J Surfact Deterg (2016) 19:11–18
DOI 10.1007/s11743-015-1736-0
ORIGINAL ARTICLE
Production of Palm-Based Esteramine Through Heterogeneous
Catalysis
Haliza Abdul Aziz2 • Mohamed Kheireddine Aroua1 • Rozita Yusoff1
Noor Azeerah Abas2 • Zainab Idris2 • Hazimah Abu Hassan2
Received: 4 May 2015 / Accepted: 12 September 2015 / Published online: 1 October 2015
Ó AOCS 2015
Abstract This study involved maximizing the conversion
of palm-based methyl palmitate to esteramine, an inter-
mediate for esterquats via transesterification with tri-
ethanolamine, aided by Ca–Al as a heterogeneous catalyst
in a 500-ml reaction unit. The effect of process parameters
on the conversion was investigated. The optimum process
parameters, consisting of a mole ratio of 1.8:1 (methyl
palmitate:triethanolamine), 170 °C, 10 mbar, 0.5 % cata-
lyst and a duration of 2 h, produced more than 90 %
conversion. Transesterification employing Ca–Al is more
environmentally friendly than the conventional approach
using sodium methoxide, simplifies the downstream sepa-
ration process and the reusability of the catalyst was suc-
cessfully tested in three subsequent cycles.
Keywords Esteramine
Transesterification
Methyl
palmitate
Heterogeneous catalyst
Esterquats
Introduction
Esterquats are well-known cationic surfactants with
potential value as active ingredients in fabric softeners and
hair conditioners. These surfactants are replacing conven-
tional distearyl dimethyl ammonium compounds because
they are more readily biodegradable. They are unique
& Haliza Abdul Aziz
liza_azi@mpob.gov.my
1 serious health hazard to humans upon contact and it is
Department of Chemical Engineering, Faculty of
Engineering, University of Malaya, 50603 Kuala Lumpur,
Malaysia
2
Advanced Oleochemical Technology Division, Malaysian
Palm Oil Board, 43000 Kajang, Selangor, Malaysia
•
because they possess at least one ester group between the
long hydrocarbon chain and triethanolamine hydroxyl
group. This ester link provides for easy hydrolysis to fatty
acids and short chain quats, where subsequently microor-
ganisms will be able to digest the fatty acid to give carbon
dioxide and water when drained into a sewage system [1–
3]. Direct esterification of fatty acids or transesterification
of methyl ester with triethanolamine results in the forma-
tion a mixture of mono, di and tri-esteramines. This mix-
ture is subsequently quaternized with alkylating agent to
introduce positive charge onto the esterquat molecule.
Synthesis of esteramine is the key step in the production of
esterquats and performing the esterification or transesteri-
fication process at optimum conditions will lead to maxi-
mum conversion to esteramine.
Typically, esterification of triethanolamine with fatty
acids has been catalyzed with a homogeneous acid catalyst,
such as hypophosphorous acid, phosphinic acid or sulfuric
acid, whereas transesterification of triethanolamine with an
alkyl ester can be carried out under the action of a basic
catalyst such as sodium or potassium alkoxides (e.g.
sodium methoxides). However, the main problem associ-
ated with these homogenous catalysts is that it is difficult to
separate them from the product [4]. Homogeneous catalysts
require a final neutralization step that leads to the forma-
tion of soaps and large amount of salts, thus increasing the
generation of waste [5]. Incorporation of homogeneous
acid catalysts may lead to significant environmental
impacts due to high toxicity and corrosiveness. Sodium
methoxide use in the transesterification process can be a
highly explosive. The use of freshly prepared 1 % sodium
methoxide solution as catalyst in a previous transesterifi-
cation process [6, 7] will not be economical for industrial
scale esteramine production.
123
12
In view of the above drawbacks, there is a need in
esteramine production for the employment of a heteroge-
neous catalyst, which will allow easier separation of the
product, avoiding neutralization and extraction steps,
reducing waste formation, lowering environmental impact,
and lowering cost through reusability. Few studies reported
on the use of heterogeneous acid catalysts via direct
esterification from fatty acids to produce esteramine.
Supported zirconium sulfate on HZSM-5 was used as the
heterogeneous catalyst in the esterification of stearic acid
with triethanolamine. However, the pore diameter of
HZSM-5 was too small to produce the esteramine [8].
Esterification of stearic acid with triethanolamine to pro-
duce triethanolamine ester using zirconium sulfate sup-
ported on MCM-41, SBA-15 (9) (pore diameter 9 nm) and
SBA-15 (6) (pore diameter 6 nm) mesoporous molecular
sieves has been reported [9]. Aluminium supported on
SBA-15 mesoporous molecular sieves has been reported to
be an efficient catalyst in esterification of stearic acid with
triethanolamine, in which their activity and selectivity is
comparable to zirconium sulfate supported on SBA-15 (6)
(pore diameter 6 nm) and better than zirconium sulfate
supported on MCM-41 and SBA-15 (9) (pore diameter
9 nm) [10]. However, production of esteramine via direct
esterification of fatty acids and triethanolamine in the
presence of solid acid catalyst requires costly corrosion-
resistant equipment. In addition, the preparation of the fatty
acid substrates produces many impurities giving a dark-
colored product. Subsequent downstream processes such as
bleaching and distillation are needed to obtain purer and
lighter-colored products that will incur extra cost of pro-
duction [11].
The employment of heterogeneous basic catalyst via
transesterification of methyl ester and triethanolamine for
production of esteramine has been explored. There are
many studies reported on the use of hydrotalcite and
hydrotalcite-like compounds (HTLC) as catalysts in
transesterification processes. HTLC containing Mg2?, Ni2?
and Al3? layered double hydroxide (LDH) have been
employed in the transesterification of soybean oil with
methanol to produce biodiesel [12]. The use of solid base
catalyst KF/Ca–Al hydrotalcite-like compounds in the
transesterification of methanol with palm oil to produce
biodiesel was reported [13]. HTLC were also employed in
the transesterification of glycerol (biodiesel by-product)
using diethyl carbonate as co-substrate to produce glycerol
carbonate and glycerol dicarbonate [14]. Transesterifica-
tion of fatty acid methyl esters and glycerol to produce
monoglycerides aided by calcined Li–Al and Mg–Al has
also been reported [15].
This paper will highlight the effect of process parame-
ters in transesterification of methyl palmitate and tri-
ethanolamine with the use of Ca–Al (HTLC) as the
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J Surfact Deterg (2016) 19:11–18
heterogeneous catalyst. To the best of our knowledge, no
research has been reported on the use of heterogeneous
catalysts for transesterification of methyl palmitate and
triethanolamine for the production of esteramine. As such,
the present study can be considered as the first experi-
mental investigation to produce esteramine via heteroge-
neous catalysis for the production of esterquats.
Experimental
Materials
Palm-based methyl palmitate (98 % purity) and tri-
ethanolamine (99.5 % purity) were obtained from com-
mercial suppliers. HTLC were developed in-house by the
Malaysian Palm Oil Board. Sodium methoxide solution
was freshly prepared from sodium metal (0.1 g) and
methanol (10 ml) as a 1 % solution [6].
Catalyst Preparation
The HTLC catalyst system was prepared by a co-precipi-
tation technique [16] at high supersaturation in a single
container of two diluted solutions A and B, in which
solution A contained divalent cation (67 g) and trivalent
cation (150 g) dissolved in 1 L deionized water. Solution B
acting as precipitating reagent was prepared by dissolving
Na2CO3 (42.4 g) and NaOH (16 g) in 0.5 L deionized
water. The prepared solutions A and B were then mixed
with a high supersaturation technique for 18 h at 80 °C
with vigorous stirring. Finally, the precipitate was filtered,
washed with deionized water up to pH 8–10 and dried at
120 °C overnight.
Catalyst Characterization
X-ray diffraction (XRD) was performed with a Bruker D8
Advance diffractometer (secondary monochromator, using
Cu Ka radiation, two theta–theta modes) equipped with
linear position sensitive detector (scintillation counter) at
room temperature. N2 adsorption/desorption isotherms
were performed with an ASAP 2010 apparatus (Mi-
cromeritics) after pretreating the samples under vacuum at
400 °C overnight, with a surface area obtained using the
Brunauer-Emmett-Teller (BET) technique over the pres-
sure range P/P0 = 0.02–0.2, where a linear relationship
was maintained. The pore size distributions were obtained
according to the Barret-Joyner Halenda (BJH) method from
the adsorption branch data. The particle size of the catalyst
was measured using sieve analysis with a stack of sieves
arranged in decreasing mesh size (850, 355, 250, 125 and
75 lm, respectively), and shaken for 10–15 min on an
J Surfact Deterg (2016) 19:11–18
Automatic Sieve Shaker D403 (Milano, Italy) to separate
the catalyst into various size ranges.
Transesterification of Palm-Based Methyl Palmitate
and Triethanolamine
Transesterification was carried out in a 500-ml reaction
flask equipped with a magnetic stirrer, a vacuum line and a
heating jacket. The reactants were mixed and heated to the
desired reaction temperature. A rotary vane vacuum pump
was used to remove the by-product methanol formed by the
reaction, to favor the forward reaction. After the reaction
was completed, the heterogeneous catalyst was separated
by vacuum filtration and the product was then analyzed
using gas chromatography. The esters formed were
expressed as equivalent to the percentage of conversion of
methyl palmitate. The effects of reaction temperature,
vacuum, catalyst dosage, agitator speed, and reaction time
on the conversion of methyl palmitate were investigated
while the mole ratios of methyl palmitate to tri-
ethanolamine were varied in order to study the effect of this
parameter on the composition of mono, di, and tri-ester-
amines. All measurements of conversion were performed
in duplicate with data reported representing average val-
ues ± standard errors.
Gas Chromatography Analysis
The separation of the product by gas chromatography was
performed using the capillary column ZB-5HT Inferno
(12 m 9 530 lm 9 15 lm). The oven temperature was
set initially at 100 °C, held for 3 min, and then increased at
6 °C/min to 350 °C. Helium was used as the carrier gas at a
flow rate of 20 ml/min. The injector temperature was set at
350 °C with split ratio at 10:1. A Flame Ionization
Detector (FID) was used with the temperature set at
360 °C.
Results and Discussion
Characterization of Catalyst
The characteristic features of a well crystallized hydrotal-
cite compound on XRD analyses can be represented by
sharp and symmetric peaks on the diffractograms [17]. The
XRD of Ca–Al, which was specifically dried at 120 °C
overnight, was found to exhibit characteristic features of the
hydrotalcite-like materials. The structure pattern on the
XRD (Fig. 1) shows peaks corresponding to (003), (006),
(012), (015) and (018) planes that matched with the calcium
aluminium hydroxide carbonate hydrate pattern, a hydro-
talcite-like compound with chemical formula of Ca0.67
13
Fig. 1 XRD pattern of Ca–Al
Table 1 N2 adsorption–desorption data of Ca–Al
Catalyst properties Unit Value
2
BET surface area (m /g) 256
Pore volume (cm3/g) 0.2704
Pore diameter (nm) 10
Al0.33 (OH)2 (CO3)0.167 (H2O)0.5. The BET surface area,
total pore volume and mesopore size of Ca–Al are sum-
marized in Table 1. The large surface area of Ca–Al of
256 m2g-1 could provide enough active sites for palm-
based methyl palmitate and triethanolamine molecules to
react effectively. Ca–Al with a pore diameter of 10 nm
could be a potential heterogeneous catalyst for the pro-
duction of esteramine, attributed to its mesoporous structure
(pore diameter ranging from 2 to 50 nm). This was based on
the published works, described that the geometric size of
mono plus di-esteramine and tri-esteramine molecules are
approximately 4 nm and 7 nm respectively [8–10].
Effect of Process Parameters on Transesterification
Effect of Reactants Mole Ratio
Higher mono-esterquat content would give better dis-
persibility and formulation stability, whereas higher tri-
esterquat content results in better softening but poor sta-
bility. Therefore, higher di-esterquat content is desirable
for ideal performance in fabric softeners [18]. To study the
effect of mole ratio of methyl palmitate to triethanolamine
(ME:TEA) on product composition, five mole ratios rang-
ing from 1.2:1 to 2:1 were investigated. Figure 2 shows
that as the mole ratio of methyl palmitate to tri-
ethanolamine was increased from 1.2:1 to 2:1, mono-
esteramine content decreased, di-esteramine content
did not change significantly and tri-esteramine content
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14 J Surfact Deterg (2016) 19:11–18

Mono-esteramine Di-esteramine Tri-esteramine conducting the reaction at 130 °C than that obtained at
60
Methyl Palmitate Triethanolamine
50 100 °C, with maximum conversion of 89.7 % within 6 h
Composition, %

40
time course. Increasing the temperature to 150 °C resulted
30
in significantly increased conversion in the beginning with
20
slowing as it approached a plateau after 4 h reaction time
with maximum conversion of 98.2 %. A similar trend was
10
observed when performing the reaction at a high temper-
0
1.2:1 1.4:1 1.6:1 1.8:1 2.0:1 ature of 170 °C, where the conversion increased rapidly,
Mole Ratio (ME:TEA) starting from 40 % to a maximum conversion of 98.6 %
within 2 h, and reaching equilibrium thereafter. Hence,
Fig. 2 Effect of mole ratio (methyl palmitate:triethanolamine) on
mono-, di- and tri-esteramine compositions. Reaction conditions:
170 °C was found to be the best temperature to perform the
150 °C, 10 mbar, 1 % catalyst dosage, 250 rpm and duration of 6 h transesterification process. This temperature was found to
be lower than those reported in the literatures, which
applied operating temperature of 190 °C for the production
increased. A maximum percentage composition of di-
of esteramine via esterification of stearic acid and tri-
esteramine of 47.9 % was observed at a mole ratio of 2:1,
ethanolamine using solid acid catalyst [8–10]. The oper-
with tri-esteramine content of 29 %. However, for better
ating temperature of 190 °C was not selected for this
fabric softener stability, tri-esteramine composition should
investigation, due to the limitation of the boiling point of
be \25 % [19]. The next highest di-esteramine composi-
methyl palmitate reported at approximately 185 °C under a
tion of 47 % was obtained at a mole ratio of 1.8:1 with a
high vacuum of 10 mbar [20].
tri-esteramine composition of 23.9 % and minimal amount
of methyl palmitate and triethanolamine residuals. There-
Effect of Vacuum
fore, the mole ratio of 1.8:1 was chosen as the optimum
ratio.
Effective methanol removal by the application of vacuum
to the system promotes higher conversion of methyl
Effect of Temperature
palmitate in the transesterification process. Several vacuum
conditions were applied in the reaction to investigate the
The effect of temperature on conversion of methyl palmi-
effect of vacuum on the conversion of methyl palmitate. As
tate, as shown in Fig. 3, was studied at 100, 130, 150 and
indicated in Fig. 4, a higher vacuum level resulted in
170 °C. From the plots, it can be observed that the con-
higher conversion of methyl palmitate. At the starting
version increases with temperature. Initially, at the reaction
point, t = 0, some reaction had taken place for all vacuum
time of 0 min (t = 0), 40 % conversion of methyl palmi-
levels. Reaction performed at the highest vacuum of
tate was achieved at 170 °C, whereas minimal conversion
10 mbar shows a significant increase in the conversion
was observed for lower temperatures. Reaction time t = 0
from 40 % at the starting point (t = 0) to the highest
refers to the time at which the desired reaction temperature
conversion of 98.6 % achieved at 2 h reaction time. After
of the transesterification process began to be realized. The
2 h, no further increase in the conversion was observed.
conversion obtained by performing the reaction at the
This result suggests that an efficient methanol removal
lowest temperature of 100 °C was only 10 % throughout
the 6 h duration. Higher conversion was observed when

10 mbar 200 mbar 500mbar without vacuum

120 120
100C 130C 150C 170C
100 100
Conversion, %
Conversion, %

80 80

60 60

40 40

20 20

0 0
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
Reaction time, min Reaction time, min

Fig. 3 Effect of temperature on conversion of methyl palmitate. Fig. 4 Effect of vacuum on conversion of methyl palmitate. Reaction
Reaction conditions: 10 mbar, 1 % catalyst dosage, 250 rpm, mole conditions: 170 °C, 1 % catalyst dosage, mole ratio of 1.8:1 (methyl
ratio of 1.8:1 (methyl palmitate:triethanolamine) and duration of 6 h palmitate:triethanolamine) and duration of 2 h

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J Surfact Deterg (2016) 19:11–18
system favored the conversion of methyl palmitate into
esteramine. A lower initial conversion (t = 0) was
observed when the reaction was performed at 200 mbar
than that obtained at 10 mbar. The initial conversion
gradually increased from 15 % to the maximum conversion
of 95 % within the first 2 h and the conversion reached
plateau after 2 h reaction time. When applying a vacuum of
200 mbar, the conversion obtained was slightly lower than
that performed at 10 mbar, due to the lower amount of
methanol removed from the reaction. Accumulation of
methanol in the system tends to promote a reversible
reaction [21] causing decomposition of esteramine into
methyl palmitate. As a result, a slightly higher amount of
unreacted methyl palmitate was present in the final prod-
uct. At a low vacuum of 500 mbar, the conversion obtained
was only up to 87.9 % after 6 h reaction time. It reveals
that under very low vacuum, there was insufficient energy
to pull the methanol away from the system. The excessive
accumulation of methanol could lead to higher decompo-
sition of esteramine into methyl palmitate, hence resulting
in a higher percentage of unconverted methyl palmitate. It
is also interesting to observe that by not applying any
vacuum to the reaction (free evaporation), a conversion of
65 % was achievable after 6 h reaction time. Therefore,
this study indicates that a high vacuum of 10 mbar was
selected to enhance the methanol removal in transesterifi-
cation reaction. This result is in agreement with the
reported work [22] utilizing high vacuum system between
1.33–6.7 mbar in the production of esteramine via esteri-
fication of fatty acids and triethanolamine in the presence
of homogeneous acid catalyst. However, an extremely high
vacuum is costly as it requires considerable amount of
energy.
Effect of Catalyst Dosage
A catalyst is known to lower the activation energy, hence
increasing the reaction rate, which indirectly lowers the
operational cost attributed to a prolonged reaction period.
Previous works on the production of esteramine via
transesterification of palm stearin methyl ester and tri-
ethanolamine employing sodium methoxide requires an
optimum catalyst dosage of 5 % [7]. Catalyst dosages
ranging from 3 to 7 % were reported in the enzymatic
synthesis of esteramine using lipase [23–27]. To determine
the effect of catalyst dosage on transesterification, Ca–Al
was incorporated at 0.1, 0.3, 0.5, 0.7 and 1 % during the
time course of the esteramine production. Figure 5 indi-
cates that the reaction rate increased with the increase in
Ca–Al dosage. When the reaction was performed with the
incorporation of only 0.1 % of Ca–Al, the maximum
conversion achieved was up to 97.4 % after a 6 h reaction
period. For the reaction employing 0.3 % of Ca–Al, the
15
120
100
Conversion, %
80
60
40
20
0.1% 0.3% 0.5% 0.7% 1%
0
0 50 100 150 200 250 300 350 400
Reaction time, min
Fig. 5 Effect of catalyst dosage on conversion of methyl palmitate.
Reaction conditions: 170 °C, 10 mbar, 250 rpm, mole ratio of 1.8:1
(methyl palmitate:triethanolamine) and duration of 6 h
maximum conversion of 98.2 % was achieved within 3 h
and remained constant after the 3 h reaction period.
Increasing the Ca–Al dosage to 0.5 % led to an increase in
the reaction rate as the maximum conversion of 98.5 %
was obtained within 2 h of reaction time and the conver-
sion reached plateau thereafter. It appears that no signifi-
cant difference on the reaction rate was observed when Ca–
Al dosage was further increased to 0.7 and 1 %. This
indicates that catalyst dosage higher than 0.5 % is not
necessary to speed up the reaction of the transesterification
process. Thus, a low Ca–Al dosage of 0.5 % is sufficient to
give maximum conversion at a high reaction rate. This is in
agreement with the published results, which utilized low
solid acid catalyst dosage of only 0.25 % for the esteramine
production via esterification of stearic acid and tri-
ethanolamine. Based on the published works, there was no
further changes in the reaction rates when the catalyst
dosage was further increased from 0.25 to 0.5, 0.75 and
1 % [8–10].
Effect of Agitator Speed
Increasing agitation speed will increase the external mass
transfer rates between bulk phases of the reactants towards
the surface of heterogeneous catalyst [25]. The influence of
agitation on conversion of methyl palmitate was studied by
varying the impeller speed at 150, 170, 200 and 250 rpm.
At 150 rpm, an apparent increase in conversion was
observed within the first 1 h and after 2 h, the reaction
reached equilibrium with a maximum conversion of
approximately 98 % (Fig. 6). Similar trends were observed
when the reaction was performed at higher agitator speeds
of 170, 200 and 250 rpm. This indicates that the effect of
agitator speed on conversion was minimal. The reaction
was observed to be free from the external mass transfer
limitation, thus favoring the kinetic control mechanism.
The transesterification can be performed at lower agitator
speed of 150 rpm. Agitator speed of 150 rpm is considered
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16 J Surfact Deterg (2016) 19:11–18

120 catalyst, leading to an increase in conversion. However, the

100
increment of the conversion was minor when the reaction
time was extended from 2 to 6 h. Hence, the time course of
Conversion, %

80 this transesterification can be established for 2 h. Published

60
works reported that solid acid-catalyzed esterification for
esteramine production [8–10] requires a duration of 6 h.
40 However, this solid catalyzed transesterification experi-
20 enced a shorter reaction time, presumably due to utilization
150 rpm 170 rpm 200 rpm 250 rpm of high vacuum in the system compared to those publica-
0
0 50 100 150 200 250 300 350 400 tions, where the removal of water (by product) from the
Reaction time, min system was performed only by purging of nitrogen.

Fig. 6 Effect of agitator speed on conversion of methyl palmitate.

Comparison of Heterogeneous Versus Homogeneous
Reaction conditions: 170 °C, 10 mbar, 0.5 % catalyst dosage, mole
ratio of 1.8:1 (methyl palmitate:triethanolamine) and duration of 6 h Catalysts for Conversion and Compositions
of Esteramine
low compared to the one reported in literature, that utilizes
Table 2 illustrates the conversion of methyl palmitate and
an optimum mechanical speed agitation of 480 rpm in
fatty esteramine compositions aided by the heterogeneous
lipase-catalyzed production of esteramine via esterification
catalysts (hydrotalcite compound and hydrotalcite-like
of oleic acid and triethanolamine [25]. Nevertheless, agi-
compounds) compared to the conventional sodium
tation at 150 rpm is preferred in this study as rates higher
methoxide employed in the previous work [7]. All reac-
than 250 rpm resulted in crushing of Ca–Al into a very fine
tions were performed by employing uncalcined hydrotal-
particles at the end of the reaction, making it difficult to
cite and hydrotalcite-like compounds, due to the high
reuse it for the next reaction cycle. A great extent of size
energy consumption in the calcination process. Based on
reduction of Ca–Al was experienced from 850 lm initially
Table 2, the non-catalytic transesterification resulted in
to approximately 75 lm after performing the reaction
very minimal conversion of palm-based methyl palmitate
under an agitation speed of 250 rpm.
into fatty esteramine with only 5.24 % of mono-esteramine
formation within 6 h reaction time. Conversion of 86.4 %
Effect of Reaction Time
with compositions of mono, di and tri-esteramine of 24.96,
40.64 and 18.40 % respectively, were obtained when the
The influence of reaction time on the percentage of con-
reaction was performed using Mg–Al. As for the reactions
version of methyl palmitate was investigated. Based on
aided by hydrotalcite-like compounds, the conversion fol-
Fig. 7, a minimal conversion of approximately 8 % was
lows the order: Ca–Al [ Zn–Al [ Cu/Zn–Al [ Cu–Al.
observed at the initial stage of the reaction (t = 0). Rapid
Conversions of more than 90 % were observed when the
increment from 8 % conversion to the maximum conver-
reaction was aided by both Zn–Al and Ca–Al. The highest
sion of 98.5 % was observed at 2 h reaction time, sug-
conversion of 98 % with composition of mono, di and tri-
gesting that increasing the reaction time promoted more
esteramine of 23.50, 47 and 23.90 % respectively, was
collisions between reactants and the heterogeneous
obtained using Ca–Al. Hence, this catalyst was selected as
the best catalyst for this study. Reactions employing Ca–Al
120 demonstrated similar conversion and fatty esteramine
compositions with the conventional approach using sodium
100
methoxide. Nevertheless, Ca–Al is preferred as it derived
Composion, %

80 from a cheap source of calcium nitrate. Besides that,

60
transesterification using Ca–Al can be a potential green
process over the conventional approach using sodium
40
methoxide for the esterquats production as sodium
20 methoxide can be a serious health hazard to humans upon
contact and it is explosive [28]. The uneconomical process
0
0 50 100 150 200 250 300 350 400 which uses freshly prepared 1 % sodium methoxide solu-
Reacon me (min) tion in methanol prior to transesterification as described in
Fig. 7 Effect of reaction time on conversion of methyl palmitate.
previous published works [6, 7] can now be replaced by a
Reaction conditions: 170 °C, 10 mbar, mole ratio of 1.8:1 (methyl viable heterogeneous transesterification employing Ca–Al.
palmitate:triethanolamine) and 0.5 % catalyst composition In addition, Ca–Al can also be easily separated from the

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Table 2 Comparison of heterogeneous versus homogeneous catalyst for conversion and compositions of fatty esteramine
Catalyst type Conversion of methyl Product composition (%)
palmitate (%)
Mono-esteramine Di-esteramine Tri-esteramine Methyl Triethanolamine
palmitate

Blanka 8.0 5.24 – – 93.02 1.74

Mg–Ala 86.4 24.96 40.64 18.40 11.17 4.83
Zn–Ala 94.1 24.20 46.20 22.10 4.93 2.57
Ca–Ala 98.0 23.50 47.0 23.90 1.70 3.90
Cu–Ala 9.0 6.0 – – 92.0 2.0
a
Cu/Zn–Al 70.3 28.37 33.04 7.05 24.09 7.45
Sodiumb methoxide 99.0 19.60 49.0 28.50 0.3 2.60
a
150 °C, 10 mbar, mole ratio of 1.8:1 (methyl palmitate:triethanolamine) and 1 % catalyst composition, 6 h duration
b
100 °C, 10 mbar, mole ratio of 1.8:1 (methyl palmitate:triethanolamine) and 5 % of sodium methoxide (1 % solution in methanol) and 2 h
duration [7]

product by vacuum filtration and reused as compared to fatty esteramine via transesterification of palm-based
that of sodium methoxide. methyl palmitate and triethanolamine.

Reusability of Catalyst
Reusability is one of the advantages of heterogeneous
catalysts over homogeneous catalysts. In this study,
reusability of Ca–Al was investigated by recycling the
catalyst from one reaction to another without washing or
drying of the catalyst cake after it was separated from the
reaction mixture via vacuum filtration. Based on Fig. 8, the
reusability of Ca–Al was successfully tested for three
subsequent cycles, where the conversion and fatty ester-
amine compositions obtained for the second and third
cycles were close to the first cycle using fresh catalyst.
After the third cycle, conversion was reduced and fatty
esteramine compositions seemed to change dramatically.
Hence, Ca–Al was found to have good stability as a reu-
sable heterogeneous catalyst as its catalytic activity was
unchanged for three subsequent cycles in the production of
Conversion Mono-esteramine Di-esteramine
100
80
Percentage, %
Conclusion
Transesterification of methyl palmitate and triethanolamine
was successfully carried out by employing Ca–Al (hydro-
talcite-like compound) for fatty esteramine production. The
influences of temperature, vacuum, catalyst dosage and
reaction time on conversion of methyl palmitate to ester-
amine were profoundly observed. The optimum conditions
were established as 170 °C, 10 mbar, 0.5 % catalyst, a
mole ratio of 1.8:1 (methyl palmitate: triethanolamine) and
a duration of 2 h. Transesterification of methyl palmitate
with triethanolamine gave a maximum conversion of
approximately 98 % when conducted under the optimum
conditions and aided by Ca–Al. The uneconomical process,
tedious separation technique and issue on safety of the
conventional approach using sodium methoxide can now
be replaced by a more environmentally friendly heteroge-
neous catalyst with a better separation process. The catalyst
was reusable and the conversions as well as fatty ester-
Tri-esteramine amine compositions were sustained for three subsequent
cycles.

Acknowledgments This work was carried out at the Center for

60
Separation Science and Technology (CSST) of University of Malaya
40 in collaboration with the Advanced Oleochemical Technology Divi-
sion of the Malaysian Palm Oil Board (MPOB). This study was
20 financially supported by the MPOB.

0
1 2 3 4
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Haliza Abdul Aziz is a research officer at the Malaysian Palm Oil
Board and is currently pursuing her master’s program at the
University of Malaya. Her research areas are mainly in the production
of surfactants.
Mohamed Kheireddine Aroua is a senior professor at the
Department of Chemical Engineering at the University of Malaya.
His research interests include CO2 capture, membrane processes,
electrochemical processes using activated carbon, biodiesel produc-
tion and conversion of bioglycerol to value added chemicals.
Rozita Yusoff is an associate professor in the Department of
Chemical Engineering at the University of Malaya. Her research
interests are mainly in the area of separation processes, advanced
material processing using microwave heating and cleaner production/
technology.
Noor Azeerah Abas is a research officer at the Malaysian Palm Oil
Board and her research areas are mainly in the development of
catalyst for oleochemical processes.
Zainab Idris is the Head of the Process Engineering and Design Unit
at the Malaysian Palm Oil Board and her research areas are mainly in
the synthesis of specialty chemicals.
Hazimah Abu Hassan is the Director of the Advanced Oleochemical
Technology Division of the Malaysian Palm Oil Board. Her research
areas are mainly in the synthesis of specialty chemicals.