Rapidly monitoring biodiesel production processes using UPLC

Peter J. Lee, Gerard C. Bondoux, and Alice J. Di Gioia Waters Corporation

Abstract: Biodiesel is gaining significant interest as the replacement for petroleum-based diesel fuel since it is renewable and cleaner-burning. Besides these environmental factors, the increase in petroleum price and the government mandates have all contributed to its popularity. Since 2007, world biodiesel production has grown at the annual compound rate of more than 33% and is expected to reach 12 billion liter by the end of 2010. Biodiesel is fatty acid methyl ester (FAME) made from vegetable oil, animal fat, or recycled restaurant grease by transesterification of triacylglycerols (TAG) with methanol in the presence of a catalyst (Scheme 1). To maximize the yield of FAME and reduce non-volatile contaminants including unreacted feedstock (TAG), reaction intermediates [mono-acylglycerols (MAG) and diacylglycerols (DAG)], unwanted hydrolysis contaminants [fatty acids (FA)], and glycerol (reaction byproduct), biodiesel manufacturers need to monitor the status of reaction and refining processes to recognize and correct any problems at an early stage. Biodiesel samples can be analyzed by GC; however, the non-volatile contaminants (FA, TAG, MAG, and DAG) require derivatization prior to GC analysis, multiple injections with different GC experimental conditions are needed to characterize FAME and impurities, which are timeconsuming and laborious. Analyzing biodiesel by conventional HPLC methods requires 30 to 80 minute run times and use halogenated solvents that are known carcinogens, restricted, and sometimes prohibited in laboratories.

ACQUITY UPLC

(Ultra Performance Liquid Chromatography) is the next generation liquid

chromatographic platform. Its fluidic modules can sustain back pressure up to 15,000 psi, enabling the use of sub-2 micron particle packed columns with high viscosity solvents to achieve high efficiency separation. This presentation discusses using a UPLC system equipped with photodiode array and evaporative light scattering detectors to analyze boidiesel samples without derivatization and halogenated solvents. Biodiesel samples were diluted with 2-propanol and analyzed in a single injection with a 12-minute UPLC gradient method using acetonitrile and 2-propanol as the weak and strong eluents.1,2 As shown in figure 1, FAME and non-volatile contaminants were well separated. This quick and reliable method can improves the production process monitoring resulting in higher yield, lower contamination and higher quality products. Compared with conventional HPLC methods, the UPLC solution shortens analysis time and reduces solvent usage, leading to cost benefits and aligning with the principles of green chemistry.

. Lee, P. J. and Di Gioia, A. J. (2007) ACQUITY UPLC/ELSD/UV one methodology for FFA, FAME & . Lee, P. J. et al. (2009) Automating calculations for rapid seed oil quality control and

TAG analysis, Waters Corporation, application note 720002155en.

2

Authenticity. Waters Corporation, application note 720002973en.

2009 Waters Corporation. Waters, UPLC, ACQUITY UPLC and The Science of Whats Possible are trademarks of Waters Corporation.