J Surfact Deterg DOI 10.



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, transmission 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 dispersed 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 triethanolamine and recycling was used. The composition of esteramine was analyzed by reversed-phase high-performance liquid chromatography. The analytic results showed that the catalytic activity and selectivity of zirconium sulfate supported 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 Á Mesoporous molecular sieve Á SBA-15 Á Stearic acid Á Triethanolamine

Introduction Esterquats have been known for a long time, and the earliest mentions in the open literature date back to the 1930s [1]. Esterquats, which are quaternary ammonium compounds with two long (C16–C18) fatty acid chains with two weak ester linkages, represent a new generation of fabric-softening agents, having replaced the dialkyldimethylammonium 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 esterification 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

T. Geng Á Q. Li College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan, People’s Republic of China T. Geng (&) Á Q. Li Á Y. Jiang Á 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


Therefore. Esterification of Stearic Acid with TEA The catalytic reaction was carried out in a four-necked flask equipped with mechanical stirrer. the mixture in the flask was cooled down to 70 °C under nitrogen atmosphere. which has not been previously reported based on the scope of our knowledge. and the product was analyzed using reversed-phase highperformance liquid chromatography (RP-HPLC).273 K at a rate of 10 K min-1. N2 adsorption–desorption isotherms were measured using Micromeritics ASAP 2010 at liquid nitrogen temperature. The temperature-programmed desorption (TPD) measurements were carried out on an TPDRO 1100 instrument (Thermo.5 to 10° with scan steps of 1° min-1. Water formed during the reaction was removed constantly with the nitrogen flow.8:1. TEOS. this material should be an excellent support for preparing supported catalysts with high activities and selectivities. Finally.J Surfact Deterg acrylic acid showed high conversion [5]. [6. stearic acid was melted completely and then solid acid catalyst and TEA were added. Stearic acid and triethanolamine (TEA) were produced by China Lianyungang Oleochemicals with a claimed purity. The preparation of 20%ZS/MCM-41 was the same as for 20%ZS/SBA-15. The acid value of the mixture was calculated by the formula: Acid value ðAVÞ ¼ where: AV V C m The acid value. and maintained at a constant temperature for 30 min. In this paper. For example. mg KOH g-1. and high hydrothermal stability. In recent years. 7]. The prepared catalysts were denoted by their weight percentage of ZS. Firstly.54056 A) at 40 kV and 100 mA. Then. 20%ZS/SBA15(6) indicated the catalysts containing 20 wt% ZS. The concentration of KOH standard solution. followed by impregnating ZS solution for 24 h. and HCl were purchased from China Tianjin Kermel Chemical Reagents Ltd. hydrochloric acid (HCl). two different pore sizes of SBA-15 (6 and 9 nm) were prepared. denoted by SBA-15(6) and SBA15(9). All flow rates mentioned are at normal temperature and pressure (NTP). 200. All chemicals used were AR grade. V Â C Â 56:1 m ð1Þ Experimental Materials The chemicals used for the synthesis of ZS/SBA-15 were tetraethyl orthosilicate (TEOS). P123 was purchased from Sigma-Aldrich USA. The volume of KOH standard solution used in the titration. and zirconium sulfate (ZrSO4Á4H2O). and the pore size was reported from the peak position of the distribution curve. large surface area. All samples were degassed at 100 °C under vacuum for 8 h. respectively. poly (ethylene glycol)block-poly (propylene glycol)-block-poly (ethylene glycol) (P123). mol L-1. The pretreatment sample was heated from 313 to 1. but the pore diameter of HZSM-5 was too small to be used in the esterification of stearic acid with TEA. ZS supported on mesoporous molecular sieve SBA-15 was prepared and used for esterification between stearic acid and TEA. the catalysts were calcined in air at 110. The conditions used were as follows: Cu Ka ˚ radiation (k = 1. 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. MCM-41 was purchased from Tianjin Chemist Scientific Ltd.990 point. reaction. significant interests have been generated in mesoporous molecular sieve materials SBA-15 owing to its larger pores. A series of catalysts containing various ZS loadings were prepared by adding a required amount of ZS aqueous solution to the SBA-15 powder. After pretreatment. USA). The SBA-15 support was treated under vacuum at room temperature for 2 h. the catalyst was removed from the mixture by filtration. The mass of the sample. The pore volume was taken at the P/P0 = 0. thicker walls. g. or 300 °C for 2 h. The acid value of the mixture was periodically checked at an interval of 1 h after 4 h of stirring. the samples were pretreated at 313 K for 1 h in a flow of ultra pure nitrogen gas (20 mL min-1). In a typical Characterization X-ray diffraction (XRD) was performed on a Rigaku D/2500. scanning angle (2h) from 0. The specific surface areas were evaluated using the Brunauer–Emmett–Teller (BET) method. After drying. ZrSO4Á4H2O. the mol ratio of stearic acid and TEA was 1. 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. mL. 123 . Pore size distribution (PSD) was calculated using the Barrett– Joyner–Halenda (BJH) method based on the adsorption branch of the isotherms. Prior to TPD studies. Preparation of Catalysts SBA-15 was synthesized according to the procedure described by Yang et al. By changing the crystallization temperature.

5 lm). and uniform channels. N2 adsorption–desorption isotherm tests were conducted to investigate the pore-structural changes for SBA-15 and the supported samples. compared with plain SBA-15(6). 3 = 20%ZS/SBA15(6). The XRD patterns of ZS/SBA-15(6) catalyst also showed typical diffraction peaks in the low 2h region. with an average pore size of 5. From Fig. TEM High-resolution TEM images of the SBA-15(6) and 20%ZS/SBA-15(6) are shown in Fig. b XRD for 30%ZS/SBA-15(6) 10000 5000 a 4000 b 8000 6000 3000 4000 1 2000 2000 1000 2 3 4 0 1 2 3 4 0 0 10 20 30 5 6 7 8 Degree 2(θ) Degree 2(θ) 123 . Intensity (a. all of the isotherms showed a typical Type IV model and had an H1 hysteresis loop.46° (110) and 1. The samples were lightly ground and then dispersed ultrasonically in ethanol. 2a. there were no diffraction peaks corresponding to ZS observed. the BET surface areas and the total pore volume of the supported catalysts became significantly smaller. In the low-angle range. and primary mesopore size are summarized in Table 1. 250 9 4. As shown in Fig. The SBA15(6) had a typical XRD pattern for hexagonal mesophase. This result indicated that ZS should be well dispersed on the SBA-15(6) surface. The BET surface area. mobile phase of ethanol–chloroform gradient elution. These results implied that most of the ZS species were located inside the pore channels. a well-ordered mesoporous molecular sieve was obtained. and this peak weakened proportionally to the increase of ZS loading. even if the ZS content reached up to 30%. the mesoporous structure of 20%ZS/ SBA-15(6) remained after supporting ZS.86° and two other weaker peaks corresponding to 1. and the time of the detection was 30 min. a typical ZS/SBA-15(6) could reach a surface area of 500 m2 g-1. it exhibited a very strong (100) diffraction peak at a 2h = 0.8 nm. the peak intensity of the ZS support decreased. C18 silica-bonded column (DIKMA Diamonsil. The surface was significantly greater than pure ZS (90 m2 g-1) [9]. 2 = 10%ZS/ SBA-15(6). The pore diameters of supported catalysts were also smaller than those of the plain SBA-15 and MCM-41. 1 = SBA-15(6). 3 and 4. Corona electron spray detector (ESA.u) Intensity (a. From Fig.6 mm. These results were in agreement with other reported values [7]. Dalian China). when ZS was supported on the plain SBA-15 and MCM-41. it could be seen that. The RP-HPLC system consisted of a high-voltage constant-current pump (Elite P230. 4 = 30%ZS/SBA-15(6). However. 2. Even so. Furthermore. These peak positions matched well with the patterns of SBA-15 in the literature [6]. 2b. This indicated that the ordering of mesopores in SBA-15 was not much affected when ZS was supported. The large surface area could make ZS/SBA-15(6) effectively catalyze the esterification reaction [10]. USA).u) Fig. As shown in Table 1. 1b.J Surfact Deterg Transmission electron micrographs (TEM) were obtained with a JEOL JEM-1011 electron microscope using an accelerating voltage of 100 kV. 1 a X-ray diffraction (XRD) patterns of samples. N2 Adsorption–Desorption Isotherms 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. illustrating that the SBA-15 was synthesized successfully. which was a typical feature of mesoporous materials. Typical N2 adsorption–desorption isotherms for samples are shown in Figs. parallel. the channels did not communicate with each other.68° (200) reflections. According to the International Union of Pure and Applied Chemistry (IUPAC) classification [8]. This indicated that the regular arrangement of mesoporous structure of SBA-15(6) was preserved in ZS/SBA-15(6). total pore volume. The SBA15(6) exhibited straight.

3 N2 adsorption– desorption isotherm of catalysts. a SBA-15(6).12 0.0 0.90 29.010 0.06 0.02 SBA-15(6) 20% ZS/SBA-15(6) SBA-15(9) 20% ZS/SBA-15(9) 0.81 59.002 0.018 0.002 5 10 15 20 25 30 b 0.006 0.000 -0.8 1.34 452.76 0.83 656.91 0.19 123 .04 3 a 3 0.88 0.84 0.91 90. b 20%ZS/SBA-15(6) Adsorbed Volume (cm /g) Adsorbed Volume (cm /g) Fig.0 0.2 0. a SBA-15(6) and 20%ZS/SBA15(6).012 0.57 BJH pore ˚ diameter (A) 60.01 0.8 1.39 500.03 0.6 0.4 0.93 315.56 90.86 Volume of pores (cm3 g-1) 1. 2 Transmission electron microscopy (TEM) image of the SBA-15(6) and 20%ZS/SBA-15(6).47 57.014 0.43 615.54 1.0 Relactive Pressure(p/p 0 ) Relactive Pressure(p/p 0 ) Pore Volume (cm /g) Pore Volume (cm /g) Fig.63 1.00 5 10 15 20 25 30 35 40 Pore Diameter (nm) Pore Diameter (nm) Table 1 N2 adsorption– desorption data Samples SBA-15(6) 10%ZS/SBA-15(6) 20%ZS/SBA-15(6) 30%ZS/SBA-15(6) SBA-15(9) 20%ZS/SBA-15(9) MCM-41 20%ZS/MCM-41 BET surface area (m2 g-1) 745. 4 Pore distribution of catalysts.0 0.J Surfact Deterg Fig.004 0.2 0. a SBA-15(6) and 20%ZS/SBA-15(6). b SBA-15(9) and 20%ZS/SBA-15(9) 800 3 700 600 500 400 300 200 100 0 800 a 3 700 600 500 400 300 200 100 0 b SBA-15(6) SBA-15(9) 20%ZS/SBA-15(9) 20%ZS/SBA-15(6) 0.73 56.23 366.19 29.4 0. b SBA15(9) and 20%ZS/SBA-15(9) 0.008 0.023.6 0.016 0.

96 2. signifying a broad distribution of surface acid sites. the content of mono.73 AV after 5 h (mgKOH g-1) 2.19 1.68 2.91 3.28 3. catalyst dosage (based on the mass of raw material) 1%. The composition of esteramines were analyzed by RP-HPLC and the results are shown in Table 3.08 1.63 AV after filtering (mgKOH g-1) – 2. calcined at 200 °C for 2 h Temperature (°C) 123 . 5. but the pore diameter did have some effects on the selectivity.J Surfact Deterg NH3-TPD The TPD of adsorbed ammonia was used to evaluate the strength of acid sites on 20%ZS/SBA-15(6). the colors of esteramine with these kinds of catalysts were milk white.2% Preparation conditions of ZS/sample: ZS loading 20%.69 2. 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. ZS/SBA-15(6) shows a profile characterized by two resolved maxima centered at 274 and 930 °C. Acid values and the colors of esteramine are compared in Table 2.65 AV after 6 h (mgKOH g-1) 2. Comparison of the Performance of Catalysts Comparison of the Catalytic Activity ZS/SBA-15 and ZS/MCM-41 are the new solid-acid catalysts with high surface area and regular pore-size distribution. but its pore diameter was smaller than the diameter of di-esteramine (about 4 nm). The profile of the ZS/SBA-15(6) sample revealed continuous NH3 desorption in the 228–580 °C and 720–1. This result suggested that ZS/SBA-15(6) contained acid sites of two different strengths. These catalysts were used to catalyze the esterification of stearic acid with TEA.21 2. so the effective surface area used in catalyzing would be reduced and the catalytic activity of 20%ZS/MCM-41 would be lower.8. n(stearic acid):n(TEA) = 1. In addition. This was because the acid of the outer surface could also catalyze the esterification reaction. The surface area of 20%ZS/ MCM-41 was larger than 20%ZS/SBA-15(6).45 Color of esteramine Milk white Milk white Milk white Milk white Reaction conditions: 190 °C. In Fig. whereas the Lewis acid sites were coordinationally deficient Zr center promoted by the electron-withdrawing neighboring sulfate group [4].71 2. so the corresponding content of esteramine should be improved. Comparison of the Selectivity 1000 200 147120 150 800 600 100 400 50 200 0 0 0 50 100 150 Time (min) Fig.and di-esteramine determined the performance of esterquats. the selectivity of ZS/SBA-15 was better than for H3PO3 and 20%ZS/MCM-41. respectively.26 3. H3PO3 dosage 0. 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. As can be seen. but the increased range was not large. Signal (mV) Table 2 Comparison of the catalytic activity of catalysts Catalysts H3PO3 20%ZS/MCM-41 20%ZS/SBA-15(6) 20%ZS/SBA-15(9) AV after 4 h (mgKOH g-1) 3.29 2. The Bronsted acid sites on ZS resulted from the weakening of the O–H bond by the neighboring sulfate group. Combined with Table 1. Phosphorous acid is the most commonly used catalyst for the esterification of stearic acid with TEA. From the data in Table 2. it could be seen that the surface area had no obvious influence on the selectivity. The proper pore diameter could increase the content of monoand di-esteramine. it could be seen that the catalytic activity of 20%ZS/SBA-15(6) was better than for 20%ZS/SBA-15(9).000 °C temperature range. 5 Ammonia temperature-programmed desorption (TPD) profile of 20%ZS/SBA-15(6) In accordance with the previous literature [11].

n(stearic acid):n(TEA) = 1. 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. 200 °C was the optimum treatment temperature. This suggested that the activity of ZS/SBA-15(6) increased with the loading.8.85 1.45 60. and 300 °C for 2 h Through the above analysis.40 15. the acid value of the product was higher than for the 20% loading. Such behavior may be explained by the acid quantity ring as the ZS loading increased. Excess of or too little crystal water would cause the acid strength of ZS to decrease.71 2. when the ZS loading was increased to 20%. the minimum acid value of the product was 1. Therefore. catalyst dosage (based on the mass of raw material) 1% Preparation conditions of ZS/SBA-15(6): ZS loading 20%. Compared with H3PO3.26 2. The effect of crystal water may be attributed to the ZS acid strength and the number of proton sites. This finding agreed well with that reported in the literature [12. Therefore. calcined at 110. It was correlated well with the surface area analysis that the BET surface area was significantly decreased upon loading the ZS to 30%.2%. 123 . For these types of catalysts in the study.38 AV after filtering (mgKOH g-1) 1.43 Reaction conditions: 190 °C. catalyst dosage (based on the mass of raw material) 1%. the catalytic activity and selectivity of 20%ZS/SBA-15(6) was the best. which stated that the control of crystal water content in ZS was essential for effective performance. but it also made the total content of mono. Optimization of Catalyst Amount The impact of the catalyst amount on the reaction rate was studied. n(stearic acid):n(TEA) = 1. and the results are shown in Table 6.68 mgKOH g-1. 200.87 20.94 18.26 Reaction conditions: 190 °C. The data from Table 6 showed that the reaction rate did not decrease in conjunction with the reduction of the catalyst amount. 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 (°C) 110 200 300 AV after 4 h (mgKOH g-1) 3. when the ZS loading increased to 30%.31 Tri-esteramine and remaining reactants (%) 23. the catalyst amount should be reduced to 0. The results are listed in Table 5. the optimal loading of ZS on SBA-15(6) was 20% and a much higher loading of ZS was unnecessary. It was observed that. 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 4.8.28 3.25%.68 2. This indicated that a small amount of the catalyst in the esterification reaction could have a good catalytic activity.02 59.J Surfact Deterg Table 3 Comparison of the composition of esteramine Catalysts H3PO3 20%ZS/MCM-41 20%ZS/SBA-15(6) 20%ZS/SBA-15(9) Mono-esteramine (%) 19.96 3.11 19. With the treatment temperature increased to 300 °C.61 67. H3PO3 dosage 0. its catalyst activity would be low.68 AV after 5 h (mgKOH g-1) 2.99 16. it could be seen that a large surface area and proper pore diameter were beneficial to the process of esterification reaction. Consequently. 13].61 21.05 1.and di-esteramine increase by 8%. However. the ZS crystal water was removed and the acidity decreased. reaction time 6 h Preparation conditions of ZS/sample: ZS loading 20%.59 AV after 6 h (mgKOH g-1) 2. 20%ZS/SBA-15(6) not only improved the conversion of stearic acid.43 Di-esteramine (%) 57. The Influence of ZS Loading The influence of ZS loading on the acid value for the reaction of stearic acid and TEA was studied.91 3. thus.

and di-esteramine of 20%ZS/SBA15(6) after being reused five times was not changed obviously.36 1.89 1.96 1. Moreover.64 1.12 2.91 2. When 20%ZS/SBA-15(6) was taken as the catalyst.12 2.44 AV after 5 h (mgKOH g-1) 2.12 2. calcined at 200 °C for 2 h The Re-use of the Catalyst At present.49 AV after 6 h (mgKOH g-1) 2.02 2. a homogeneous catalyst is commonly used in the esterification reaction. calcined at 200 °C for 2 h Table 7 The re-use of the 20%ZS/SBA-15(6) No.58 1. However. the composition of the esteramine (the catalyst reused for the fifth time) was analyzed. catalyst dosage (based on the mass of raw material) 1% Preparation conditions of ZS/SBA-15(6): ZS loading 10.35 Reaction conditions: 190 °C. it not only improved the conversion of stearic acid.28 2. the content of mono.81 2.07 2.91 4.8 Preparation conditions of ZS/SBA-15(6): ZS loading 20%.02 2. n(stearic acid):n(TEA) = 1. and large acid sites generated by the well-dispersed ZS. The solid-acid catalyst could be removed by filtration and could be reused. of recyclings 1 2 3 4 5 AV after 4 h (mgKOH g-1) 2. the results are shown in Table 7.58 Reaction conditions: 190 °C.90 AV after 5 h (mgKOH g-1) 2.13 AV after filtering (mgKOH g-1) 2.81 1.90 2. 20%ZS/SBA-15(6) had good stability and can be reused at least five times. n(stearic acid):n(TEA) = 1.62 1. Conclusions Solid-acid catalysts ZS/SBA-15(6) were prepared.91 3. These materials had large surface area.07 2.96 3. and 30%. but it also made the total content of mono.25% Preparation conditions of ZS/SBA-15(6): ZS loading 20%. When 20%ZS/SBA-15(6) was reused five times.27 1. 20.73 Reaction conditions: 190 °C.65 1.68 AV after 6 h (mgKOH g-1) 1. the residue of catalyst in the product would impact its use. and used for the esterification of stearic acid and TEA successfully.89 AV after filtering (mgKOH g-1) 1. This showed that the selectivity to mono.55 1.72 1.90 3. the catalytic activity of the catalyst did not decrease obviously.79 1.68 2.91 3.07 2.68 1.75 1. this catalyst was difficult to separate with the product and could not be used repeatedly.5 0. catalyst dosage (based on the mass of raw material) 0.30 and 67. characterized.8.J Surfact Deterg Table 5 The influence of ZS loading on SBA-15 on the acid value of esteramine Catalysts 10%ZS/SBA-15(6) 20%ZS/SBA-15(6) 30%ZS/SBA-15(6) AV after 4 h (mgKOH g-1) 3.25 AV after 4 h (mgKOH g-1) 2.75 0.23 AV after 5 h (mgKOH g-1) 2.72%. respectively.8. At the same time. n(stearic acid):n(TEA) = 1. uniform channels.28 3.and diesteramine increase by 8% in comparison with the commonly used H3PO3. This illustrated that 20%ZS/SBA-15(6) had good stability and was an efficient catalyst for the esterification of stearic acid and TEA.and di-esteramine were 16.75 1.12 AV after 6 h (mgKOH g-1) 1.60 1.75 AV after filtered (mgKOH g-1) 1. In addition. calcined at 200 °C for 2 h Table 6 Impact of catalyst amount on the reaction rate Catalyst amount (%) 1 0.12 2. These results indicated that ZS/SBA-15(6) was an efficient 123 .

D. Meng XJ. References 1. Khanna RK (2006) Synthesis. and the China Research Institute of Daily Chemical Industry for funding support. Zhang BG. Evans DG. He J. Duan X (1999) Theoretical study on the layered structure of zirconium sulfate tetrahydrate. His research interests are the engineering development related to the manufacture of surfactants and physicohemistry. Park JK (2008) Bifunctionalized mesoporous molecular sieve for perchlorate removal. Zhu HO (2004) Alkylation of 1-dodecene with benzene over H3PW12O40 supported on mesoporous silica SBA-15. Chem Res Chin Univ 23:349 6. Keys R. J Surfact Deterg 5:211 12.J Surfact Deterg solid-acid catalyst for the esterification of stearic acid with TEA and could replace H3PO3. In addition. Koehle HJ. Wang JH.D. Wang J. Schuth F. Microporous Mesoporous Mater 110:260 5. Doerr M (2002) Upgrading triethanolamine esterquat performance to new levels. Catal Lett 93:209 11. J Petrochem Univ 13:41 4. Fender M. J Beijing Univ Chem Tech 26:67 13. the Natural Science Foundation of Shanxi (2008021017). Lv Q (2000) A new type of solid acid catalyst and its application to the esterification of acrylic acid with various alcohols. Kim TH. Cao WL. Zhang H. Juan JC. Liu HL (2006) Effect of crystallization temperature on structure and morphology of mesoporous SBA15. the application effect would not be affected by the residue of catalyst. Zhang LZ. Wang ZX. at Taiyuan University of Technology. Toney CJ. Xu K. Cao WL. Jang M. Li L. Duan X (2002) Design and studies on catalytic performance and structure of Hb-supported zirconium catalysts. She is working at China (RIDCI). J Oleo Sci 56:269 2. Microporous Mesoporous Mater 108:22 9. Yang CM. Mishra S. Wei Wang is working at China (RIDCI). Tyagi VK. Chin J Process Eng 6:499 8. Qiuxiao Li is a dean of China (RIDCI). Duan X. Li JC. Zhang JC. from Beijing University of chemistry. Tyagi VK (2007) Ester quats: the novel class of cationic fabric softeners. Kalwei M. characterization and performance of tallow fatty acids and triethanolamine based esterquats. Frank P. Acknowledgments We thank the National 11th Five-Year Technology Support Project (2007BAE52B00). Sun P. Zhou LH. Wang ZX (1996) Study on the decomposition of zirconium sulfate tetrahydrate with temperature programmed techniques. Watts M. Tyagi R. Mou CY (2008) Characterizations of aluminum-promoted sulfated zirconia on mesoporous MCM-41 silica: butane isomerization. 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. His research interests are the synthesis and investigation of softener. Yajie Jiang received her M. 123 . Jiang YJ. Zhang JC (2007) Preparation and catalytic application of novel water tolerant solid acid catalysts of zirconium sulfate/HZSM-5. J Oleo Sci 55:337 3. J Beijing Univ Chem Tech 23:58 10. Yarmo MA. Appl Catal A 254:289 7. Li F. Li F. Friedli FE. Chao KJ (2003) Gold nanoparticles in SBA-15 showing catalytic activity in CO oxidation.

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