Abstract
A series of Cu-based catalysts were prepared and employed in the N-ethylation of ethylenediamine with ethanol in a fixed-bed reactor. Satisfying results were obtained using Cu-Zn-La/Al2O3 as a catalyst. In addition, Cu-Zn-La/SiO2, Cu-Zn-La/Al2O3 and Cu-Zn-La/HZSM-5 were characterized by the Brunauer-Emmett-Teller method (BET), H2- temperature program reduction (H2-TPR), X-ray diffraction (XRD), transmission electron microscopic measurements (TEM) and NH3-temperature programmed desorption (NH3-TPD) in order to investigate the influence of supports on their catalytic performance. It was found that both the BET surface area and the acidity of the support are key factors in the catalytic performance. Moreover, reaction parameters including temperature, hydrogen pressure and liquid hourly space velocity were optimized. Under optimal conditions, a 73.3 % conversion of ethylenediamine and a 71.2 % selectivity of N-ethylethylenediamine were achieved. Finally, the lifetime of the catalysts was evaluated and the reaction proceeded con-tinuously for over 200 h.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Bernady, K. F., & Mogolesko, P. D. (1980). U.S. Patent No. 4,217,308. Washington, DC, USA: US Patent and Trademark Office.
Buchwald, S. L., Mauger, C., Mignani, G., & Scholz, U. (2006). Industrial-scale palladium-catalyzed coupling of aryl halides and amines-A personal account. Advanced Synthesis & Catalysis, 348, 23–40. DOI: 10.1002/adsc.200690001.
Chen, H. G., Zhang, T., Qian, C., & Chen, X. Z. (2010). A novel method for N-alkylation of aliphatic amines with ethers over γ-Al2O3. Chemical Papers, 64, 537–540. DOI: 10.2478/s11696-010-0033–7.
Hamid, M. H. S. A., Allen, C. L., Lamb, G. W., Maxwell, A. C., Maytum, H. C., Watson, A. J., & Williams, J. M. J. (2009). Ruthenium-catalyzed N-alkylation of amines and sulfonamides using borrowing hydrogen methodology. Journal of the American Chemical Society, 131, 1766–1774. DOI: 10.1021/ja807323a.
Liu, H. H., Chuah, G. K., & Jaenicke, S. (2012). N-alkylation of amines with alcohols over alumina-entrapped Ag catalysts using the “borrowing hydrogen” methodology. Journal of Catalysis, 292, 130–137. DOI: 10.1016/j.jcat.2012.05.007.
Michlik, S., & Kempe, R. (2010). New iridium catalysts for the efficient alkylation of anilines by alcohols under mild conditions. Chemistry-A European Journal, 16, 13193–13198. DOI: 10.1002/chem.201001871.
Salvatore, R. N., Nagle, A. S., & Jung, K. W. (2002). Cesium effect: High chemoselectivity in direct N-alkylation of amines. The Journal of Organic Chemistry, 67, 674–683. DOI: 10.1021/jo010643c.
Song, F. E., Tan, Y. S., Xie, H. J., Zhang, Q. D., & Han, Y. Z. (2014). Direct synthesis of dimethyl ether from biomass-derived syngas over Cu-ZnO-Al2O3-ZrO2(x)/γ-Al2O3 bifunctional catalysts: Effect of Zr-loading. Fuel Processing Technology, 126, 88–94. DOI: 10.1016/j.fuproc.2014.04.021.
Song, G., Tian, J., Chen, L. G., & Li, Y. (2015). Facile and efficient reductive N-alkylation of nitrobenzenes with alcohols catalyzed by Cu-Cr/γ-Al2O3. Research on Chemical Intermediates, 41, 5399–5409. DOI: 10.1007/s11164-014-1641-6.
Sun, M., Du, X. B., Kong, X. J., Lu, L., Li, Y., & Chen, L. G. (2012). The reductive amination of cyclohexanone with 1,6-diaminohexane over alumina B modified Cu–Cr–La/γ-Al2O3. Catalysis Communications, 20, 58–62. DOI: 10.1016/j.catcom.2012.01.004.
Tahara, S., Nishihira, K., Miyatake, T., Sawada, H., & Kita, J. (1983). U.S. Patent No. 4,373,107. Washington, DC, USA: U.S. Patent and Trademark Office.
Wang, H. F., Chen, L. G., Bai, G. Y., Luan, D. Z., Li, Y., Yan, X. L., Zhang, Y. C., & Xing, J. D. (2007). Study on deactivation of Cu–Zn–Al catalysts in the synthesis of N-ethylethylenediamine. Catalysis Communications, 8, 145149. DOI: 10.1016/j.catcom.2006.05.041.
Wu, Z. W., Yang, F., Wang, H. B., Ma, J. C., Chen, L. G., & Li, Y. (2012). A general process for the cyclization of aminoalcohols to the corresponding amines over Cu–Cr–La/gg-Al2O3. Reaction Kinetics, Mechanisms and Catalysis, 106, 485–493. DOI: 10.1007/s11144-012-0447-z.
Yamakawa, T., Tsuchiya, I., Mitsuzuka, D., & Ogawa, T. (2004). Alkylation of ethylenediamine with alcohols by use of Cu-based catalysts in the liquid phase. Catalysis Communications, 5, 291–295. DOI: 10.1016/j.catcom.2004.03.004.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Fang, WW., Mu, MM., Tian, J. et al. Continuous synthesis of N-ethylethylenediamine over supported Cu-Zn-La catalysts. Chem. Pap. 70, 430–435 (2016). https://doi.org/10.1515/chempap-2015-0233
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1515/chempap-2015-0233