Chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism and kinetics

doi:10.1016/j.cjche.2019.03.005

Abstract

Abstract: The chitosan was found to possess an excellent catalytic performance in n-butyraldehyde selfcondensation to 2E2H. Under suitable conditions, the conversion of n-butyraldehyde, the yield and selectivity of 2E2H separately attained 96.0%, 86.0% and 89.6%. The chitosan catalyst could be recovered and used for 5 times without a significant deactivation after being treated with ammonium hydroxide. In order to elucidate the reaction mechanism, the adsorption and desorption of n-butyraldehyde on the surface of chitosan were studied using in situ FT-IR spectroscopy analysis. The result showed that n-butyraldehyde interacts with-NH₂ group of chitosan to form an intermediate species with an enamine structure. Then the reaction process of n-butyraldehyde self-condensation was monitored by React-IR technique and it was found that n-butyraldehyde self-condensation to 2-ethyl-3-hydroxyhexanal followed by a dehydration reaction to 2-ethyl-2-hexenal. On this basis, chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism was speculated and its reaction kinetics was investigated. The self-condensation reaction follows auto-catalytic reaction characteristics and then the corresponding kinetic model was established.

Key words: n-Butyraldehyde, Chitosan, Reaction, Mechanism, Kinetics, Autocatalysis

摘要： The chitosan was found to possess an excellent catalytic performance in n-butyraldehyde selfcondensation to 2E2H. Under suitable conditions, the conversion of n-butyraldehyde, the yield and selectivity of 2E2H separately attained 96.0%, 86.0% and 89.6%. The chitosan catalyst could be recovered and used for 5 times without a significant deactivation after being treated with ammonium hydroxide. In order to elucidate the reaction mechanism, the adsorption and desorption of n-butyraldehyde on the surface of chitosan were studied using in situ FT-IR spectroscopy analysis. The result showed that n-butyraldehyde interacts with-NH₂ group of chitosan to form an intermediate species with an enamine structure. Then the reaction process of n-butyraldehyde self-condensation was monitored by React-IR technique and it was found that n-butyraldehyde self-condensation to 2-ethyl-3-hydroxyhexanal followed by a dehydration reaction to 2-ethyl-2-hexenal. On this basis, chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism was speculated and its reaction kinetics was investigated. The self-condensation reaction follows auto-catalytic reaction characteristics and then the corresponding kinetic model was established.

关键词: n-Butyraldehyde, Chitosan, Reaction, Mechanism, Kinetics, Autocatalysis

Xiaoxu Han, Ying Li, Hualiang An, Xinqiang Zhao, Yanji Wang. Chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism and kinetics[J]. Chinese Journal of Chemical Engineering, 2019, 27(10): 2447-2454.

Xiaoxu Han, Ying Li, Hualiang An, Xinqiang Zhao, Yanji Wang. Chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism and kinetics[J]. 中国化学工程学报, 2019, 27(10): 2447-2454.

References

[1] P. Moggi, G. Albanesi, Gas phase aldol condensation of n-butyraldehyde to 2-ethylhexenal, Appl. Catal. 68(1) (1991) 285-300.
[2] A.N. Ko, C.H. Hu, J. Chen, Efficient direct synthesis of 2-ethylhexanal from n-butyraldehyde and hydrogen using palladium modified base catalysts, Appl. Catal. A Gen. 184(2) (1999) 211-217.
[3] C.N. Chen, L.L. Wu, H.L. An, X.Q. Zhao, Progress on the catalyst for the synthesis of 2-ethy-2-hexenal via n-butyraldehyde self-condensation, Chem. 76(4) (2013) 313-318.
[4] H. Tsuji, F. Yagi, H. Hattori, H. Kita, Self-condensation of n-butyraldehyde over solid base catalysis, J. Catal. 148(2) (1994) 759-770.
[5] G. Zhang, H. Hattori, K. Tanabe, Aldol addition of n-butyraldehyde over solid base catalysts, Bull. Chem. Soc. Jpn. 62(6) (1998) 2070-2072.
[6] H. Lou, H. Sun, J.Z. Duan, Y.Q. Ding, J.X. Han, W. Li, X.M. Zheng, Method and preparation of n-butyraldehyde condensation reaction of magnesia catalyst, China Pat., 102070419A (2011).
[7] Y.Y. Zhang, Self-Condensation of n-Butyraldehyde to 2-Ethyl-2-Hexenal Over Novel Catalytic, M. S. Thesis Shanghai Normal University, Shanghai, 2010.
[8] B.J. Arena, J.S. Holmgren, 2-Ehyl-2-hexenal by aldol condensation of butyraldehyde in a continuous process, US Pat., 5144089(1992).
[9] A.A. Schutz, Process for aldol condensation, US Pat., 5055620(1991).
[10] C.A. Hamilton, S.D. Jackson, G.J. Kelly, Solid base catalysts and combined solid base hydrogenation catalysts for the aldol condensation of branched and linear aldehydes, Appl. Catal. A Gen. 263(1) (2004) 63-70.
[11] L. Cui, H.Q. Lv, Z.F. Wang, J.S. Yao, Z. Li, L J. Dong, L.B. Hou, Application of a solid base catalyst for aldol condensation reaction, China Pat., 102019177A (2011).
[12] B. Su, W.Z. Lang, Q.Y. Zeng, X.W. Liu, J.C. Yang, Y.J. Guo, Preparation of organic functionalized mesoporous catalysts and their applications to the self-condensation reaction of n-butanal to 2-ethylhexenal, Chin. J. Process. Eng. s445-446(6) (2010) 180-186.
[13] F.M. Kerton, Y. Liu, K.W. Omari, K. Hawboldt, Green chemistry and the ocean-based biorefinery, Green Chem. 15(4) (2013) 860-871.
[14] N. Yan, X. Chen, Sustainability:Don't waste seafood waste, Nature 524(7564) (2015) 155-157.
[15] L. Jia, X. Liu, Y. Qiao, C.M. Pedersen, Z. Zhang, H. Ge, X. Wen, X. Wen, Y. Wang, Mechanism of the self-condensation of GlcNH₂:Insights from in situ NMR spectroscopy and DFT study, Appl. Catal. B Environ. 202(2017) 420-429.
[16] L. Jia, Z. Zhang, Y. Qiao, C.M. Pedersen, H. Ge, Z. Wei, T. Deng, J. Ren, X. Liu, Y. Wang, X. Hou, Product distribution control for glucosamine condensation:Nuclear magnetic resonance (NMR) investigation substantiated by density functional calculations, Ind. Eng. Chem. Res. 56(11) (2017) 2925-2934.
[17] Y. Wang, C.M. Pedersen, T. Deng, Y. Qiao, X. Hou, Direct conversion of chitin biomass to 5-hydroxymethylfurfural in concentrated ZnCl₂ aqueous solution, Bioresour. Technol. 143(2013) 384-390.
[18] H. Kayser, C.R. Müller, C.A. García-González, Dried chitosan-gels as organocatalysts for the production of biomass-derived platform chemicals, Appl. Catal. A Gen. 445(2012) 180.
[19] P.K. Sahu, P.K. Sahu, S.K. Gupta, D.D. Agarwal, Chitosan:An efficient, reusable, and biodegradable catalyst for green synthesis of heterocycles, Ind. Eng. Chem. Res. 53(6) (2014) 2085-2091.
[20] K.R. Reddy, K. Rajgopal, C.U. Maheswari, M.L. Kantam, Chitosan hydrogel:A green and recyclable biopolymer catalyst for aldol and Knoevenagel reactions, New J. Chem. 30(2006) 1549-1552.
[21] A. Ricci, L. Bernardi, C. Gioia, S. Vierucci, M. Robitzer, F. Quignard, Chitosan aerogel:A recyclable, heterogeneous organocatalyst for the asymmetric direct aldol reaction in water, Chem. Commun. 46(34) (2010) 6288-6290.
[22] S. Shylesh, D. Hanna, J. Gomes, C.G. Canlas, M. Headgordon, A.T. Bell, The role of hydroxyl group acidity on the activity of silica-supported secondary amines for the self-condensation of n-butanal, ChemSusChem. 8(3) (2014) 466-472.
[23] S. Lee, A. Varma, Kinetic study of biphasic aldol condensation of n-butyraldehyde using stirred cell, Chem. Eng. Sci. 104(50) (2013) 619-629.
[24] W.D. Zhu, A.N. Ko, J. Chin, Vapor-phase aldolization of n-butyraldehyde to 2-ethyl-2-hexenal over solid-base catalysts, Chem. Soc. 47(6) (2000) 1237-1242.
[25] X.L. Zhang, H.L. An, H.Q. Zhang, X.Q. Zhao, Y.J. Wang, n-Butyraldehyde selfcondensation catalyzed by sulfonic acid functionalized ionic liquids, Ind. Eng. Chem. Res. 53(43) (2014) 16707-16714.
[26] C. Xiong, N. Liang, H.L. An, X.Q. Zhao, Y.J. Wang, n-Butyraldehyde self-condensation catalyzed by Ce-modified γ-Al₂O₃, RSC Adv. 5(125) (2015) 103523-103533.
[27] C.N. Chen, Self-Condensation of N-Butyraldehyde to 2-Ethyl-2-Hexenal over H4SiW12O40/SiO2 Catalyst, M. S. Thesis Hebei University of Technology, Tianjin, 2010.
[28] O. Levenspiel, Chemical Reaction Engineering, Wiley, New York, 1972.