Abstract
In this study, SnCl4 was chosen as a solid catalyst for esterification of free fatty acids (FFA) in Zanthoxylum bungeanum seed oil (ZSO). A central composite rotatable design was used to investigate the effect of the methanol-to-oil molar ratio, catalyst amount and reaction time on the SnCl4-catalyzed esterification of FFA. The methanol-to-oil molar ratio and reaction time clearly affected the conversion efficiency of FFA in the test ranges. Response surface methodology was used to optimize the conditions for SnCl4-catalyzed esterification. A quadratic polynomial equation was obtained for conversion efficiency of FFA by multiple regression analysis and verification experiments confirmed the validity of the predicted model. Under the optimum conditions, the conversion efficiency of FFA in vegetable oil reached above 96 %. This study demonstrates the effectiveness of SnCl4 as an acid catalyst for the reduction of high FFA content in vegetable oils to a low level by one-step esterification.
Similar content being viewed by others
Abbreviations
- CCRD:
-
Central composite rotatable design
- FAME:
-
Fatty acid methyl esters
- FFA:
-
Free fatty acids
- RSM:
-
Response surface methodology
- ZSO:
-
Zanthoxylum bungeanum seed oil
References
Zhang Y, Dubé MA, McLean DD, Kates M (2003) Biodiesel production from waste cooking oil: 2. Economic assessment and sensitivity analysis. Bioresour Technol 90:229–240
Zhang J, Chen S, Yang R, Yan Y (2010) Biodiesel production from vegetable oil using heterogenous acid and alkali catalyst. Fuel 89:2939–2944
He DP (2005) Technology of oils and fats refining. Chemical Industry Press, Beijing
Van Gerpen J, Shanks B, Pruszko R, Clements D, Knothe G (2004) Biodiesel production technology, NREL/SR-510-36244, pp 52–55
Berchmans HJ, Hirata S (2008) Biodiesel production from crude Jatropha curcas L. seed oil with a high content of free fatty acids. Bioresour Technol 99:1716–1721
Di Serio M, Tesser R, Dimiccoli M, Cammarota F, Nastasi M, Santacesaria E (2005) Synthesis of biodiesel via homogeneous Lewis acid catalyst. J Mol Catal A Chem 239:111–115
Cardoso AL, Neves SCG, da Silva MJ (2009) Kinetic study of alcoholysis of the fatty acids catalyzed by Tin chloride(II): an alternative catalyst for biodiesel production. Energy Fuels 23:1718–1722
Soriano NU Jr, Venditti R, Argyropoulos DS (2009) Biodiesel synthesis via homogeneous Lewis acid-catalyzed transesterification. Fuel 88:560–565
Bahamonde Santos AM, Martinez M, Aracil Mira J (1996) Comparative study of Lewis acid type catalysts on the esterification of octanoic acid and n-octyl alcohol. Chem Eng Technol 19:538–542
Abreu FR, de Lima DG, Hamú EH, Einloft S, Rubim GC, Suarez PAZ (2003) New metal catalysts for soybean oil transesterification. J Am Oil Chem Soc 80:601–604
Ferreira DAC, Meneghetti MR, Meneghetti SMP, Wolf CR (2007) Methanolysis of soybean oil in the presence of tin(IV) complexes. Appl Catal A Gen 317:58–61
de Mendonca DR, da Silva JPV, de Almeida RM, Wolf CR, Meneghetti MR, Meneghetti SMP (2009) Transesterification of soybean oil in the presence of diverse alcoholysis agents and Sn(IV) organometallic complexes as catalysts, employing two different types of reactors. Appl Catal A Gen 365:105–109
National standard of the People’s Republic of China: animal and vegetable fats and oils—determination of acid value and of acidity. GB/T 5530–1998
Nakamura R, Komura K, Sugi Y (2008) The esterification of glycerine with lauric acid catalyzed by multi-valent metal salts-Selective formation of mono- and dilaurins. Catal Commun 9:511–515
Ieda N, Mantri K, Miyata Y, Ozaki A, Komura K, Sugi Y (2008) Esterification of long-chain acids and alcohols catalyzed by ferric chloride hexahydrate. Ind Eng Chem Res 47:8631–8638
Available online at http://www.msds.com/index.asp, last visited: 31 March 2012
Gan S, Ng HK, Ooi CW, Motala NO, Ismail MAF (2010) Ferric sulphate catalysed esterification of free fatty acids in waste cooking oil. Bioresour Technol 101:7338–7343
Zhang J, Jiang J (2008) Acid-catalyzed esterification of Zanthoxylum bungeanum seed oil with high free fatty acids for biodiesel production. Bioresour Technol 99:8995–8998
Gelbard G, Brès O, Vargas RM, Vielfaure F, Schuchardt UF (1995) 1H nuclear magnetic resonance determination of the yield of the transesterification of rapeseed oil with methanol. J Am Oil Chem Soc 72:1239–1241
Knothe G (2001) Determining the blend level of mixtures of biodiesel with conventional diesel fuel by fiber-optic near-infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy. J Am Oil Chem Soc 78:1025–1028
Knothe G (2001) Monitoring a progressing transesterification reaction by fiber-optic near-infrared spectroscopy with correlation to 1H nuclear magnetic resonance spectroscopy. J Am Oil Chem Soc 77:489–493
Mello VM, Oliveira FCC, Fraga WG, do Nascimento CJ, Suarez PAZ (2008) Determination of the content of fatty acid methyl esters (FAME) in biodiesel samples obtained by esterification using 1H-NMR spectroscopy. Magn Reson Chem 46:1051–1054
Acknowledgments
This work was supported by Northwest A&F University Key Research Project for Young Staff (project number: Z111020903) and the Program for New Century Excellent Young Talents of Shaanxi Province (Project number: 2011kjxx36).
Author information
Authors and Affiliations
Corresponding author
About this article
Cite this article
Zhang, J., Liu, J. & Ma, H. Esterification of Free Fatty Acids in Zanthoxylum bungeanum Seed Oil for Biodiesel Production by Stannic Chloride. J Am Oil Chem Soc 89, 1647–1653 (2012). https://doi.org/10.1007/s11746-012-2067-1
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11746-012-2067-1