In situ Real-Time Multivariate Analysis of Methanolysis Monitoring of Sunflower Oil Using FTIR
The combination of world population and the third industrial revolution led to high demand for fuels. On the other hand, the decrease of global fossil 8fuels deposits and the environmental air pollution caused by these fuels has compounded the challenges the world faces due to its need for energy. Therefore, new forms of environmentally friendly and renewable fuels such as biodiesel are needed. The primary analytical techniques for methanolysis yield monitoring have been chromatography and spectroscopy, these methods have been proven reliable but are more demanding, costly and do not provide real-time monitoring. In this work, the in situ monitoring of biodiesel from sunflower oil using FTIR (Fourier Transform Infrared) has been studied; the study was performed using EasyMax Mettler Toledo reactor equipped with a DiComp (Diamond) probe. The quantitative monitoring of methanolysis was performed by building a quantitative model with multivariate calibration using iC Quant module from iC IR 7.0 software. 15 samples of known concentrations were used for the modelling which were taken in duplicate for model calibration and cross-validation, data were pre-processed using mean centering and variance scale, spectrum math square root and solvent subtraction. These pre-processing methods improved the performance indexes from 7.98 to 0.0096, 11.2 to 3.41, 6.32 to 2.72, 0.9416 to 0.9999, RMSEC, RMSECV, RMSEP and R2Cum, respectively. The R2 value of 1 (training), 0.9918 (test), 0.9946 (cross-validation) indicated the fitness of the model built. The model was tested against univariate model; small discrepancies were observed at low concentration due to unmodelled intermediates but were quite close at concentrations above 18%. The software eliminated the complexity of the Partial Least Square (PLS) chemometrics. It was concluded that the model obtained could be used to monitor methanol of sunflower oil at industrial and lab scale.Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 264
 J. M. Marchetti, V. U. Miguel, and A. F. Errazu, “Possible methods for biodiesel production,” Renew. Sustain. Energy Rev., vol. 11, no. 6, pp. 1300–1311, 2007.
 M. R. Avhad, M. Sanchez, A. Bouaid, M. Martinez, J. Aracil, and J. M. Marchetti, “Modeling chemical kinetics of avocado oil ethanolysis catalyzed by solid glycerol-enriched calcium oxide,” Energy Convers. Manag., vol. 126, pp. 1168–1177, 2016.
 D. Y. C. Leung, X. Wu, and M. K. H. Leung, “A review on biodiesel production using catalyzed transesterification,” Appl. Energy, vol. 87, no. 4, pp. 1083–1095, 2010.
 A. E. Atabani, A. S. Silitonga, H. C. Ong, T. M. I. Mahlia, H. H. Masjuki, I. A. Badruddin, and H. Fayaz, “Non-edible vegetable oils: A critical evaluation of oil extraction, fatty acid compositions, biodiesel production, characteristics, engine performance and emissions production,” Renew. Sustain. Energy Rev., vol. 18, pp. 211–245, 2013.
 H. Pourzolfaghar, F. Abnisa, W. Mohd, and A. Wan, “A review of the enzymatic hydroesterification process for biodiesel production,” Renew. Sustain. Energy Rev., vol. 61, pp. 245–257, 2016.
 M. Yusoff, J. Brask, P. Munk, and Z. Guo, “Journal of Molecular Catalysis B : Enzymatic Kinetic model of biodiesel production catalyzed by free liquid lipase from Thermomyces lanuginosus,” "Journal Mol. Catal. B, Enzym., vol. 133, pp. 55–64, 2016.
 J. Amoah, E. Quayson, S. Hama, A. Yoshida, T. Hasunuma, C. Ogino, and A. Kondo, “Simultaneous conversion of free fatty acids and triglycerides to biodiesel by immobilized Aspergillus oryzae expressing Fusarium heterosporum lipase,” Biotechnol. J., vol. 12, no. 3, 2017.
 G. Baskar, A. Gurugulladevi, T. Nishanthini, R. Aiswarya, and K. Tamilarasan, “Optimization and kinetics of biodiesel production from Mahua oil using manganese doped zinc oxide nanocatalyst,” Renew. Energy, vol. 103, pp. 641–646, 2017.
 C. Muthukumaran, R. Praniesh, P. Navamani, R. Swathi, G. Sharmila, and N. Manoj, “Process optimization and kinetic modeling of biodiesel production using non-edible Madhuca indica oil,” Fuel, vol. 195, pp. 217–225, 2017.
 P. Verma and M. P. Sharma, “Comparative analysis of effect of methanol and ethanol on Karanja biodiesel production and its optimisation,” Fuel, vol. 180, pp. 164–174, 2016.
 M. Ilmi, A. Hommes, J. G. M. Winkelmana, C. Hidayatc, and H. J. Heeres, “Enzymatic biodiesel synthesis using novel process intensification principles,” Biochem. Eng. J., vol. 114, pp. 110–118, 2017.
 A. Demirbas, “Biofuels securing the planet’s future energy needs,” Energy Convers. Manag., vol. 50, no. 9, pp. 2239–2249, 2009.
 A. P. S. Chouhan and A. K. Sarma, “Modern heterogeneous catalysts for biodiesel production: A comprehensive review,” Renew. Sustain. Energy Rev., vol. 15, no. 9, pp. 4378–4399, 2011.
 R. Richard, Y. Li, B. Dubreuil, S. Thiebaud-Roux, and L. Prat, “On-line monitoring of the transesterification reaction between triglycerides and ethanol using near infrared spectroscopy combined with gas chromatography,” Bioresour. Technol., vol. 102, no. 12, pp. 6702–6709, 2011.
 G. F. Zagonel, P. Peralta-Zamora, and L. P. Ramos, “Multivariate monitoring of soybean oil ethanolysis by FTIR,” Talanta, vol. 63, no. 4, pp. 1021–1025, 2004.
 M. R. Avhad and J. M. Marchetti, “A review on recent advancement in catalytic materials for biodiesel production,” Renew. Sustain. Energy Rev., vol. 50, pp. 696–718, 2015.
 N. Lukovi, Z. Kneževi, and D. Bezbradica, “Biodiesel Fuel Production by Enzymatic Transesterification of Oils: Recent Trends, Challenges and Future Perspectives,” Dr. Maximi., InTech, 2011, pp. 47–72.
 Y. M. Sani, W. M. A. Daud, and A. R. Abdul Aziz, “Biodiesel Feedstock and Production Technologies: Successes, Challenges and Prospects,” Biodiesel - Feed. Prod. Appl., pp. 77–101, 2012.
 H. H. Mardhiah, H. C. Ong, H. H. Masjuki, S. Lim, and H. V. Lee, “A review on latest developments and future prospects of heterogeneous catalyst in biodiesel production from non-edible oils,” Renew. Sustain. Energy Rev., vol. 67, pp. 1225–1236, 2017.
 H. J. Kim, B. S. Kang, M. J. Kim, Y. M. Park, D. K. Kim, J. S. Lee, and K. Y. Lee, “Transesterification of vegetable oil to biodiesel using heterogeneous base catalyst,” Catal. Today, vol. 93–95, pp. 315–320, 2004.
 P. D. Patil and S. Deng, “Optimization of biodiesel production from edible and non-edible vegetable oils,” Fuel, vol. 88, no. 7, pp. 1302–1306, 2009.
 J. Zhang, S. Chen, R. Yang, and Y. Yan, “Biodiesel production from vegetable oil using heterogenous acid and alkali catalyst,” Fuel, vol. 89, no. 10, pp. 2939–2944, 2010.
 K. Thinnakorn and J. Tscheikuna, “Transesterification of palm olein using sodium phosphate impregnated on an alumina support,” Appl. Catal. A Gen., vol. 484, pp. 122–133, 2014.
 J. Amoah, S. H. Ho, S. Hama, A. Yoshida, A. Nakanishi, T. Hasunuma, C. Ogino, and A. Kondo, “Lipase cocktail for efficient conversion of oils containing phospholipids to biodiesel,” Bioresour. Technol., vol. 211, no. April, pp. 224–230, 2016.
 M. Y. Firdaus, Z. Guo, and S. N. Fedosov, “Development of kinetic model for biodiesel production using liquid lipase as a biocatalyst, esterification step,” Biochem. Eng. J., vol. 105, pp. 52–61, 2016.
 G. Knothe and L. F. Razon, “Biodiesel fuels,” Prog. Energy Combust. Sci., vol. 58, pp. 36–59, 2017.
 M. H. M. Killner, J. J. R. Rohwedder, and C. Pasquini, “A PLS regression model using NIR spectroscopy for on-line monitoring of the biodiesel production reaction,” Fuel, vol. 90, no. 11, pp. 3268–3273, 2011.
 S. Al-zuhair, F. Wei, and L. Song, “Proposed kinetic mechanism of the production of biodiesel from palm oil using lipase,” Process Biochem., vol. 42, pp. 951–960, 2007.
 M. K. Lam, K. T. Lee, and A. R. Mohamed, “Homogeneous, heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to biodiesel: A review,” Biotechnol. Adv., vol. 28, no. 4, pp. 500–518, 2010.
 Samir Najem Aldeen Khurshid, “Biodiesel Production by Using Heterogeneous Catalysts,” R. Inst. Technol., no. March, pp. 1–63, 2014.
 N. S. Talha and S. Sulaiman, “Overview of Catalysts in Biodiesel Production,” ARPN J. Eng. Appl. Sci., vol. 11, no. 1, pp. 439–448, 2016.
 P. M. Ejikeme, I. D. Anyaogu, C. L. Ejikeme, N. P. Nwafor, C. A. C. Egbuonu, K. Ukogu, J. A. Ibemesi, I. Chemistry, and F. Polytechnic, “Catalysis in Biodiesel Production by Transesterification Processes-An Insight,” vol. 7, no. 4, pp. 1120–1132, 2010.
 M. L. T. Cossio, L. F. Giesen, G. Araya, M. L. S. Pérez-Cotapos, R. L. VERGARA, M. Manca, R. A. Tohme, S. D. Holmberg, T. Bressmann, D. R. Lirio, J. S. Román, R. G. Solís, S. Thakur, S. N. Rao, E. L. Modelado, A. D. E. La, C. Durante, U. N. A. Tradición, M. En, E. L. Espejo, D. E. L. A. S. Fuentes, U. A. De Yucatán, C. M. Lenin, L. F. Cian, M. J. Douglas, L. Plata, and F. Héritier, New and Future Developments in Catalysis: Catalytic Biomass Conversion, vol. XXXIII, no. 2. 2012.
 A. Guldhe, B. Singh, T. Mutanda, K. Permaul, and F. Bux, “Advances in synthesis of biodiesel via enzyme catalysis: Novel and sustainable approaches,” Renew. Sustain. Energy Rev., vol. 41, pp. 1447–1464, 2015.
 M. R. Monteiro, A. R. P. Ambrozin, L. M. Lião, and A. G. Ferreira, “Critical review on analytical methods for biodiesel characterization,” Talanta, vol. 77, no. 2, pp. 593–605, 2008.
 W. B. Zhang, “Review on analysis of biodiesel with infrared spectroscopy,” Renew. Sustain. Energy Rev., vol. 16, no. 8, pp. 6048–6058, 2012.
 N. Mahamuni, I. Devices, Y. Adewuyi, N. Carolina, and T. St, “Fourier Transform Infrared Spectroscopy ( FTIR ) Method To Monitor Soy Biodiesel and Soybean Oil in Transesterification ... Fourier Transform Infrared Spectroscopy ( FTIR ) Method To Monitor Soy Biodiesel and Soybean Oil in Transesterification Reactions,” vol. 76, no. April, pp. 3773–3782, 2017.
 T. Yuan, E. Akochi-Koble, D. Pinchuk, and F. de Voort, “FTIR On-line Monitoring of Biodiesel Transesterification,” Int. J. Renew. Energy Biofuels, vol. 2014, pp. 1–13, 2014.
 M. A. Dubé, S. Zheng, D. D. McLean, and M. Kates, “A comparison of attenuated total reflectance-FTIR spectroscopy and GPC for monitoring biodiesel production,” JAOCS, J. Am. Oil Chem. Soc., vol. 81, no. 6, pp. 599–603, 2004.
 G. Knothe, “Analyzing Biodiesel : Standards and Other Methods,” vol. 83, no. 10, pp. 823–833, 2006.
 S. N. Rabelo, V. P. Ferraz, L. S. Oliveira, and A. S. Franca, “FTIR Analysis for Quantification of Fatty Acid Methyl Esters in Biodiesel Produced by Microwave-Assisted Transesterification,” Int. J. Environ. Sci. Dev., vol. 6, no. 12, pp. 964–969, 2015.
 C. L. Cunha, A. S. Luna, R. C. G. Oliveira, G. M. Xavier, M. L. L. Paredes, and A. R. Torres, “Predicting the properties of biodiesel and its blends using mid-FT-IR spectroscopy and first-order multivariate calibration,” Fuel, vol. 204, pp. 185–194, 2017.
 A. Purandaradas, T. Silambarasan, K. Murugan, R. Babujanarthanam, A. D. Gandhi, K. V. Dhandapani, D. Anbumani, and P. Kavitha, “Development and quantification of biodiesel production from chicken feather meal as a cost-effective feedstock by using green technology,” Biochem. Biophys. Reports, vol. 14, no. January, pp. 133–139, 2018.
 O. Mowla, E. Kennedy, and M. Stockenhuber, “In-situ FTIR study on the mechanism of both steps of zeolite-catalysed hydroesterification reaction in the context of biodiesel manufacturing,” Fuel, vol. 232, no. January, pp. 12–26, 2018.
 P. Mohamed Shameer and K. Ramesh, “FTIR assessment and investigation of synthetic antioxidant on the fuel stability of Calophyllum inophyllum biodiesel,” Fuel, vol. 209, no. January, pp. 411–416, 2017.
 S. M. De Lima, B. F. A. Silva, D. V. Pontes, C. F. Pereira, L. Stragevitch, and M. F. Pimentel, “In-line monitoring of the transesterification reactions for biodiesel production using NIR spectroscopy,” Fuel, vol. 115, pp. 46–53, 2014.
 P. Chand, C. V. Reddy, J. G. Verkade, T. Wang, and D. A. Grewell, “Novel Characterization Method of Biodiesel Produced from Soybean Oil using Thermogravimetric Analysis,” 2008.
 A. Oleszko, J. Hartwich, A. Wójtowicz, G. Marlena, and H. Huras, “Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy Comparison of FTIR-ATR and Raman spectroscopy in determination of VLDL triglycerides in blood serum with PLS regression,” vol. 183, pp. 239–246, 2017.
 J. F. de Souza, Adriana Velloso A. Cajaiba da Silva, “Biodiesel Synthesis Evaluated by Using Real-Time ATR-FTIR,” Org. Process Res. Dev., 2012.
 D. Mueller, M. F. Ferrão, L. Marder, A. Ben da Costa, and R. de C. de S. Schneider, “Fourier transform infrared spectroscopy (FTIR) and multivariate analysis for identification of different vegetable oils used in biodiesel production.,” Sensors (Basel)., vol. 13, no. 4, pp. 4258–4271, 2013.
 P. Singh, H. C. Andola, M. S. M. Rawat, G. J. N. Pant, and V. K. Purohit, “Fourier Transform Infrared (FT-IR) Spectroscopy in An-Overview,” Research Journal of Medicinal Plants, vol. 5, no. 2. pp. 127–135, 2011.
 G. Knothe, “Rapid monitoring of transesterification and assessing biodiesel fuel quality by near-infrared spectroscopy using a fiber-optic probe,” JAOCS, J. Am. Oil Chem. Soc., vol. 76, no. 7, pp. 795–800, 1999.
 M. G. Siatis, N. G., Kimbaris, A. C., Pappas, C. S., Tarantilis, P. A. & Polissiou, “Improvement of Biodiesel Production Based on the Application of Ultrasound: Monitoring of the Procedure by FTIR Spectroscopy,” J. Am. Oil Chem. Soc., no. 83, pp. 853–857, 2006.
 G. N. and T. Y. A. Abbaszadeh, B. Ghobadian, “an Experimental Investigation of the Effective,” Int. J. Automot. Mech. Eng., vol. 9, no. June, pp. 1525–1537, 2014.
 U. Guth, “Fast and Effective DoE Studies For Innovative Chemical Development,” White Paper, 2016. (Online) Available: http: //www.mt.com/easymax. (Accessed: 19-Jun-2017).
 M. J. Simon, “Concrete Mixture Optimization Using Statistical Methods : Final Report.”