Kinetics of Direct Amidation of Stearic Acid with Ethanolamines: Experimental Studies and Mathematical Modeling

Abstract

This paper presents the results of the study of kinetics of stearic acid direct amidation with mono- and diethanolamines in a closed thermodynamic system. The rate constants of stearic acid ethanolamides synthesis at different temperatures and the activation energy values of these reactions were determined experimentally. It has been demonstrated that the reaction of stearic acid amidation with ethanolamine in a closed system is run until the equilibrium acid--amide, which is shifted towards the reaction products, and the equilibrium constants of this reaction have been determined. Also, it has been shown that the reaction of stearic acid with diethanolamine has a more complicated kinetic behavior than that with monoethanolamine, and it does not end at the stage of diethanolamide formation as far as a number of side reactions take place. A mathematical model for the process of stearic acid amidation, which takes into consideration contributions both of the main reaction and of the number of side-reactions, has been developed. The model adequacy is supported with high correlation between predicted values and experimental ones. Using this model the reaction rate constants and their activation energy values have been calculated

The work was funded by Russian Foundation for Basic Research (project no. 20-33-90148)

Please cite this article as:

Yanovsky V.A. Andropov M.O. Romanenko S.V., et al. Kinetics of direct amidation of stearic acid with ethanolamines: experimental studies and mathematical modeling. Herald of the Bauman Moscow State Technical University, Series Natural Sciences, 2024, no. 6 (117), pp. 124--141. EDN: AZTHSR

References

[1] Zoller U., ed. Handbook of detergents. Part F: Production. CRC Press, 2008.

[2] Farn R.J. Chemistry and technology of surfactants. Wiley-Blackwell, 2006.

[3] Fainerman V.B., Mobius D., Miller R., eds. Surfactants: chemistry, interfacial properties, applications. Elsevier, 2002.

[4] Maag H. Fatty acid derivatives: important surfactants for household, cosmetic and industrial purposes. J. Am. Oil Chem. Soc., 1984, vol. 61, no. 2, pp. 259--267. DOI: https://doi.org/10.1007/BF02678778

[5] Caenn R., Darley H.C.H., Gray G.R. Composition and properties of drilling and completion fluids.

[6] Growcock F.B., Pate A.D. The revolution in non-aqueous drilling fluids. AADE National Tech. Conf. and Exhibition, 2011, art. AADE-11-NTCE-33.

[7] Chambers M.R., Hebert D.B., Shuchart C.E. Successful application of oil-based drilling fluids in subsea horizontal, gravel-packed wells in West Africa. In: SPE Int. Symposium on Formation Damage Control, 2000, paper SPE-58743-MS. DOI: https://doi.org/10.2118/58743-MS

[8] Minaev K., Epikhin A., Novoseltsev D., et al. Research of inverted emulsions properties on the base of new emulsifiers. IOP Conf. Ser.: Earth Environ. Sci., 2014, vol. 21, art. 012033. DOI: http://dx.doi.org/10.1088/1755-1315/21/1/012033

[9] Sheng J.J. Polymer flooding. In: Modern Chemical Enhanced Oil Recovery. Gulf Professional, 2011, pp. 101--206. DOI: https://doi.org/10.1016/B978-1-85617-745-0.00005-X

[10] Varadaraj R., Bragg J.R., Peiffer D.G. Stability enhanced water-in-oil emulsion and method for using same. Patent US 7186673. Appl. 28.02.2001, publ.24.06.2004.

[11] Bampfield H.A., Cooper J., Emulsion explosives. In: Encyclopedia of emulsion technology. Vol. 7. Marcel Dekker, 1985, pp. 281--306.

[12] Myers D. Surfactant science and technology. Wiley, 2005.

[13] Kumar D., Kim S.M., Ali A. One step synthesis of fatty acid diethanolamides and methyl esters from triglycerides using sodium doped calcium hydroxide as a nanocrystalline heterogeneous catalyst. New J. Chem., 2015, vol. 39, no. 9, pp. 7097--7104. DOI: https://doi.org/10.1039/C5NJ00388A

[14] Karaulov A.E., Rybin V.G., Kuklev D.V., et al. Synthesis of fatty-acid ethanolamides from linum catharticum oils and cololabis saira fats. Chem. Nat. Compd., 2004, vol. 40, no. 3, pp. 222--226. DOI: https://doi.org/10.1023/B:CONC.0000039128.78645.a8

[15] Feairheller S.H., Bistline Jr R.G., Bilyk A., et al. A novel technique for the preparation of secondary fatty amides. III. Alkanolamides, diamides and aralkylamides. J. Am. Oil Chem. Soc., 1994, vol. 71, no. 8, pp. 863--866. DOI: https://doi.org/10.1007/BF02540463

[16] Handbook on soaps, detergents & acid slurry. Asia Pacific Business Press, 2006.

[17] Adewuyi A. Synthesis and surface-active property of diethanolamide and epoxidised diethanolamide surfactant from the seed oil of Baphia nitida. Arab. J. Chem., 2019, vol. 12, no. 7, pp. 1545--1551. DOI: https://doi.org/10.1016/j.arabjc.2014.10.021

[18] Yanovsky V.A., Churkin R.A., Andropov M.O., et al. Synthesis and study of properties of emulsifiers for reverse emulsions based on derivatives of acids of tall oil distillate and ethanolamines. Vestnik Tomskogo gosudarstvennogo universiteta [Tomsk State University Journal], 2013, no. 370, pp. 194--199 (in Russ.). EDN: PZXNJT

[19] Butler R.N., O’Regan C.B., Moynihan P. Reactions of fatty acids with amines. Part 2. Sequential thermal reactions of stearic (octadecanoic) acid with some 1,2- and 1,3-aminoalcohols and bis-amines. J. Chem. Soc., Perkin Trans. 1, 1978, iss. 4, pp. 373--377. DOI: https://doi.org/10.1039/P19780000373

[20] Sagnella S.M., Conn С.Е., Krodkiewska I., et al. Nonionic diethanolamide amphiphiles with unsaturated C18 hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behavior. Phys. Chem. Chem. Phys., 2011, vol. 13, iss. 29, pp. 13370--13381. DOI: https://doi.org/10.1039/C1CP21808E

[21] Kamyshan M.A., Pavlov G.M. Kinetics of the process of amidation of fatty acids with monoethanolamine. Izvestiya vysshikh uchebnykh zavedeniy. Pishchevaya tekhnologiya [Izvestiya vuzov. Food Technology], 1963, no. 4, pp. 61--65 (in Russ.).

[22] Gorodnov V.P., Petrov A.A. Obezvozhivanie nefti i ochistka stochnykh vod [Oil Dehydration and Wastewater Treatment]. Moscow, Nedra Publ., 1971.

[23] Richmond J.M., ed. Cationic surfactants. Organic chemistry. CRC Press, 1990.

[24] Smith M.B., March J. Addition to carbon-hetero multiple bonds. In: March’s Advanced Organic Chemistry. Wiley, 2006, pp. 1251--1476. DOI: https://doi.org/10.1002/9780470084960.ch16

[25] Perreux L., Loupy F., Volatron F. Solvent-free preparation of amides from acids and primary amines under microwave irradiation. Tetrahedron, 2002, vol. 58, iss. 11, pp. 2155--2162. DOI: https://doi.org/10.1016/S0040-4020(02)00085-6

[26] Trowbridge J.R., Falk R.A., Krems I.J. Fatty acid derivatives of diethanolamine. J. Org. Chem., 1955, vol. 20, iss. 8, pp. 990--995. DOI: https://doi.org/10.1021/jo01365a005