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Continuous synthesis of N-ethylethylenediamine over supported Cu–Zn–La catalysts

  • Wang-Wang Fang , Man-Man Mu , Jun Tian , Li-Gong Chen and Yang Li EMAIL logo
Published/Copyright: February 2, 2016
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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 continuously for over 200 h.

Acknowledgements

Financial support was provided by the National Natural Science Foundation of China (Grant No. 21476163).

References

Bernady, K. F., & Mogolesko, P. D. (1980). U.S. Patent No. 4,217,308. Washington, DC, USA: US Patent and Trademark Office.Search in Google Scholar

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.200690001.10.1002/adsc.200690001Search in Google Scholar

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/s11696-010-0033-7.10.2478/s11696-010-0033-7Search in Google Scholar

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.10.1021/ja807323aSearch in Google Scholar PubMed

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.2012.05.007.10.1016/j.jcat.2012.05.007Search in Google Scholar

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.201001871.10.1002/chem.201001871Search in Google Scholar PubMed

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.10.1021/jo010643cSearch in Google Scholar PubMed

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-Al2O3bifunctional catalysts: Effect of Zr-loading. Fuel Processing Technology, 126, 88–94. DOI: 10.1016/j.fuproc.2014.04.021.10.1016/j.fuproc.2014.04.021Search in Google Scholar

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/s11164-014-1641-6.10.1007/s11164-014-1641-6Search in Google Scholar

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.2012.01.004.10.1016/j.catcom.2012.01.004Search in Google Scholar

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.Search in Google Scholar

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, 145– 149. DOI: 10.1016/j.catcom.2006.05.041.10.1016/j.catcom.2006.05.041Search in Google Scholar

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/γ-Al2O3. Reaction Kinetics, Mechanisms and Catalysis, 106, 485–493. DOI: 10.1007/s11144-012-0447-z.10.1007/s11144-012-0447-zSearch in Google Scholar

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.2004.03.004.10.1016/j.catcom.2004.03.004Search in Google Scholar

Received: 2015-6-13
Revised: 2015-9-9
Accepted: 2015-10-5
Published Online: 2016-2-2
Published in Print: 2016-4-1

© 2015 Institute of Chemistry, Slovak Academy of Sciences

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