Kinetic study for the oxidation of cyclohexanol and cyclohexanone with nitric acid to adipic acid

doi:10.1016/j.cjche.2020.05.011

Abstract

Abstract: The adipic acid is an important intermediate in the production of nylon, polyurethane and polyester resins. The industrial approach for preparing adipic acid is through the liquid catalytic oxidation of KA oil with nitric acid. In this work, a comprehensive model is developed for this reaction based on the kinetic study conducted in a continuous flow tubular reactor. The kinetic model fits well with the experimental results across the experimental conditions, and the average relative error between the calculated and experimental values is 5.7%. Results show that there was an induction period at the early stage of reaction. Moreover, it is found that at temperature range of 328-358 K, the formation rate of adipic acid strongly dependents on the temperature and nitric acid concentration. The developed model is used to predict the yield of adipic acid at 359-368 K. The work in this study could provide much knowledge for industrial tubular reactor design.

Key words: Adipic acid, Nitric acid, Tubular reactor, Kinetic model

摘要： The adipic acid is an important intermediate in the production of nylon, polyurethane and polyester resins. The industrial approach for preparing adipic acid is through the liquid catalytic oxidation of KA oil with nitric acid. In this work, a comprehensive model is developed for this reaction based on the kinetic study conducted in a continuous flow tubular reactor. The kinetic model fits well with the experimental results across the experimental conditions, and the average relative error between the calculated and experimental values is 5.7%. Results show that there was an induction period at the early stage of reaction. Moreover, it is found that at temperature range of 328-358 K, the formation rate of adipic acid strongly dependents on the temperature and nitric acid concentration. The developed model is used to predict the yield of adipic acid at 359-368 K. The work in this study could provide much knowledge for industrial tubular reactor design.

关键词: Adipic acid, Nitric acid, Tubular reactor, Kinetic model

Detao Pan, Guangxiao Li, Yuanhai Su, Huilong Wei, Zhenghong Luo. Kinetic study for the oxidation of cyclohexanol and cyclohexanone with nitric acid to adipic acid[J]. Chinese Journal of Chemical Engineering, 2021, 29(1): 183-189.

Detao Pan, Guangxiao Li, Yuanhai Su, Huilong Wei, Zhenghong Luo. Kinetic study for the oxidation of cyclohexanol and cyclohexanone with nitric acid to adipic acid[J]. 中国化学工程学报, 2021, 29(1): 183-189.

References

[1] S. Van de Vyver, Y. Román-Leshkov, Emerging catalytic processes for the production of adipic acid, Catal. Sci. Technol. 3(6) (2013) 1465-1479.
[2] D. René, J. Villermaux, P. Marchal, et al., Crystallization and precipitation engineering-IV. Kinetic model of adipic acid crystallization, Chem. Eng. Sci. 46(4) (1991) 1129-1136.
[3] M.L. Guo, Catalytic oxidation of cyclohexene to adipic acid with a reaction-controlled phase-transfer catalyst, Chinese J. Catal. 24(7) (2003) 483-484.
[4] K. Sato, M. Aoki, R.A. Noyori, A "green" route to adipic acid:direct oxidation of cyclohexenes with 30 percent hydrogen peroxide, Science 281(5383) (1998) 1646-1647.
[5] A.K. Patra, A. Dutta, A. Bhaumik, Mesoporous core-shell Fenton nanocatalyst:a mild, operationally simple approach to the synthesis of adipic acid, Chem. Eur. J. 19(37) (2013) 12388-12395.
[6] M.J. Shang, T. Noel, Y.H. Su, V. Hessel, High pressure direct synthesis of adipic acid from cyclohexene and hydrogen peroxide via capillary microreactors, Ind. Eng. Chem. Res. 55(2016) 2669-2676.
[7] J. Jian, K. You, Q. Luo, H.X. Gao, F.F. Zhao, P. Liu, Q. Ai, H.A. Luo, Supported Ni-Al-VPO/MCM-41 as efficient and stable catalysts for highly selective preparation of adipic acid from cyclohexane with NO₂, Ind. Eng. Chem. Res. 55(13) (2016) 3729-3735.
[8] M.J. Gilkey, A.V. Mironenko, D.G. Vlachos, B.J. Xu, Adipic acid production via metalfree selective hydrogenolysis of biomass-derived retrahydrofuran-2,5-dicarboxylic acid, ACS Cata 7(2017) 6619-6634.
[9] S. Benadji, T. Mazari, L. Dermeche, N. Salhi, E. Cadot, C. Rabia, Clean alternative for adipic acid synthesis via liquid-phase oxidation of cyclohexanone and cyclohexanol over H₃-2_xCo_xPMo₁₂O₄₀ catalysts with hydrogen peroxide, Cata. Letters 143(8) (2013) 749-755.
[10] P.L. Mills, R.V. Chaudhari, Reaction engineering of emerging oxidation processes, Catal. Today 48(1) (1999) 17-29.
[11] Z. Serinyel, O. Herbinet, O. Frottier, P. Dirrnberger, V. Warth, P.A. Glaude, F. BattinLeclerc, An experimental and modeling study of the low- and high-temperature oxidation of cyclohexane, Combust. Flame 160(11) (2013) 2319-2332.
[12] E.J. Silke, W.J. Pitz, C.K. Westbrook, M. Ribaucour, Detailed chemical kinetic modeling of cyclohexane oxidation, J. Phys. Chem. A 111(19) (2007) 3761-3775.
[13] R. Pohorecki, J. Baldyga, W. Moniuk, W. Podgorska, A. Zdrojkowski, P.T. Wierzchowski, Kinetic model of cyclohexane oxidation, Chem. Eng. Sci. 56(4) (2001) 1285-1291.
[14] R. Pohorecki, W. Moniuk, P.T. Wierzchowski, Kinetic model of uncatalyzed oxidation of cyclohexane, Chem. Eng. Res. Des. 87(3) (2009) 349-356.
[15] H. Nagahara, M. Ono, M. Konishi, Y. Fukuoka, Partial hydrogenation of benzene to cyclohexene, Appl.Surf. Sci. 121(6) (1997) 448-451.
[16] S.I. Niwa, F. Mizukami, S. Isoyama, Y. Tsuchiya, K. Shimizu, S. Juichi, Partial hydrogenation of benzene with ruthenium catalysts prepared by a chemical mixing procedure:Preparation and properties of the catalysts, J. Chem.Tech. Biot. 36(5) (2007) 236-246.
[17] L.J. Simon, J.G.V. Ommen, A. Jentys, J.A. Lercher, Sulfur tolerance of Pt/mordenites for benzene hydrogenation:Do Brønsted acid sites participate in hydrogenation? Catal. Today 73(1) (2002) 105-112.
[18] P.T. Maréco, J.R. Mahoungou, J. Barbier, Benzene hydrogenation on platinum and iridium catalysts. Variation of the toxicity of sulfur with the nature of the support, Appl. Cata. A-GEN 101(1) (1993) 143-149.
[19] G. Neri, A.M. Visco, A. Donato, C. Milone, M. Malentacchi, G. Gubitosa, Hydrogenation of phenol to cyclohexanone over palladium and alkali-doped palladium catalysts, Appl.Cata. A-GEN 110(1) (1994) 49-59.
[20] P. Yolanda, M. Fajardo, A. Corma, Highly selective palladium supported catalyst for hydrogenation of phenol in aqueous phase, Cata. Commun. 12(12) (2011) 1071-1074.
[21] A. Castellan, J.C.J. Bart, S. Cavallaro, Nitric acid reaction of cyclohexanol to adipic acid, Catal. Today 9(3) (1991) 255-283.
[22] H.C. Godt, J.F. Quinn, A study of the nitric acid oxidation of cyclohexanol to adipic acid, J. Am. Chem. Soc. 78(7) (1956) 1461-1464.
[23] W.J. van Asselt, D.W. van Krevelen, Preparation of adipic acid by oxidation of cyclohexanol and cyclohexanone with nitric acid:Part I. Reaction mechanism, Recueil 82(1963) 51-67.
[24] E.H. Hoffmann, A. Tilgner, R. Wolke, O. Boge, A. Walter, H. Herrmann, Oxidation of substituted aromatic hydrocarbons in the tropospheric aqueous phase:kinetic mechanism development and modeling, Phys. Chem. Chem. Phys. 20(2018) 10960-10977.
[25] A. Castellan, J.C.J. Bart, S. Cavallaro, Synthesis of adipic acid via the nitric acid oxidation of cyclohexanol in a two-step batch process, Catal. Today 9(1991) 285-299.
[26] A. Castellan, Synthesis of adipic acid via nitric acid oxidation of cyclohexanol in a two-step continuous process, Catal. Today 9(1991) 301-322.
[27] G.F. Froment, K.B. Bischoff, Chemical Reactor Analysis and Design, Wiley, New York, 1990.
[28] W.J. van Asselt, D.W. van Krevelen, Preparation of adipic acid by oxidation of cyclohexanol and cyclohexanone with nitric acid:Part Ⅱ. Reaction kinetics of the decomposition of 6-hydroxyimino-6-nitro hexanoic acid, Recueil 82(1963) 429-437.
[29] W.J. van Asselt, D.W. Van Krevelen, Preparation of adipic acid by oxidation of cyclohexanol and cyclohexanone with nitric acid:Part Ⅲ. Reaction kinetics of the oxidation, Recueil 82(1963) 438-449.
[30] W.J. van Asselt, D.W. van Krevelen, Adipic acid formation by oxidation of cyclohexanol and cyclohexanone with nitric acid:measurements in a continuous stirred tank reactor reactor stability, Chem. Eng. Sci. 18(8) (1963) 471-483.
[31] Y. Qu, C. Fang, M. Duan, J.D. Wang, Investigations on the reaction kinetics and the catalytic effect of Cu(Ⅱ) and V(V) in the oxidation of cyclohexanol by nitric acid, Reaction Kinet. Mech. Cata. 112(1) (2014) 209-226.
[32] J.R. Lindsay Smith, D.I. Richards, C.B. Thomas, M. Whittaker, The formation of glutaric and succinic acids in the oxidation of cyclohexanol by nitric acid, J. Chem. Soc. Perk. Trans. 2(1992) 605-611.
[33] J.R. Lindsay Smith, D.I. Richards, C.B. Thomas, M. Whittaker, The role of vanadium(V) in the oxidation of cyclohexanol to adipic acid by nitric acid, J. Chem. Soc. Perk. Trans. 2(1985) 1677-1682.
[34] J.R. Lindsay Smith, C.B. Thomas, M. Whittaker, The oxidation of α-substituted cyclohexanols by nitric acid, J. Chem. Soc. Perk. Trans 2(1993) 2191-2194.