A comparison of the catalytic hydrogenation of 2-amylanthraquinone and 2-ethylanthraquinone over a Pd/Al <sub>2</sub>O<sub>3</sub> catalyst

doi:10.1007/s11705-016-1604-0

Front. Chem. Sci. Eng.

2017, Vol. 11

Issue (2) : 177-184 https://doi.org/10.1007/s11705-016-1604-0

RESEARCH ARTICLE

A comparison of the catalytic hydrogenation of 2-amylanthraquinone and 2-ethylanthraquinone over a Pd/Al ₂O₃ catalyst

Enxian Yuan¹, Xiangwei Ren³, Li Wang^1,²(

), Wentao Zhao³

¹. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
². Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
³. School of Science, Tianjin University, Tianjin 300072, China

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Abstract

The hydrogenation of 2-ethylanthraquinone (eAQ), 2-tert-amylanthraquinone (taAQ) and their mixtures with molar ratios of 1:1 and 1:2 to the corresponding hydroquinones (eAQH₂ and taAQH₂) were studied over a Pd/Al₂O₃ catalyst in a semi-batch slurry reactor at 60 °C and at 0.3 MPa. Compared to eAQ, TaAQ exhibited a significantly slower hydrogenation rate (about half) but had a higher maximum yield of H₂O₂ and a smaller amount of degradation products. This can be ascribed to the longer and branched side chain in taAQ, which limits its accessibility to the Pd surface and its diffusion through the pores of the catalyst. Density functional theory calculations showed that it is more difficult for taAQ to adsorb onto a Pd (111) surface than for eAQ. The hydrogenation of the eAQ/taAQ mixtures had the slowest rates, lowest H₂O₂yields and the highest amounts of degradation products.

Keywords hydrogenation hydrogen peroxide anthraquinone Pd catalyst AO process

Corresponding Author(s): Li Wang

Online First Date: 30 December 2016 Issue Date: 12 May 2017

Cite this article:

Enxian Yuan,Xiangwei Ren,Li Wang, et al. A comparison of the catalytic hydrogenation of 2-amylanthraquinone and 2-ethylanthraquinone over a Pd/Al ₂O₃ catalyst[J]. Front. Chem. Sci. Eng., 2017, 11(2): 177-184.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-016-1604-0
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I2/177

Fig.1 Secheme 1The main steps of the AO process and typical side reactions that occur during the hydrogenation step

Fig.2 (a) XRD pattern, (b) nitrogen adsorption-desorption isotherm (inset: pore size distribution), (c) SEM image (inset: TEM image) and (d) XPS spectra of the Pd/Al₂O₃ catalyst (experimental data: dotted line, fitted data: solid line)

Fig.3 Ratio of hydrogen consumption to the initial amount of aAQ (R_hc) for different aAQs (catalyst amount= 10 g/L, c⁰_aAQ = 0.45 mol/L, 0.3 MPa and 60 °C)

Fig.4 Yield of H₂O₂ obtained using different aAQs (catalyst amount= 10 g/L, c⁰_aAQ = 0.45 mol/L, 0.3 MPa and 60 ºC)

Fig.5 Yield of by-products for (a) eAQ and (b) taAQ hydrogenation (catalyst amount= 10 g/L, c⁰_aAQ= 0.45 mol/L, 0.3 MPa and 60 °C)

Fig.6 Yield of by-products for (a) 1eAQ+ 1taAQ and (b) 1eAQ+ 2taAQ hydrogenation (catalyst amount= 10 g/L,c⁰_aAQ = 0.45 mol/L, 0.3 MPa and 60 °C)

Tab.1 Adsorption and desorption energies of aAQs, C?O bond lengths and C?Pd and O?Pd distances of adsorbed aAQs

Fig.7 Optimized structure of aAQ adsorbed on the Pd (111) facet: (a) eAQ and (b) taAQ ( : Pd; : C; : O; : H)

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