Esterification of rosin with methyl alcohol for fuel applications
DOI:
https://doi.org/10.17533/udea.redin.20201214Keywords:
hydrocarbons, acidity, chromatographic analysis, materials science, calciumAbstract
Oleoresin is obtained via tapping of pine trees and as a by-product of Kraft process in the pulp industry. Because of its low production cost, it is an attractive source for biofuels. Oleoresin is composed mainly of rosin (around 80%, a solid mixture of isomeric abietic acids), and it cannot be used directly as fuel in engines. However, the methyl ester of rosin has lower boiling and melting points than rosin, and it is highly soluble in hydrocarbons. Esterification of rosin with methyl alcohol was evaluated over acid and basic heterogeneous catalysts in the presence of several solvents. In contrast to acid catalysts, basic materials were active in the reaction. In particular, a low-cost calcium-based material showed the best performance. A 55% conversión of rosin with complete selectivity to methyl esters was obtained with 40% wt. Loading of the calcium-based material (respect to rosin), under mild conditions (atmospheric pressure, 64 °C and 3.5 h) and without solvent. Other catalysts, such as magnesium oxide, titanium dioxide, and alumina, achieved up to 30% conversion. Calcium carbonate and calcium hydroxide were the main phases in the calcium-based material, suggesting that the strength of basic sites can be an important property of the catalyst activity. A calcium-based material was used in five reaction cycles, obtaining a significant reduction in the activity attributed to the leaching of some phases of the catalyst.
Downloads
References
R. Höfer, “The pine biorefinery platform chemicals value chain,” in Industrial biorefineries & white biotechnology, A. Pandey, R. Höfer, M. Taherzadeh, M. Nampoothiri, and C. Larroche, Eds. Amsterdam, NL: Elsevier, 2015, pp. 127–155.
I. T. Clark and E. E. Harris, “Catalytic cracking of rosin2,” J. Am. Chem. Soc., vol. 74, no. 4, February 1 1952. [Online]. Available: https://doi.org/10.1021/ja01124a046
J. Mikulec, A. Kleinová, J. Cvengroš, L. Joríková, and M. Banič, “Catalytic transformation of tall oil into biocomponent of diesel fuel,” Int. J. Chem. Eng., vol. 2012, March 2012. [Online]. Available: https://doi.org/10.1155/2012/215258
J. M. Anthonykutty and et al, “Value added hydrocarbons from distilled tall oil via hydrotreating over a commercial NiMo catalyst,” Ind. Eng. Chem. Res., vol. 52, no. 30, July 2 2013. [Online]. Available: https://doi.org/10.1021/ie400790v
A. Bernas, T. Salmiand, D. Y. Murzin, J. P. Mikkola, and M. Rintola, “Catalytic transformation of abietic acid to hydrocarbons,” Top. Catal., vol. 55, no. 7-10, July 2012. [Online]. Available: https: //doi.org/10.1007/s11244-012-9846-7
D. García and et al, “Improvements of thermal and thermochemical properties of rosin by chemical transformation for its use as biofuel,” Waste and Biomass Valorization, vol. 11, November 2020. [Online]. Available: https://doi.org/10.1007/s12649-019-00863-y
N. Xiao, J. Jian, D. Wei, and C. Xia, “Study on synthesis and properties of biodiesel oil from rosin,” Chem. Ind. For. Prod., vol. 27, no. 4, pp. 79–81, 2012.
M. Ash and I. Ash, Handbook of Paint and Coating Raw Materials, 2nd ed. Endicott, USA: Synapse Information Resources Inc, 2013.
M. Ash, Handbook of Plastics and Rubber Additives, 2nd ed. Endicott, USA: Synapse Information Resources Inc, 2004.
A. Wypych, Databook of Plasticizers, 2nd ed. Toronto, CA: ChemTec Publishing, 2017.
R. Lewis, Sax’s Dangerous Properties of Industrial Materials, 12th ed. New York, USA: John Wiley & Sons, 2012.
E. P. Hurtado and A. L. Villa, “Kinetics of nopyl acetate synthesis by homogeneously catalyzed esterification of acetic acid with nopol,” Revista Facultad de Ingeniería Universidad de Antioquia, no. 89, October 2 2018. [Online]. Available: http://dx.doi.org/10.17533/udea.redin.n89a03
W. L. Boatright and A. D. Crum, “Nonpolar-volatile lipids from soy protein isolates and hexane-defatted flakes,” J. Am. Oil Chem. Soc., vol. 74, April 1997. [Online]. Available: http://dx.doi.org/10.1007%2Fs11746-997-0107-z
L. Shi, Y. Shi, L. Fu, X. Cong, and Z. Peng, “Synthesis of methyl abietate catalyzed by acidic functional ionic liquid sulfonic alkylimidazole p-toluenesulfonate,” Chemistry and Industrial of Forest Products, vol. 27, no. S1, pp. 11–14, Mar. 2007.
P. Mäki, B. Holmbom, T. Salmi, and D. Y. Murzin, “Recent progress in synthesis of fine and specialty chemicals from wood and other biomass by heterogeneous catalytic processes,” Catal. Rev. Sci. Eng., vol. 49, no. 3, June 2007. [Online]. Available: https://doi.org/10.1080/01614940701313127
J. D. Hind, T. T. Kanno, and C. S. Miner, “Ester gum by esterification of rosin with glycerol,” Ind. Eng. Chem., vol. 46, no. 3, March 1 1954. [Online]. Available: https://doi.org/10.1021/ie50531a021
X. Wang and et al, “Catalytic methyl esterification of colophony over ZnO/SFCCR with subcritical CO2: Catalytic performance, reaction pathway and kinetics,” R. Soc. open Sci., vol. 5, no. 5, May 2018. [Online]. Available: https://doi.org/10.1098/rsos.172124
Y. Liu and et al, “Synthesis of rosin methyl ester using PTSA/ZrO2/Mo-MCM-41 mesoporous molecular sieves,” Catal. Letters, vol. 149, no. 2, July 2019. [Online]. Available: https://doi.org/10.1007/s10562-019-02782-y
L. Wang and et al, “A supported nano ZnO catalyst based on a spent fluid cracking catalyst (FC3R) for the heterogeneous esterification of rosin,” React. Kinet. Mech. Catal., vol. 119, no. 1, April 2016. [Online]. Available: https://doi.org/10.1007/s11144-016-1022-9
D. F. Zinkel and J. Rusell, Naval stores: Production, chemistry, utilization. New York, USA: Pulp Chemicals Association, 1989.
J. A. Hudy, “Resin acids. Gas chromatography of their methyl esters,” Anal. Chem., vol. 31, no. 11, November 1 1959. [Online]. Available: https://doi.org/10.1021/ac60155a017
J. K. Volkman, D. G. Holdsworth, and D. E. Richardson, “Determination of resin acids by gas chromatography and high-performance liquid chromatography in paper mill effluent, river waters and sediments from the upper Derwent Estuary, Tasmania,” J. Chromatogr. A, vol. 643, no. 1-2, July 23 1993. [Online]. Available: https://doi.org/10.1016/0021-9673(93)80555-M
A. Montenegro and J. E. Rodríguez, “Synthesising highly reactive Tin oxide using Tin(II) 2-ethylhexanoate polynucleation as precursor,” Ing. e Investig., vol. 29, no. 1, pp. 47–52, Jan. 2009.
E. K. Plyler, “Infrared Spectra of Methanol, Ethanol, and nPropanol,” J. Res. Natl. Bur. Stand., vol. 48, no. 4, pp. 281–286, Apr. 1952.
M. Mandal, P. Borgohain, P. Begum, R. C. Deka, and T. K. Maji, “Property enhancement and DFT study of wood polymer composites using rosin derivatives as co-monomers,” New J. Chem, vol. 42, no. 3, January 2018. [Online]. Available: https://doi.org/10.1039/C7NJ03825A
R. T. Morrison and R. N. Boyd, Química orgánica, 5th ed. Nucalpan de Juarez, MEX: Pearson Educación, 1998.
M. Becerra, A. Centeno, and S. A. Giraldo, “Triglyceride transesterification in heterogeneous reaction system with calcium oxide as catalyst,” Revista Facultad de Ingeniería Universidad de Antioquia, no. 57, pp. 7–13, Jan. 2011.
M. J. Varady, “Fuel reformation and hydrogen generation in direct droplet impingement reactors,” Ph. D. dissertation, School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia, 2010.
G. Wypych, Handbook of Fillers, 3rd ed. Toronto, CA: ChemTec Publishing, 2010.
P. G. Jessop, D. A. Jessop, D. Fua, and L. Phan, “Solvatochromic parameters for solvents of interest in green chemistry,” Green Chemistry, vol. 14, no. 5, 2012. [Online]. Available: https://doi.org/10.1039/C2GC16670D
S. Yan, H. Lu, and B. Liang, “Supported CaO catalysts used in the transesterification of rapeseed oil for the purpose of biodiesel production,” Energy and Fuels, vol. 22, no. 1, January 2008. [Online]. Available: https://doi.org/10.1021/ef070105o
M. Galván, J. Hernández, L. Baños, J. Noriega, and M. E. Rodríguez, “Characterization of calcium carbonate, calcium oxide, and calcium hydroxide as starting point to the improvement of lime for their use in construction,” J. Mater. Civ. Eng., vol. 21, no. 11, pp. 625–708, Nov. 2009.
M. I. Zaki, H. Knözinger, B. Tesche, and G. A. H. Mekhemera, “Influence of phosphonation and phosphation on surface acid– base and morphological properties of CaO as investigated by in situ FTIR spectroscopy and electron microscopy,” J. Colloid Interface Sci., vol. 303, no. 1, November 1 2016. [Online]. Available: https://doi.org/10.1016/j.jcis.2006.07.011
R. S. Putra and et al, “Enhanced Electro-Catalytic Process on the Synthesis of FAME Using CaO from Eggshell,” Energy Procedia, vol. 105, May 2017. [Online]. Available: https://doi.org/10.1016/j.egypro.2017.03.316
S. Kaewdaeng, P. Sintuya, and R. Nirunsin, “Biodiesel production using calcium oxide from river snail shell ash as catalyst,” Energy Procedia, vol. 138, October 2017. [Online]. Available: https://doi.org/10.1016/j.egypro.2017.10.057
A. Abad, M. Arno, L. R. Domingo, and R. J. Zaragoza, “Synthesis of (+)-podocarp-8(14)-en-13-one and methyl-(+)-13-oxo-podocarp8(14)-en-18-oate from abietic acid,” Tetrahedron, vol. 41, no. 21, 1985. [Online]. Available: https://doi.org/10.1016/S0040-4020(01)96734-1
Published
How to Cite
Issue
Section
License
Copyright (c) 2020 Revista Facultad de Ingeniería Universidad de Antioquia
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
Revista Facultad de Ingeniería, Universidad de Antioquia is licensed under the Creative Commons Attribution BY-NC-SA 4.0 license. https://creativecommons.org/licenses/by-nc-sa/4.0/deed.en
You are free to:
Share — copy and redistribute the material in any medium or format
Adapt — remix, transform, and build upon the material
Under the following terms:
Attribution — You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use.
NonCommercial — You may not use the material for commercial purposes.
ShareAlike — If you remix, transform, or build upon the material, you must distribute your contributions under the same license as the original.
The material published in the journal can be distributed, copied and exhibited by third parties if the respective credits are given to the journal. No commercial benefit can be obtained and derivative works must be under the same license terms as the original work.
Twitter