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Front. Chem. Sci. Eng. 2011, 5(3): 325329 DOI 10.

1007/s11705-010-0574-x

RESEARCH ARTICLE

Transesterication of soybean oil to biodiesel over kalsilite catalyst


Guang WEN, Zifeng YAN ()
School of Chemistry & Chemical Engineering, China University of Petroleum, Qingdao 266555, China

Higher Education Press and Springer-Verlag Berlin Heidelberg 2011

Abstract The transesterication reaction of soybean oil with methanol over kalsilite-based heterogeneous catalysts was investigated. The kalsilite was synthesized from potassium silicate, potassium hydroxide, and aluminum nitrate aqueous solutions by controlling the pH value at 13. After calcination in air at 1200C, a very porous kalsilite (KAlSiO4) was obtained with surface pores ranging from 0.2 to 1.0 m. However, this kalsilite had relatively low catalytic activity for the transesterication reaction. A biodiesel yield of 54.4% and a kinematic viscosity of 7.06 cSt were obtained at a high reaction temperature of 180C in a batch reactor. The catalytic activity of kalsilite was signicantly enhanced by introducing a small amount of lithium nitrate in the impregnation method. A biodiesel yield of 100% and a kinematic viscosity of 3.84 cSt were achieved at a temperature of only 120C over this lithium modied catalyst (2.3 wt-% Li). The test of this lithium modied catalyst in pellet form in a laboratory-scale xedbed reactor showed that it maintained a stable catalytic performance with a biodiesel yield of 100% over the rst 90 min. Keywords kalsilite, heterogeneous catalyst, transesterication, biodiesel

Introduction

Although interest in biodiesel is rapidly increasing, the process for biodiesel synthesis has not changed much in the last two decades. Biodiesel is now synthesized commercially through transesterication of soybean oil with methanol in the presence of sodium hydroxide or potassium hydroxide as a homogeneous catalyst [1]. The removal of the homogeneous alkaline catalyst for purication of biodiesel and glycerol is an energy and laborReceived November 9, 2010; accepted February 15, 2011 E-mail: zfyancat@upc.edu.cn

intensive operation that produces a waste stream [2]. This process is far from being efcient, and the production cost of biodiesel is generally much higher than that of petroleum-based diesel. The development and use of effective heterogeneous catalysts can signicantly simplify the downstream purication process by removing the neutralization and washing steps. Signicant efforts have been made in academics and industry toward developing these heterogeneous catalysts. Hydrogenized guanidines on organic polymers [3], metal salts of amino acids [4], basic resins [5], alkali metal exchanged zeolites [6], zeolite Y [7], calcium acetate and barium acetate [8], titanium-based mixed oxide [9], Na/NaOH/-Al2O3 [10], immobilized lipases [11], tin oxide [12], Li/CaO [13,14], zinc aluminate [15], Li/ZnO [16] and K/KOH/-Al2O3 [17] were studied by different research groups. Generally, these catalysts are difcult to meet the requirements for an effective heterogeneous catalyst for biodiesel commercial production due to one or more following problems: low catalytic activity leading to unfavorable yields or reaction times (for example, using Li/CaO as catalyst [14], the biodiesel yield of 90% is obtained in 1h reaction time at 60C), low thermal stability, low resistance to leaching of the active species out of the support, and the requirement for very high reaction temperature or very high methanol usage. Kalsilite (KAlSiO4) is a type of basic silicate mineral. It has framework aluminosilicates containing a random network of tetrahedral Si and Al units with charge balancing alkali metal ions, conventionally produced at high pH by condensing a source of alumina and silica with an alkali silicate solution. The presence of the alkali metal ions in the crystal structure of the kalsilite prevents the leaching of the ions from the kalsilite even at relatively high temperatures. Kalsilite has macropores and strongly basic potassium active sites. These properties, along with its insolubility in vegetable oil and methanol, make kalsilite a promising candidate for transesterication of triglycerides to produce biodiesel. Kalsilite is currently

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used as a catalyst additive in ammonia synthesis and hydrogen production from steam reforming. However, the industrial grade kalsilite is produced by calcining FLINT CLAY (Al2O3$2SiO2$2H2O) with KOH at 1000C. This solid reaction method produces kalsilite with large particles, non-homogeneous composition, and irregular pore size and structure, which make it unsuitable for the transesterication reaction. In this study, a coprecipitation method was used to synthesize kalsilite and its catalytic activity for transesterication of soybean oil to biodiesel was explored. Property modication by lithium addition into the kalsilite was studied in order to improve its catalytic performance for the transesterication reaction.

recorded from 2 = 7 to 70 with a 0.2 step and 10 s counting time.


2.2 Catalytic activity testing in batch reactor

2
2.1

Experiment
Catalyst preparation and characterization

KAlSiO4 was prepared by mixing 1000 mL of 0.3 mol/L potassium silicate (K2O$3.9SiO2, Alfa Aesar) aqueous solution with 3000 mL of 2.0 mol/L potassium hydroxide aqueous solution and then 1000 mL of 1.0 mol/L aluminum nitrate (Al(NO3)3$9H2O, Alfa Aesar) aqueous solution was added dropwise into the above mixture under continuous magnetic stirring. The addition rate of the aluminum nitrate solution was controlled to maintain the pH of the solution at 13. Deionized water was used throughout all the experiments. The resulting slurry was stirred for an additional 15 min and aged quiescently at 25C for 2 h. After washing thoroughly with water, the slurry was dried at 120C in air for 4 h and calcined in air at two different temperatures: 1000C and 1200C. The resulting materials were designated KS-1000 and KS1200, respectively. Lithium nitrate was added to KS-1200 by impregnation using lithium nitrate aqueous solution. After the impregnation, the material was dried at 120C for 6 h and calcined in air at 545C for 3 h. The resulting powder catalyst was called KSLI and had a lithium loading of 2.3 wt-%. For continuous ow xed-bed reactor testing, the powder KSLI catalyst was extruded into cylindrical pellets with a diameter of 0.8 mm and a length of 2.4 mm using a BGT high throughput bench scale extruder according to the following procedure: the KSLI powder was mixed with water to obtain a paste (37 wt-% water), which was then extruded, dried at 120C for 2 h, and calcined at 545C for 3 h. The resulting pellets are referred to as KSLI-P. A Leica 440 scanning electron microscope (SEM) equipped with energy-dispersive X-ray spectroscopy (EDS) at 25 kV was used to analyze the surface morphology and particle size of the prepared catalytic materials. Powder X-ray diffraction (XRD) patterns were recorded on a Scintac LT-801 using CuK radiation (l = 1.540 598 ) at 45 kV and 40 mA. Step-scan data were

The transesterication of rened soybean oil with methanol was performed in a Parr 1000 mL Bolted Closure Stirred Reactor, tted with mechanical stirrer, temperature control, and sample outlet. The rened soybean oil sample had a free fatty acid content of 0.2 mg KOH/g and a viscosity of 33.3 cSt at 40C. 15 g of catalyst powder and 150 g of methanol were added to the reactor and mixed while stirring. Then 300 g of soybean oil were added into the reactor, and the resulting mixture was stirred at 1100 rpm. The catalyst powder was suspended and in intimate contact with the mixture of oil and methanol. Liquid samples were drawn through the lter at the sample outlet at one-minute intervals. The sample was then left to settle. The biodiesel yield was determined using a HP 5890 Series II Gas Chromatograph (GC) installed with a ame ionization detector and DB-5 capillary column (15 m 0.32 mm 0.25 m, J&W Scientic). The kinematic viscosity of the biodiesel was measured using Cannon Ubbelohde Shear Dilution (CUSD) Viscometers according to ASTM D 445. To examine the effect of temperature on the biodiesel yield, reactions were conducted at different temperatures of 120C, 140C, 160C, and 180C with different reaction times. The overall reaction can be represented as Scheme 1.

Scheme 1 The overall transesterication

2.3

Catalytic activity testing in a xed-bed reactor

The transesterication were carried out in a laboratoryscale stainless steel xed-bed reactor with a reactor tube of 14 mm in diameter and 112 mm in length. The catalyst pellets KSLI-P were randomly packed within the reactor tube, providing a large surface area per unit volume of reaction. Frits inside the inlet and outlet caps were used to keep the pellets in the reactor. The premixed reactants, soybean oil and methanol, were fed into the reactor in a co-current downow mode by a high pressure metering pump. The ow rates of soybean oil and methanol were 1.19 mL/min and 0.31 mL/min, respectively. A tubular furnace was used to maintain the reaction temperature. After the liquid mixture exited the reactor, methanol in the liquid was vaporized and traveled into the condenser, while the biodiesel and glycerol settled into the tank. The liquid methanol was recycled to the methanol tank.

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3
3.1

Results and discussion


Catalyst physical properties

As shown in Fig. 1, the XRD pattern of KL-1000 is almost identical to that of KL-120, the dried sample, clearly indicating that the calcination at up to 1000C in air did not produce kalsilite. However, the calcination at 1200C produced very crystallized kalsilite (KSiAlO4), and no other potassium phase was observed, suggesting a state of complete charge compensation by K+ for the substitution of Al3+ for Si4+, which was selected for the catalytic activity testing.

became the dominant factors. The effect of the reaction time was investigated at 140C. As shown in Fig. 3, increasing the reaction time from 2 to 5 min increased the biodiesel yield from 40% to 51% and reduced the biodiesel viscosity from 9.71 to 7.53 cSt.
3.3 The catalytic activity of Li modied kalsilite

Fig. 1 XRD patterns of the catalyst materials prepared

The SEM images and the EDS of the KL-1200 are shown in Fig. 2. The catalyst powder was in the form of agglomerates, consisting of very ne particles. The catalyst was very porous with surface pores ranging from 0.2 to 1.0 m, which provided passages for the reactants to access the active sites. The EDS showed strong K, Al, and Si signals, which is consistent with the kalsilite composition.
3.2 The effect of reaction temperature and time on the catalytic activity of kalsilite

KS-1200 kalsilite with the low catalytic activity in the temperature range of 120C to 180C is not a good candidate for industrial application. To improve catalytic activity, lithium nitrate was introduced into the KS-1200 kalsilite by the impregnation method as described in section 2.1. Because of the low amount of lithium added, no Li containing phases in the XRD pattern (not shown here) were detected. The introduction of lithium nitrate into the kalsilite signicantly increased the catalytic activity, as shown in Fig. 4. The biodiesel yield at 120C was only 19.8% over KS-1200, but increased to 100% over KSLI under the same reaction conditions.The KSLI was calcined at 545C, so the lithium still exists as LiNO3 because the decomposition temperature of LiNO3 is 600C. LiNO3 was inert in the transesterication reaction, so the inuence of trace homogeneous Li+ species was insignicant and would not be responsible for the improved activity [13,14]. The signicantly high catalytic activity of the KSLI may result from a synergistic interaction between Li and KAlSiO4 to produce more LiKAlO2 superbasic sites, which were considered to be the active species of this catalyst [18]. In addition, because the atomic radii of K+ and Li+ are very different, the displacement of K+ by smaller radius Li+ would generate crystal defects and new active sites O2, which may also contribute to the increase in the catalytic activity.
3.4 The catalytic performance of KSLI-P in a xed-bed reactor

The KS-1200 kalsilite catalyst was tested in a high temperature and high pressure batch reactor for the transesterication of soybean oil with methanol. The effect of reaction temperature was studied in the range of 120C to 180C. As shown in Fig. 3, the reaction temperature had a signicant effect on the biodiesel yield. The biodiesel yield increased with an increase in reaction temperature. The biodiesel yield was 19.8% at 120C and increased to 51.6% at 160C. The kinematic viscosity of the biodiesel obtained at 120C was 19.39 cSt and 7.44 cSt at 160C. However, the effect became less pronounced at high temperatures (between 160C and 180C). This implies that at high temperature the mass transfer and the nature of the active catalytic sites, rather than the reaction rate,

The xed-bed testing was conducted in the laboratory scale reactor as described in detail in section 2.3. The reaction temperature was controlled at 120C, and the system pressure was controlled at 0.7 MPa. KSLI-P pellets, which had a diameter of 0.8 mm and a length of 2.4 mm, were used as the catalyst. As shown in Fig. 5, the pellet catalyst KSLI-P exhibited stable catalytic activity during the rst 90 min of operation for the transesterication of soybean oil with methanol. The biodiesel yield was 100%, and the viscosity was around 3.86 cSt. However, the biodiesel yield started to decrease after 90 min and was only 91.1% after 180 min. Concomitant with the decrease in the biodiesel yield, the biodiesel viscosity increased from 3.9 cSt at 90 min to 4.54 cSt at 180 min. This result clearly shows the deactivation of the KSLI-P over time. The leaching of the Li or K from the catalyst, the poisoning of the active sites by the impurities contained in the soybean oil and methanol, including moisture in the soybean oil and

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Fig. 2 SEM images and EDS of kalsilite KS-1200 powder catalyst

Fig. 3 The effects of reaction temperature and time over kalsilite KS-1200
soybean oil: methanol: catalyst powder (weight ratio) = 100 50 5; stirring rate: 1100 rpm

Fig. 4 Catalytic activity of Li modied kalsilite


soybean oil: methanol: catalyst (weight ratio) = 100 50 5; stirring rate: 1100 rpm; time: 2 min

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methanol, or phosphorus, metals, and free fatty acid in the soybean oil, and the potential interaction between the glycerol byproduct and the catalyst are the focus of the deactivation study in the future. After understanding the catalyst deactivation mechanism, we could improve catalyst stability by further modication.

Fig. 5 Biodiesel yield in xed-bed reactor lled with kalsilite KSLI-P pellets
soybean oil: methanol: catalyst powder (weight ratio) = 100 50 5; stirring rate: 1100 rpm

Conclusions

Kalsilite synthesized by the method used in this study has suitable physical properties as a heterogeneous catalyst. With the addition of LiNO3, this catalyst exhibited high catalytic performance for the transesterication reaction of soybean oil with methanol to produce biodiesel. A biodiesel yield of 100% and a kinematic viscosity of 3.84 cSt could be obtained at 120C by using the lithium modied catalyst in a batch reactor. This catalyst, in pellet form, also showed stable catalytic performance in the rst 90 min of xed-bed reactor testing. Further modication is needed to make this catalyst a candidate for commercial application.

References
1. Boz N, Degirmenbasi N, Kalyon D. Conversion of biomass to fuel: transesterication of vegetable oil to biodiesel using KF loaded nano--Al2O3 as catalyst. Applied Catalysis B: Environmental, 2009, 89(34): 590596 2. Kouzu M, Yamanaka S Y, Hidaka J S, Tsunomori M. Heterogeneous catalysis of calcium oxide used for transesterication of soybean oil with reuxing methanol. Applied Catalysis A: General,

2009, 355(12): 9499 3. Schuchardt U, Sercheli R, Vargas R M. Transesterication of vegetable oils: a review. Journal of the Brazilian Chemical Society, 1998, 9(3): 199210 4. Peter S K F, Ganswindt R, Neuner H P, Weidner E. Alcoholysis of triacylglycerols by heterogeneous catalysis. European Journal of Lipid Science and Technology, 2002, 104(6): 324330 5. Bondioli P. The preparation of fatty acid esters by means of catalytic reactions. Topics in Catalysis, 2004, 27(14): 7782 6. Suppes G J, Dasari M A, Doskocil E J, Mankidy P J, Goff M J. Transesterication of soybean oil with zeolite and metal catalysts. Applied Catalysis A: General, 2004, 257(2): 213223 7. Brito A, Borges M E, Otero N. Zeolite Y as a heterogeneous catalyst in biodiesel fuel production from used vegetable oil. Energy & Fuels, 2007, 21(6): 32803283 8. Basu H N, Norris M E. Process for production of esters for use as a diesel fuel substitute using a non-alkaline catalyst. US Patent, 5525126, 1996 9. Oku T, Nonoguchi M, Moriguchi T. Method of production of fatty acid alkyl esters and/or glycerin and fatty acid alkyl ester-containing composition. WIPO Patent, 021697, 2005 10. Kim H J, Kang B S, Kim M J, Park Y M, Kim D K, Lee J S, Lee K Y. Transesterication of vegetable oil to biodiesel using heterogeneous base catalyst. Catalysis Today, 2004, 93-95: 315320 11. Balco V M, Paiva A L, Malcata F X. Bioreactors with immobilized lipases: state of the art. Enzyme and Microbial Technology, 1996, 18 (6): 392416 12. Abreu F R, Alves M B, Macdo C C S, Zara L F, Suarez P A Z. New multi-phase catalytic systems based on tin compounds active for vegetable oil transesterication reaction. J Mol Catal A: Chemical, 2005, 227(12): 263267 13. Watkins R S, Lee A F, Wilson K. Li-CaO catalysed triglyceride transesterication for biodiesel applications. Green Chemistry, 2004, 6(7): 335340 14. Alonso D M, Mariscal R, Granados M L, Maireles-Torres P. Biodiesel preparation using Li/CaO catalysts: activation process and homogeneous contribution. Catalysis Today, 2009, 143(12): 167 171 15. Bournay L, Hillion G, Boucot P, Chodorge J A, Bronner C, Forestiere A. Process for producing alkyl esters from a vegetable or animal oil and an aliphatic monoalcohol. US Patent, 6878837, 2005 16. Xie W, Yang Z, Chun H. Catalytic properties of lithium-doped ZnO catalysts used for biodiesel preparations. Industrial & Engineering Chemistry Research, 2007, 46(24): 79427949 17. Ma H, Li S, Wang B, Wang R, Tian S. Transesterication of rapeseed oil for synthesizing biodiesel by K/KOH/-Al2O3 as heterogeneous base catalyst. Journal of the American Oil Chemists Society, 2008, 85(3): 263270 18. Xie W, Li H. Alumina-supported potassium iodide as a heterogeneous catalyst for biodiesel production from soybean oil. J Mol Catal A: Chemical, 2006, 225(12): 19

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