Fractionation of fatty acid methyl esters via urea inclusion and its application to improve the low-temperature performance of biodiesel

Document Type : Research Paper

Authors

Agricultural and Biological Engineering Department, Purdue University, West Lafayette, IN 47907, USA.

Abstract

Biodiesel is viewed as the alternative to petroleum diesel, but its poor low-temperature performance constrains its utilization. Cloud point (CP), the onset temperature of thermal crystallization, appropriately shows the low-temperature performance. The effective way to reduce CP is to remove saturated fatty acid methyl esters (FAMEs). Compared to current methods, this work describes an extraordinary approach to fractionating FAMEs by forming solid urea inclusion compounds (UICs). Urea inclusion fractionation reduces the CPs by removing high melting-point linear saturated FAME components. Urea inclusion fractionation in this study was performed under various processing conditions: mass ratios of urea to FAMEs to solvents, various solvents, FAMEs from various feedstocks, and processing temperatures. Supersaturation of urea in the solution is the driving force, and it significantly affects yield, composition, CP, separation efficiency, and selectivity. Through a single urea inclusion fractionation process, FAMEs, except palm oil FAMEs, resulted in CP reduction ranging from 20 to 42 oC with a yield of 77–80% depending on the compositions. CP of palm oil FAMEs could reach as low as -17 oC with a yield of 46% after twice urea inclusion fractionation. According to the model prediction, the cetane number after urea inclusion fractionation decreased about 0.7–2 but was still higher than the minimum biodiesel requirement. Oxidation stability after urea inclusion decreased according to the proposed model, but this can be mitigated by adding antioxidants. Emission evaluation after urea inclusion fractionation indicated decreased hydrocarbons, carbon monoxide, and particulate matter. However, it resulted in the increasing emission of nitrogen oxides. 

Graphical Abstract

Fractionation of fatty acid methyl esters via urea inclusion and its application to improve the low-temperature performance of biodiesel

Highlights

  • Supersaturation of urea in solution regulates the urea inclusion fractionation process.
  • The yield loss can be minimized through hexane extraction.
  • Urea inclusion fractionation can reduce CP by over 20 oC for biodiesels containing less than 20% saturated FAMEs.
  • CP of palm oil FAMEs reached as low as -17 oC after double urea inclusion fractionation.

Keywords

References

  1. Atabani, A.E., Silitonga, A.S., Badruddin, I.A., Mahlia, T.M.I., Masjuki, H.H., Mekhilef, S., 2012. A comprehensive review on biodiesel as an alternative energy resource and its characteristics. Renew. Sust. Energy Rev. 16(4), 2070-2093.
  2. Bai, H., Tian, J., Talifu, D., Okitsu, K., Abulizi, A., 2022. Process optimization of esterification for deacidification in waste cooking oil: RSM approach and for biodiesel production assisted with ultrasonic and solvent. Fuel, 318, 123697.
  3. Bi, Y., Ding, D., Wang, D., 2010. Low-melting-point biodiesel derived from corn oil via urea complexation. Bioresour. Technol. 101(4), 1220-1226.
  4. Bist, S., Tao, B.Y., Mohtar, S., 2009. Method for separating saturated and unsaturated fatty acid esters and use of separated fatty acid esters. US20090199462A1.
  5. Boey, P.L., Maniam, G.P., Hamid, S.A., 2009. Biodiesel production via transesterification of palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst. Bioresour. Technol. 100(24), 6362-6368.
  6. Bouaid, A., Hahati, K., Martinez, M., Aracil, J., 2014. Biodiesel production from biobutanol. improvement of cold flow properties. Chem. Eng. J. 238, 234-241.
  7. Cardoso, C.C., Celante, V.G., De Castro, E.V.R., Pasa, V.M.D., 2014. Comparison of the properties of special biofuels from palm oil and its fractions synthesized with various alcohols. Fuel. 135, 406-412.
  8. Cetinkaya, M., Karaosmanoǧlu, F., 2004. Optimization of base-catalyzed transesterification reaction of used cooking oil. Energy Fuels. 18(6), 1888-1895.
  9. Chiu, C.W., Schumacher, L.G., Suppes, G.J., 2004. Impact of cold flow improvers on soybean biodiesel blend. Biomass Bioenergy. 27(5), 485-491.
  10. Dunn, R.O., 2009. Effects of minor constituents on cold flow properties and performance of biodiesel. Prog. Energy Combust. Sci. 35(6), 481-489.
  11. Dunn, R.O., Shockley, M.W., Bagby, M.O., 1997. Winterized methyl esters from soybean oil: an alternative diesel fuel with improved low-temperature flow properties. SAE Trans. 640-649.
  12. Dunn, R.O., 2011. Improving the cold flow properties of biodiesel by fractionation, in: Ng, T.-B. (Ed.), Soybean - Applications and Technology. Intech. Croatia, pp. 211-240.  
  13. Foon, C.S., Liang, Y.C., Lida, N., Mat, H., May, C.Y., Institusi, P., Bangi, B.B., Pantai, L., Lumpur, K., 2006. Crystallisation and Melting Behavior of Methyl Esters of Palm Oil. Am. J. Appl. Sci. 3(5), 1859-1863.
  14. González Gómez, M.G., Howard-Hildige, R., Leahy, J.J., Rice, B., 2002. Winterisation of waste cooking oil methyl ester to improve cold temperature fuel properties. Fuel. 81(1), 33-39.
  15. Hayes, D.G., Bengtsson, Y.C., Van Alstine, J.M., Setterwall, F., 1998. Urea complexation for the rapid, ecologically responsible fractionation of fatty acids from seed oil. J. Am. Oil Chem. Soc. 75(10), 1403-1409.
  16. Hazrat, M.A., Rasul, M.G., Mofijur, M., Khan, M.M.K., Djavanroodi, F., Azad, A.K., Bhuiya, M.M.K., Silitonga, A.S., 2020. A mini review on the cold flow properties of biodiesel and its blends. Front. Energy Res. 326.
  17. Imahara, H., Minami, E., Hari, S., Saka, S., 2008. Thermal stability of biodiesel in supercritical methanol. Fuel. 87(1), 1-6.
  18. Kalligeros, S., Zannikos, F., Stournas, S., Lois, E., Anastopoulos, G., Teas, C., Sakellaropoulos, F., 2003. An investigation of using biodiesel/marine diesel blends on the performance of a stationary diesel engine. Biomass Bioenergy. 24(2), 141-149.
  19. Lapuerta, M., Rodríguez-Fernández, J., Fernández-Rodríguez, D., Patiño-Camino, R., 2018. Cold flow and filterability properties of n-butanol and ethanol blends with diesel and biodiesel fuels. Fuel. 224, 552-559.
  20. Lee, F.M., Lahti, L.E., 1972. Solubility of urea in water-alcohol mixtures. J. Chem. Eng. Data 17(3), 304-306.
  21. Lee, I., Johnson, L.A., Hammond, E.G., 1996. Reducing the crystallization temperature of biodiesel by winterizing methyl soyate. J. Am. Oil Chem. Soc. 73(5), 631-636.
  22. Lee, Y.H., Choi, K.S., Jang, Y.S., Shin, J.A., Lee, K.T., Choi, I.H., 2014. Improvement of Low-temperature fluidity of biodiesel from vegetable oils and animal fats using urea for reduction of total saturated FAME. J. Korean Appl. Sci. Technol. 31(1), 113-119.
  23. McCormick, R., 2006. DOE / GO-102006-2358 Third Edition September 2006.
  24. Menkiel, B., Donkerbroek, A., Uitz, R., Cracknell, R., Ganippa, L., 2014. Combustion and soot processes of diesel and rapeseed methyl ester in an optical diesel engine. Fuel. 118, 406-415.
  25. Mishra, S., Anand, K., Mehta, P.S., 2016. Predicting the Cetane Number of Biodiesel Fuels from Their Fatty Acid Methyl Ester Composition. Energy Fuels. 30(12), 10425-10434.
  26. Monthly Energy Review, 2022. U.S. Energy Information Administration.
  27. Monthly Biodiesel Production Report, 2021. U.S. Energy Information Administration.
  28. Moser, B.R., 2009. Comparative oxidative stability of fatty acid alkyl esters by accelerated methods. J. Am. Oil Chem. Soc. 86(7), 699-706.
  29. Nainwal, S., Sharma, N., Sharma, A. Sen, Jain, Shivani, Jain, Siddharth, 2015. Cold flow properties improvement of Jatropha curcas biodiesel and waste cooking oil biodiesel using winterization and blending. Energy. 89, 702-707.
  30. Nowatzki, J., Shrestha, D., Swenson, A., Wiesenborn, D., 2019. Biodiesel cloud point and cold weather issues. Farm-Energy.
  31. Park, J.Y., Kim, D.K., Lee, J.P., Park, S.C., Kim, Y.J., Lee, J.S., 2008. Blending effects of biodiesels on oxidation stability and low temperature flow properties. Bioresour. Technol. 99(5), 1196-1203.
  32. Pullen, J., Saeed, K., 2014. Experimental study of the factors affecting the oxidation stability of biodiesel FAME fuels. Fuel Process. Technol. 125, 223-235.
  33. Rashid, U., Anwar, F., 2008. Production of biodiesel through optimized alkaline-catalyzed transesterification of rapeseed oil. Fuel. 87(3), 265-273.
  34. Schlenk, H., 1954. Urea inclusion compounds of fatty acids. Prog. Chem. Fats Other Lipids. 2, 243-246.
  35. Senra, M., McCartney, S.N., Soh, L., 2019. The effect of bio-derived additives on fatty acid methyl esters for improved biodiesel cold flow properties. Fuel. 242, 719-727.
  36. Sharma, Y.C., Singh, B., 2009. Development of biodiesel: Current scenario. Renew. Sust. Energy Rev. 13(6–7), 1646–1651.
  37. Shrestha, D.S., Van Gerpen, J., Thompson, J., 2008. Effectiveness of cold flow additives on various biodiesels, diesel, and their blends. Trans. ASABE. 51(4), 1365-1370.
  38. Sierra-Cantor, J.F., Guerrero-Fajardo, C.A., 2017. Methods for improving the cold flow properties of biodiesel with high saturated fatty acids content: a review. Renew. Sust. Energy Rev. 72, 774-790.
  39. Silitonga, A.S., Ong, H.C., Mahlia, T.M.I., Masjuki, H.H., Chong, W.T., 2014. Biodiesel conversion from high FFA crude Jatropha curcas, Calophyllum inophyllum and Ceiba pentandra Energy Procedia. 61, 480-483.
  40. Smith, P.C., Ngothai, Y., Nguyen, Q.D., O’Neill, B.K., 2009. Alkoxylation of biodiesel and its impact on low-temperature properties. Fuel. 88(4), 605-612.
  41. Su, Y.C., Liu, Y.A., Diaz Tovar, C.A., Gani, R., 2011. Selection of prediction methods for thermophysical properties for process modeling and product design of biodiesel manufacturing. Ind. Eng. Chem. Res., 50(11), 6809–6836.
  42. Tajima, H., Abe, M., Komatsu, H., Yamagiwa, K., 2021. Feasibility of additive winterization of biodiesel fuel derived from various eatable oils and fat. Fuel. 305, 121479.
  43. Tang, H., Salley, S.O., Ng, K.S., 2008. Fuel properties and precipitate formation at low temperature in soy-, cottonseed-, and poultry fat-based biodiesel blends. Fuel. 87(13-14), 3006-3017.
  44. Thurston, G.D., 2022. Fossil fuel combustion and PM2.5 mass air pollution associations with mortality. Environ. Int. 160, 107066.
  45. Vohra, K., Vodonos, A., Schwartz, J., Marais, E.A., Sulprizio, M.P., Mickley, L.J., 2021. Global mortality from outdoor fine particle pollution generated by fossil fuel combustion: results from GEOS-Chem. Environ. Res. 195, 110754.
  46. Wang, X., Xiaohan, W., Chen, Y., Jin, W., Jin, Q., Wang, X., 2020. Enrichment of branched chain fatty acids from lanolin via urea complexation for infant formula use. LWT. 117, 108627.
  47. Yeong, S.P., San Chan, Y., Law, M.C., Ling, J.K.U., 2021. Improving cold flow properties of palm fatty acid distillate biodiesel through vacuum distillation. J. Bioresour. Bioprod. 7(1), 43-51.
  48. Yovany Benavides, A., Benjumea, P.N., Agudelo, J.R., 2008. El fraccionamiento por cristalización del biodiesel de aceite de palma como alternativa para mejorar sus propiedades de flujo a baja temperature. Rev. Facultad. Ing. Universidad Antioquia. (43), 07-17.
  49. Zhu, L., Cheung, C.S., Huang, Z., 2016. Impact of chemical structure of individual fatty acid esters on combustion and emission characteristics of diesel engine. Energy. 107, 305-320.
  50. Zhu, L., Cheung, C.S., Zhang, W.G., Huang, Z., 2011. Combustion, performance and emission characteristics of a di diesel engine fueled with ethanol-biodiesel blends. Fuel. 90(5), 1743-1750.

Files

Cited by

Share

How to cite

Statistics