J Surfact Deterg
DOI 10.1007/s11743-010-1196-5
ORIGINAL ARTICLE
Esterification of Stearic Acid with Triethanolamine
over Zirconium Sulfate Supported on SBA-15 Mesoporous
Molecular Sieve
Tao Geng • Qiuxiao Li • Yajie Jiang •
Wei Wang
Received: 27 December 2009 / Accepted: 23 March 2010
Ó AOCS 2010
Abstract Zirconium sulfate supported on SBA-15
(pore diameter about 6 nm) mesoporous molecular sieve
was synthesized. Various techniques, such as nitrogen
adsorption–desorption isotherms, X-ray diffraction, trans-
mission electron microscopy, and temperature-programmed
desorption, were used to characterize the prepared catalysts.
It was shown that the catalyst exhibited straight, parallel, and
uniform channels, zirconium sulfate had been finely dis-
persed on the surface of SBA-15, and most of the zirconium
sulfate species were located inside the pore channels. The
catalyst contained two kinds of acid sites with different
strengths. Zirconium sulfate supported on SBA-15 was used
to catalyze the esterification of stearic acid with triethanol-
amine and recycling was used. The composition of ester-
amine was analyzed by reversed-phase high-performance
liquid chromatography. The analytic results showed that the
catalytic activity and selectivity of zirconium sulfate sup-
ported on SBA-15 in the esterification of stearic acid and
triethanolamine was better than that of phosphorous acid,
zirconium sulfate supported on MCM-41, and zirconium
sulfate supported on SBA-15.
Keywords Zirconium sulfate  Mesoporous molecular
sieve  SBA-15  Stearic acid  Triethanolamine
T. Geng  Q. Li
College of Chemistry and Chemical Engineering,
Taiyuan University of Technology, Taiyuan,
People’s Republic of China
T. Geng (&)  Q. Li  Y. Jiang  W. Wang
China Research Institute of Daily Chemical Industry,
34 Wenyuan Street, Taiyuan 030001, Shanxi,
People’s Republic of China
e-mail: ridcigt@163.com
Introduction
Esterquats have been known for a long time, and the ear-
liest mentions in the open literature date back to the 1930s
[1]. Esterquats, which are quaternary ammonium com-
pounds with two long (C16–C18) fatty acid chains with
two weak ester linkages, represent a new generation of
fabric-softening agents, having replaced the dialkyldime-
thylammonium salts (e.g., DTDMAC and DSDMAC). This
new generation of fabric-softening agents combines a good
environmental profile with the structural features required
for an effective fabric conditioner [2]. Most often, the
esterquats are prepared by reacting triethanolamine (TEA)
with fatty acids, followed by reaction with an alkylating
agent to the corresponding quaternary. The esteramine is
the mixture of mono-, di-, and tri-esteramine, but the
ultimate performance of esterquats is related to the content
of mono- and di-esterquat. Therefore, the synthesis of
esteramine is the key step in the preparation of esterquats;
in this step, the mono- and di-esteramine content should be
increased.
The present paper centered on the study of the esterifi-
cation of stearic acid with TEA to prepare esteramine.
Esterification of fatty acid with TEA has been performed
by using homogeneous catalysts such as phosphorous acid,
sodium methoxide, para-toluene sulfonic acid, sulfuric
acid, and so on. But these catalysts are toxic, corrosive, and
often hard to separate and reuse. Thus, solid-acid catalysts
are desirable for environmentally friendly processes.
Among the solid acids, zirconium sulfate (ZS) has
attracted considerable interest because it is more active and
selective for the esterification of carboxylic acids [3].
However, the catalytic activity of ZS is limited by the
available specific surface area [4]. It was reported that the
supported ZS on HZSM-5 used in the esterification of
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acrylic acid showed high conversion [5], but the pore
diameter of HZSM-5 was too small to be used in the
esterification of stearic acid with TEA. In recent years,
significant interests have been generated in mesoporous
molecular sieve materials SBA-15 owing to its larger
pores, thicker walls, large surface area, and high hydro-
thermal stability. Therefore, this material should be an
excellent support for preparing supported catalysts with
high activities and selectivities.
In this paper, ZS supported on mesoporous molecular
sieve SBA-15 was prepared and used for esterification
between stearic acid and TEA, which has not been previ-
ously reported based on the scope of our knowledge.
Experimental
Materials
The chemicals used for the synthesis of ZS/SBA-15 were
tetraethyl orthosilicate (TEOS), poly (ethylene glycol)-
block-poly (propylene glycol)-block-poly (ethylene glycol)
(P123), hydrochloric acid (HCl), and zirconium sulfate
(ZrSO44H2O). All chemicals used were AR grade. TEOS,
ZrSO44H2O, and HCl were purchased from China Tianjin
Kermel Chemical Reagents Ltd. P123 was purchased from
Sigma-Aldrich USA. Stearic acid and triethanolamine
(TEA) were produced by China Lianyungang Oleochemi-
cals with a claimed purity. MCM-41 was purchased from
Tianjin Chemist Scientific Ltd.
Preparation of Catalysts
SBA-15 was synthesized according to the procedure
described by Yang et al. [6, 7]. By changing the crystal-
lization temperature, two different pore sizes of SBA-15 (6
and 9 nm) were prepared, denoted by SBA-15(6) and SBA-
15(9), respectively. A series of catalysts containing various
ZS loadings were prepared by adding a required amount of
ZS aqueous solution to the SBA-15 powder. The SBA-15
support was treated under vacuum at room temperature for
2 h, followed by impregnating ZS solution for 24 h. After
drying, the catalysts were calcined in air at 110, 200, or
300 °C for 2 h. The prepared catalysts were denoted by
their weight percentage of ZS. For example, 20%ZS/SBA-
15(6) indicated the catalysts containing 20 wt% ZS. The
preparation of 20%ZS/MCM-41 was the same as for
20%ZS/SBA-15.
Esterification of Stearic Acid with TEA
The catalytic reaction was carried out in a four-necked
flask equipped with mechanical stirrer. In a typical
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J Surfact Deterg
reaction, the mol ratio of stearic acid and TEA was 1.8:1.
Firstly, stearic acid was melted completely and then solid
acid catalyst and TEA were added. The esterification was
carried out under a nitrogen flow of 200 mL/min for 6 h
with the temperature of 190 °C and continued stirring.
Water formed during the reaction was removed constantly
with the nitrogen flow. Then, the mixture in the flask was
cooled down to 70 °C under nitrogen atmosphere. Finally,
the catalyst was removed from the mixture by filtration,
and the product was analyzed using reversed-phase high-
performance liquid chromatography (RP-HPLC). The acid
value of the mixture was periodically checked at an
interval of 1 h after 4 h of stirring. The acid value of the
mixture was calculated by the formula:
V  C  56:1
Acid value ðAVÞ ¼ ð1Þ
m
where:
AV The acid value, mg KOH g-1.
V The volume of KOH standard solution used in the
titration, mL.
C The concentration of KOH standard solution, mol
L-1.
m The mass of the sample, g.
Characterization
X-ray diffraction (XRD) was performed on a Rigaku
D/2500. The conditions used were as follows: Cu Ka
radiation (k = 1.54056 Å) at 40 kV and 100 mA, scanning
angle (2h) from 0.5 to 10° with scan steps of 1° min-1.
N2 adsorption–desorption isotherms were measured
using Micromeritics ASAP 2010 at liquid nitrogen tem-
perature. All samples were degassed at 100 °C under
vacuum for 8 h. The specific surface areas were evaluated
using the Brunauer–Emmett–Teller (BET) method. Pore
size distribution (PSD) was calculated using the Barrett–
Joyner–Halenda (BJH) method based on the adsorption
branch of the isotherms, and the pore size was reported
from the peak position of the distribution curve. The pore
volume was taken at the P/P0 = 0.990 point.
The temperature-programmed desorption (TPD) mea-
surements were carried out on an TPDRO 1100 instrument
(Thermo, USA). Prior to TPD studies, the samples were
pretreated at 313 K for 1 h in a flow of ultra pure nitrogen
gas (20 mL min-1). After pretreatment, the sample was
saturated with pure anhydrous ammonia gas (20 mL
min-1) at 313 K for 2 h to remove the physical adsorption
ammonia. The pretreatment sample was heated from 313 to
1,273 K at a rate of 10 K min-1, and maintained at a
constant temperature for 30 min. All flow rates mentioned
are at normal temperature and pressure (NTP).
J Surfact Deterg
Transmission electron micrographs (TEM) were
obtained with a JEOL JEM-1011 electron microscope
using an accelerating voltage of 100 kV. The samples were
lightly ground and then dispersed ultrasonically in ethanol.
The RP-HPLC system consisted of a high-voltage con-
stant-current pump (Elite P230, Dalian China), Corona
electron spray detector (ESA, USA), C18 silica-bonded
column (DIKMA Diamonsil, 250 9 4.6 mm, 5 lm),
mobile phase of ethanol–chloroform gradient elution, and
the time of the detection was 30 min.
Results and Discussion
Characterization of the Catalysts
XRD
Figure 1a shows the XRD patterns of SBA-15(6) and ZS/
SBA-15(6) catalysts with various ZS loadings. The SBA-
15(6) had a typical XRD pattern for hexagonal mesophase.
In the low-angle range, it exhibited a very strong (100)
diffraction peak at a 2h = 0.86° and two other weaker
peaks corresponding to 1.46° (110) and 1.68° (200)
reflections. These peak positions matched well with the
patterns of SBA-15 in the literature [6], illustrating that the
SBA-15 was synthesized successfully.
The XRD patterns of ZS/SBA-15(6) catalyst also
showed typical diffraction peaks in the low 2h region. This
indicated that the regular arrangement of mesoporous
structure of SBA-15(6) was preserved in ZS/SBA-15(6).
However, compared with plain SBA-15(6), the peak
intensity of the ZS support decreased, and this peak
weakened proportionally to the increase of ZS loading.
From Fig. 1b, it could be seen that, even if the ZS content
reached up to 30%, there were no diffraction peaks cor-
responding to ZS observed. This result indicated that ZS
should be well dispersed on the SBA-15(6) surface.
Fig. 1 a X-ray diffraction 10000
(XRD) patterns of samples. a b
1 = SBA-15(6), 2 = 10%ZS/
8000
SBA-15(6), 3 = 20%ZS/SBA-
15(6), 4 = 30%ZS/SBA-15(6).
Intensity (a.u)
b XRD for 30%ZS/SBA-15(6) 6000
4000
2000
0 4
1 2
TEM
High-resolution TEM images of the SBA-15(6) and
20%ZS/SBA-15(6) are shown in Fig. 2. As shown in
Fig. 2a, a well-ordered mesoporous molecular sieve was
obtained, with an average pore size of 5.8 nm. The SBA-
15(6) exhibited straight, parallel, and uniform channels.
Furthermore, the channels did not communicate with each
other. From Fig. 2b, the mesoporous structure of 20%ZS/
SBA-15(6) remained after supporting ZS.
N2 Adsorption–Desorption Isotherms
N2 adsorption–desorption isotherm tests were conducted to
investigate the pore-structural changes for SBA-15 and the
supported samples. Typical N2 adsorption–desorption iso-
therms for samples are shown in Figs. 3 and 4.
According to the International Union of Pure and
Applied Chemistry (IUPAC) classification [8], all of the
isotherms showed a typical Type IV model and had an H1
hysteresis loop, which was a typical feature of mesoporous
materials. This indicated that the ordering of mesopores in
SBA-15 was not much affected when ZS was supported.
The BET surface area, total pore volume, and primary
mesopore size are summarized in Table 1. These results
were in agreement with other reported values [7]. As
shown in Table 1, when ZS was supported on the plain
SBA-15 and MCM-41, the BET surface areas and the total
pore volume of the supported catalysts became signifi-
cantly smaller. The pore diameters of supported catalysts
were also smaller than those of the plain SBA-15 and
MCM-41. These results implied that most of the ZS species
were located inside the pore channels.
Even so, a typical ZS/SBA-15(6) could reach a surface
area of 500 m2 g-1. The surface was significantly greater
than pure ZS (90 m2 g-1) [9]. The large surface area could
make ZS/SBA-15(6) effectively catalyze the esterification
reaction [10].
5000
4000
Intensity (a.u)
3000
2000
1
1000
2
3
0
3 4 5 6 7 8 0 10 20 30
Degree 2(θ) Degree 2(θ)
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Fig. 2 Transmission electron microscopy (TEM) image of the SBA-15(6) and 20%ZS/SBA-15(6). a SBA-15(6). b 20%ZS/SBA-15(6)

Fig. 3 N2 adsorption– 800 800

a b

Adsorbed Volume (cm /g)

desorption isotherm of catalysts.
Adsorbed Volume (cm /g)

700 700

3
3

a SBA-15(6) and 20%ZS/SBA-

600 600
15(6). b SBA-15(9) and
20%ZS/SBA-15(9) 500 500

400 SBA-15(6) 400

300 300
SBA-15(9)
200 200
20%ZS/SBA-15(6) 20%ZS/SBA-15(9)
100 100

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relactive Pressure(p/p 0 ) Relactive Pressure(p/p 0 )

Fig. 4 Pore distribution of a 0.018

catalysts. a SBA-15(6) and 0.04 b
0.016
Pore Volume (cm /g)

Pore Volume (cm /g)

20%ZS/SBA-15(6). b SBA- 0.014

3

15(9) and 20%ZS/SBA-15(9) 0.03 0.012

0.010
0.02 SBA-15(6) 0.008 SBA-15(9)
20% ZS/SBA-15(6) 0.006 20% ZS/SBA-15(9)
0.01 0.004
0.002
0.000
0.00
-0.002
5 10 15 20 25 30 35 40
5 10 15 20 25 30
Pore Diameter (nm) Pore Diameter (nm)

Table 1 N2 adsorption–
Samples BET surface Volume of BJH pore
desorption data
area (m2 g-1) pores (cm3 g-1) diameter (Å)

SBA-15(6) 745.43 1.12 60.81

10%ZS/SBA-15(6) 615.39 0.88 59.47
20%ZS/SBA-15(6) 500.93 0.76 57.73
30%ZS/SBA-15(6) 315.34 0.54 56.56
SBA-15(9) 452.23 1.06 90.91
20%ZS/SBA-15(9) 366.63 0.84 90.19
MCM-41 1,023.83 0.91 29.90
20%ZS/MCM-41 656.86 0.57 29.19

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NH3-TPD Comparison of the Performance of Catalysts

The TPD of adsorbed ammonia was used to evaluate the
strength of acid sites on 20%ZS/SBA-15(6). Many
reports had focused on the identification of different acid
sites of ZS and showed the coexistence of Bronsted and
Lewis acid sites on the surface. The Bronsted acid sites
on ZS resulted from the weakening of the O–H bond
by the neighboring sulfate group, whereas the Lewis
acid sites were coordinationally deficient Zr center pro-
moted by the electron-withdrawing neighboring sulfate
group [4].
In Fig. 5, ZS/SBA-15(6) shows a profile characterized
by two resolved maxima centered at 274 and 930 °C,
respectively. This result suggested that ZS/SBA-15(6)
contained acid sites of two different strengths. The profile
of the ZS/SBA-15(6) sample revealed continuous NH3
desorption in the 228–580 °C and 720–1,000 °C tempera-
ture range, signifying a broad distribution of surface acid
sites.
Comparison of the Catalytic Activity
ZS/SBA-15 and ZS/MCM-41 are the new solid-acid cata-
lysts with high surface area and regular pore-size distri-
bution. Phosphorous acid is the most commonly used
catalyst for the esterification of stearic acid with TEA.
These catalysts were used to catalyze the esterification of
stearic acid with TEA. Acid values and the colors of est-
eramine are compared in Table 2. From the data in
Table 2, it could be seen that the catalytic activity of
20%ZS/SBA-15(6) was better than for 20%ZS/SBA-15(9).
This was because 20%ZS/SBA-15(6) had a larger surface
area than 20%ZS/SBA-15(9)—the large surface area could
make the reactants contact the active sites effectively and
improve the catalytic activity. The surface area of 20%ZS/
MCM-41 was larger than 20%ZS/SBA-15(6), but its pore
diameter was smaller than the diameter of di-esteramine
(about 4 nm), so the effective surface area used in cata-
lyzing would be reduced and the catalytic activity of
20%ZS/MCM-41 would be lower. In addition, the colors of
esteramine with these kinds of catalysts were milk white.

Comparison of the Selectivity

147120

200 1000

In accordance with the previous literature [11], the content

800
150 of mono- and di-esteramine determined the performance of
Signal (mV)

esterquats, so the corresponding content of esteramine

Temperature (°C)

600 should be improved. The composition of esteramines were

100
analyzed by RP-HPLC and the results are shown in
400 Table 3. As can be seen, the selectivity of ZS/SBA-15 was
50 better than for H3PO3 and 20%ZS/MCM-41. Combined
200 with Table 1, it could be seen that the surface area had
0 no obvious influence on the selectivity, but the pore
0
diameter did have some effects on the selectivity. The
0 50 100 150 proper pore diameter could increase the content of mono-
Time (min)
and di-esteramine, but the increased range was not large.
Fig. 5 Ammonia temperature-programmed desorption (TPD) profile This was because the acid of the outer surface could also
of 20%ZS/SBA-15(6) catalyze the esterification reaction.

Table 2 Comparison of the catalytic activity of catalysts

Catalysts AV after 4 h AV after 5 h AV after 6 h AV after filtering Color of
(mgKOH g-1) (mgKOH g-1) (mgKOH g-1) (mgKOH g-1) esteramine

H3PO3 3.26 2.69 2.29 – Milk white

20%ZS/MCM-41 3.21 2.71 2.19 2.08 Milk white
20%ZS/SBA-15(6) 2.91 2.28 1.96 1.68 Milk white
20%ZS/SBA-15(9) 3.73 3.65 2.63 2.45 Milk white
Reaction conditions: 190 °C, n(stearic acid):n(TEA) = 1.8, catalyst dosage (based on the mass of raw material) 1%, H3PO3 dosage 0.2%
Preparation conditions of ZS/sample: ZS loading 20%, calcined at 200 °C for 2 h

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Table 3 Comparison of the composition of esteramine

Catalysts Mono-esteramine (%) Di-esteramine (%) Tri-esteramine and remaining reactants (%)

H3PO3 19.11 57.02 23.87

20%ZS/MCM-41 19.99 59.61 20.40
20%ZS/SBA-15(6) 16.61 67.45 15.94
20%ZS/SBA-15(9) 21.43 60.31 18.26
Reaction conditions: 190 °C, n(stearic acid):n(TEA) = 1.8, catalyst dosage (based on the mass of raw material) 1%, H3PO3 dosage 0.2%,
reaction time 6 h
Preparation conditions of ZS/sample: ZS loading 20%, calcined at 200 °C for 2 h

Table 4 Effect of calcinations temperature of the catalyst on the acid value of the esteramine
Treatment temperature AV after 4 h AV after 5 h AV after 6 h AV after filtering
(°C) (mgKOH g-1) (mgKOH g-1) (mgKOH g-1) (mgKOH g-1)

110 3.26 2.71 2.05 1.85

200 2.91 2.28 1.96 1.68
300 3.68 3.59 3.38 2.43
Reaction conditions: 190 °C, n(stearic acid):n(TEA) = 1.8, catalyst dosage (based on the mass of raw material) 1%
Preparation conditions of ZS/SBA-15(6): ZS loading 20%, calcined at 110, 200, and 300 °C for 2 h

Through the above analysis, it could be seen that a large
surface area and proper pore diameter were beneficial to
the process of esterification reaction. For these types of
catalysts in the study, the catalytic activity and selectivity
of 20%ZS/SBA-15(6) was the best. Compared with H3PO3,
20%ZS/SBA-15(6) not only improved the conversion of
stearic acid, but it also made the total content of mono- and
di-esteramine increase by 8%.
Optimization of ZS/SBA-15(6)
Effect of Treatment Temperature of ZS/SBA-15(6)
The influence of treatment temperature on the activity of
catalysts is listed in Table 4. The acid value of the product
was minimum when 20%ZS/SBA-15(6) calcined at 200 °C
for 2 h was used as the catalyst. This finding agreed well
with that reported in the literature [12, 13], which stated
that the control of crystal water content in ZS was essential
for effective performance. The effect of crystal water may
be attributed to the ZS acid strength and the number of
proton sites. Excess of or too little crystal water would
cause the acid strength of ZS to decrease, thus, its catalyst
activity would be low. With the treatment temperature
increased to 300 °C, the ZS crystal water was removed and
the acidity decreased. Therefore, 200 °C was the optimum
treatment temperature.
The Influence of ZS Loading
The influence of ZS loading on the acid value for the
reaction of stearic acid and TEA was studied. The results
are listed in Table 5. It was observed that, when the ZS
loading was increased to 20%, the minimum acid value of
the product was 1.68 mgKOH g-1. This suggested that the
activity of ZS/SBA-15(6) increased with the loading. Such
behavior may be explained by the acid quantity ring as the
ZS loading increased. However, when the ZS loading
increased to 30%, the acid value of the product was higher
than for the 20% loading. It was correlated well with the
surface area analysis that the BET surface area was sig-
nificantly decreased upon loading the ZS to 30%. Conse-
quently, the optimal loading of ZS on SBA-15(6) was 20%
and a much higher loading of ZS was unnecessary.
Optimization of Catalyst Amount
The impact of the catalyst amount on the reaction rate
was studied, and the results are shown in Table 6. The
data from Table 6 showed that the reaction rate did not
decrease in conjunction with the reduction of the catalyst
amount. This indicated that a small amount of the catalyst
in the esterification reaction could have a good catalytic
activity. Therefore, the catalyst amount should be reduced
to 0.25%.

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Table 5 The influence of ZS loading on SBA-15 on the acid value of esteramine

Catalysts AV after 4 h AV after 5 h AV after 6 h AV after filtering
(mgKOH g-1) (mgKOH g-1) (mgKOH g-1) (mgKOH g-1)

10%ZS/SBA-15(6) 3.07 2.81 2.36 2.27

20%ZS/SBA-15(6) 2.91 2.28 1.96 1.68
30%ZS/SBA-15(6) 4.44 3.49 3.13 2.35
Reaction conditions: 190 °C, n(stearic acid):n(TEA) = 1.8, catalyst dosage (based on the mass of raw material) 1%
Preparation conditions of ZS/SBA-15(6): ZS loading 10, 20, and 30%, calcined at 200 °C for 2 h

Table 6 Impact of catalyst amount on the reaction rate

Catalyst amount AV after 4 h AV after 5 h AV after 6 h AV after filtered
(%) (mgKOH g-1) (mgKOH g-1) (mgKOH g-1) (mgKOH g-1)

1 2.91 2.28 1.96 1.68

0.75 2.91 2.12 1.89 1.62
0.5 3.07 2.02 1.81 1.55
0.25 2.90 2.12 1.75 1.58
Reaction conditions: 190 °C, n(stearic acid):n(TEA) = 1.8
Preparation conditions of ZS/SBA-15(6): ZS loading 20%, calcined at 200 °C for 2 h

Table 7 The re-use of the 20%ZS/SBA-15(6)

No. of recyclings AV after 4 h AV after 5 h AV after 6 h AV after filtering
(mgKOH g-1) (mgKOH g-1) (mgKOH g-1) (mgKOH g-1)

1 2.90 2.12 1.75 1.58

2 2.91 2.12 1.72 1.60
3 3.07 2.02 1.75 1.64
4 2.90 2.12 1.79 1.65
5 3.23 2.68 1.89 1.73
Reaction conditions: 190 °C, n(stearic acid):n(TEA) = 1.8, catalyst dosage (based on the mass of raw material) 0.25%
Preparation conditions of ZS/SBA-15(6): ZS loading 20%, calcined at 200 °C for 2 h

The Re-use of the Catalyst
At present, a homogeneous catalyst is commonly used in
the esterification reaction. However, this catalyst was dif-
ficult to separate with the product and could not be used
repeatedly. In addition, the residue of catalyst in the
product would impact its use. The solid-acid catalyst could
be removed by filtration and could be reused; the results are
shown in Table 7. When 20%ZS/SBA-15(6) was reused
five times, the catalytic activity of the catalyst did not
decrease obviously. At the same time, the composition of
the esteramine (the catalyst reused for the fifth time) was
analyzed; the content of mono- and di-esteramine were
16.30 and 67.72%, respectively. This showed that the
selectivity to mono- and di-esteramine of 20%ZS/SBA-
15(6) after being reused five times was not changed obvi-
ously. This illustrated that 20%ZS/SBA-15(6) had good
stability and was an efficient catalyst for the esterification
of stearic acid and TEA.
Conclusions
Solid-acid catalysts ZS/SBA-15(6) were prepared, charac-
terized, and used for the esterification of stearic acid and
TEA successfully. These materials had large surface area,
uniform channels, and large acid sites generated by the
well-dispersed ZS. When 20%ZS/SBA-15(6) was taken as
the catalyst, it not only improved the conversion of stearic
acid, but it also made the total content of mono- and di-
esteramine increase by 8% in comparison with the com-
monly used H3PO3. Moreover, 20%ZS/SBA-15(6) had
good stability and can be reused at least five times. These
results indicated that ZS/SBA-15(6) was an efficient

123

solid-acid catalyst for the esterification of stearic acid with
TEA and could replace H3PO3. In addition, the application
effect would not be affected by the residue of catalyst.
Acknowledgments We thank the National 11th Five-Year Tech-
nology Support Project (2007BAE52B00), the Natural Science
Foundation of Shanxi (2008021017), and the China Research Institute
of Daily Chemical Industry for funding support.
References
1. Mishra S, Tyagi VK (2007) Ester quats: the novel class of cat-
ionic fabric softeners. J Oleo Sci 56:269
2. Tyagi R, Tyagi VK, Khanna RK (2006) Synthesis, character-
ization and performance of tallow fatty acids and triethanolamine
based esterquats. J Oleo Sci 55:337
3. Cao WL, Zhang JC, Lv Q (2000) A new type of solid acid cat-
alyst and its application to the esterification of acrylic acid with
various alcohols. J Petrochem Univ 13:41
4. Wang JH, Mou CY (2008) Characterizations of aluminum-pro-
moted sulfated zirconia on mesoporous MCM-41 silica: butane
isomerization. Microporous Mesoporous Mater 110:260
5. Jiang YJ, Juan JC, Meng XJ, Cao WL, Yarmo MA, Zhang JC
(2007) Preparation and catalytic application of novel water tol-
erant solid acid catalysts of zirconium sulfate/HZSM-5. Chem
Res Chin Univ 23:349
6. Yang CM, Kalwei M, Schuth F, Chao KJ (2003) Gold nanopar-
ticles in SBA-15 showing catalytic activity in CO oxidation. Appl
Catal A 254:289
7. Zhou LH, Zhang LZ, Liu HL (2006) Effect of crystallization
temperature on structure and morphology of mesoporous SBA-
15. Chin J Process Eng 6:499
8. Kim TH, Jang M, Park JK (2008) Bifunctionalized mesoporous
molecular sieve for perchlorate removal. Microporous Mesopor-
ous Mater 108:22
123
J Surfact Deterg
9. Li F, He J, Zhang BG, Sun P, Duan X, Wang ZX (1996) Study on
the decomposition of zirconium sulfate tetrahydrate with tem-
perature programmed techniques. J Beijing Univ Chem Tech
23:58
10. Wang J, Zhu HO (2004) Alkylation of 1-dodecene with benzene
over H3PW12O40 supported on mesoporous silica SBA-15. Catal
Lett 93:209
11. Friedli FE, Koehle HJ, Fender M, Watts M, Keys R, Frank P,
Toney CJ, Doerr M (2002) Upgrading triethanolamine esterquat
performance to new levels. J Surfact Deterg 5:211
12. Li L, Xu K, Li F, Wang ZX, Duan X (1999) Theoretical study on
the layered structure of zirconium sulfate tetrahydrate. J Beijing
Univ Chem Tech 26:67
13. Li JC, Zhang H, Evans DG, Duan X (2002) Design and studies on
catalytic performance and structure of Hb-supported zirconium
catalysts. J Fuel Chem Technol 30:358
Author Biographies
Tao Geng is a senior chemistry engineer with China Research
Institute of Daily Chemical Industry (RIDCI) and is currently working
on his Ph.D. at Taiyuan University of Technology. His research
interests are the synthesis and investigation of softener.
Qiuxiao Li is a dean of China (RIDCI). His research interests are the
engineering development related to the manufacture of surfactants
and physicohemistry.
Yajie Jiang received her M.D. from Beijing University of chemistry.
She is working at China (RIDCI).
Wei Wang is working at China (RIDCI).