. The rate is determined
reacting liquid film
by the two film resistances and the major resistance comes from gly-
Vlf = volume of liquid film
cerol film.
dNTG
= the rate of change in number of moles of triglyceride due to
dt
reaction rTGlf =
1
CCi CTGlf
1 SA
+
kAaf a kAlf a (15)

6
D.N. Thoai, et al. Fuel 256 (2019) 115831

Fig. 2. Liquid-liquid transesterification model.

4.4. Liquid-liquid transesterification model in the final stages
As more than 85 mol% of triglyceride has been reacted, the glycerol
shell is thick enough and does not allow the alkoxide and alcohol to
diffuse easily, so concentrations of them at the edge of glycerol shell are
very low. At this stage the solubility of alcohol in FAME phase is good
but the CAi and CCi are still low due to low CAf and CCf in the glycerol
shell. Triglyceride concentration is low and the reaction may be as-
sumed to occur in the main body of ester-triglyceride phase as a
homogeneous reaction. Then the reaction may depend on the remaining

7
D.N. Thoai, et al.
Fig. 3. Three stages of liquid-liquid transesterification.
CTGb and CCi in the main body of ester-triglyceride phase. Thus, the
reaction rate simply depends on the concentration of catalyst and tri-
glyceride according to the following equation.
rTGb = kCCi CTGb
This final stage model could be applied to the second stage in in-
dustrial two-stage transesterification. A fresh alcohol-catalyst solution
is added to a glycerol-free triglyceride/FAME phase to get increased CCi
and lower resistance in triglyceride film that enhance the reaction rate.
These three stages of our model could be related to several prior
studies, such as Darnoko and Cheryan [5], Pisarello and Querini [19],
Encinar et al. [20], Rashid and Anwar [21], Aniya et al. [22], and Wu
et al. [23], and are illustrated in Fig. 3.
This kinetics model should be verified in future work. The conver-
sion extent of triglyceride and concentration of catalyst should be re-
corded versus time of reaction. The initial concentration of triglyceride
may be varied when blending with FAME. The main difficulty is in
determining CTGlf .
4.5. Variables affecting the rate of reaction
4.5.1. Amount of catalyst
The amount of alkaline catalyst is the most influential variable in
the transesterification reaction. Alkaline catalyst needs an alcohol car-
rier as a companion, and doesn’t like to stay in the ester-oil phase. Our
rate equation model put the alkoxide catalyst in it. Usually, the primary
requirement for a reaction to occur is that the atoms or molecules must
collide and interact with each other. So, the catalyst should be present
preferably in a proper molar ratio to the triglyceride, rather than being
dosed by wt%. Optimizing alkoxide catalyst use is necessary for high
biodiesel yield with reasonable expenses. The amount of catalyst is
related to the reaction time for obtaining the desired standard ester
purity. A high amount of alkoxide gives quicker reactions but higher
expenses and more waste.
4.5.2. Alcohol:Oil molar ratio
The alcohol:oil molar ratio does vary with time. For example
halfway into conversion the molar ratio of alcohol:oil from the initial
6:1 has become about 9:1; and at 90% conversion the ratio is 33:1. In
our model, this variable plays an important role to the volume of liquid
film. For higher molar ratio, there is more alcohol than oil by volume.
On considering the same drop size (the same agitation speed), there will
be more drops and larger liquid film volume (Vlf). The rate expression is
expressed per volume of liquid film. Even at the same mole ratio of
alkoxide to triglyceride, the entering moles of alkoxide that accom-
panies alcohol into the liquid film are higher due to more diffusing
alcohol, and this gives higher reaction rates. This variable also has an
effect on the liquid film resistance ( SA ).
kAlf a
Fuel 256 (2019) 115831
5. Conclusion
The rate limiting mechanisms in transesterification with alkaline
catalyst for biodiesel production were inspected experimentally.
Following conclusions are drawn:
• The reactions are of liquid-liquid type.
• The reaction zone in the liquid triglyceride film is maintained by
diffusion of alcohol and catalyst.
• Alcohol accompanies alkoxide to the liquid film zone.
• The rate determining step in transesterification with alkaline cata-
lyst is the step with nucleophilic attack at the carbonyl group of
triglyceride. So, the concentration of alkoxide is a key factor in the
initial stages of reaction.
• Transesterification is a fast reaction and its rate progressively
changes with the amount of glycerol produced. The initial reaction
is fast and depends on the concentrations of triglyceride and alkaline
catalyst.
(16)
• The products of transesterification play an important role in the
later stages of reaction, especially glycerol, as it goes to the alcohol
phase and forms a glycerol shell. This shell restricts the mass
transfer of alcohol and catalyst from the inner core of alcohol dro-
plet to the reaction zone in oil-ester film, while ester products go
back to the continuous oil phase and dilute the triglyceride.
• A very significant side reaction is the saponification that produces
soap as a barrier compound that stays at the outer surface of the
disperse alcohol-glycerol phase. The intermediate products from
transesterification of triglyceride, such as diglyceride and mono-
glyceride, also act as barrier compounds, especially when alcohol or
catalyst is lacking. Water and free fatty acids are critical impurities
contributing to soap formation.
• The kinetics and rate-determining steps in the intermediate stage
depend on the diffusion of alkoxide catalyst through a barrier shell
of glycerol and emulsifiers.
• The final step of reaction should be of second order in alkoxide and
triglyceride concentrations.
This kinetic model of liquid-liquid reaction should be also applied to
transesterification when acid-catalyzed. As the rate of conversion when
acid-catalyzed is much lower than when alkaline-catalyzed, the liquid
FAME-triglyceride film is less polar and the generated glycerol goes
back to form a thin shell that resists mass transfer of alcohol and acid.
The esterification reaction model is another interesting matter to ex-
plore. The fact that these are liquid-liquid reactions may change earlier
hypotheses regarding the kinetics of transesterification.
Acknowledgement
Financial support to this work from the Prince of Songkla University
(PSU), Hat Yai, Thailand through Thailand’s Education Hub for
Southern Region of ASEAN countries (TEH-AC) and the Graduate
School of PSU is gratefully acknowledged. Appreciation is also extended
to the Department of Chemical Engineering and the Specialized R & D
Center for Alternative Energy from Palm Oil and Oil Crops, and the PSU
Faculty of Engineering. The authors would like to acknowledge the PSU
Research and Development Office (RDO) and Dr. Seppo Karrila for re-
viewing the manuscript.
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