Development of an <i>in-situ</i> H<sub>2</sub> reduction and moderate oxidation method for 3,5-dimethylpyridine hydrogenation in trickle bed reactor

doi:10.1007/s11705-022-2243-2

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (12) : 1807-1817 https://doi.org/10.1007/s11705-022-2243-2

RESEARCH ARTICLE

Development of an in-situ H₂ reduction and moderate oxidation method for 3,5-dimethylpyridine hydrogenation in trickle bed reactor

Tao Lin^1,^2,^3,^4,^5,^6,⁷, Xiaoxun Ma^1,^4,^5,^6,⁷(

)

¹. School of Chemical Engineering, Northwest University, Xi’an 710069, China
². Kaili Catalyst & New Materials Co., Ltd. Xi’an 710201, China
³. Shaanxi Key Laboratory of Catalytic Materials and Technology, Xi’an 710201, China
⁴. Chemical Engineering Research Center of the Ministry of Education (MOE) for Advanced Use Technology of Shanbei Energy, Xi’an 710069, China
⁵. Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Xi’an 710069, China
⁶. Collaborative Innovation Center for Development of Energy and Chemical Industry in Northern Shaanxi, Xi’an 710069, China
⁷. International Scientific and Technological Cooperation Base of the Ministry of Science and Technology (MOST) for Clean Utilization of Hydrocarbon Resources, Xi’an 710069, China

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Abstract

The Ru/C catalyst prepared by impregnation method was used for hydrogenation of 3,5-dimethylpyridine in a trickle bed reactor. Under the same reduction conditions (300 °C in H₂), the catalytic activity of the non-in-situ reduced Ru/C-n catalyst was higher than that of the in-situ reduced Ru/C-y catalyst. Therefore, an in-situ H₂ reduction and moderate oxidation method was developed to increase the catalyst activity. Moreover, the influence of oxidation temperature on the developed method was investigated. The catalysts were characterized by Brunauer–Emmett–Teller method, hydrogen temperature programmed reduction H₂-TPR, hydrogen temperature-programmed dispersion (H₂-TPD), X-ray diffraction, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, O₂ chemisorption and oxygen temperature-programmed dispersion (O₂-TPD) analyses. The results showed that there existed an optimal Ru/RuO_x ratio for the catalyst, and the highest 3,5-dimethylpyridine conversion was obtained for the Ru/C-i1 catalyst prepared by in-situ H₂ reduction and moderate oxidation (oxidized at 100 °C). Excessive oxidation (200 °C) resulted in a significant decrease in the Ru/RuO_x ratio of the in-situ H₂ reduction and moderate oxidized Ru/C-i2 catalyst, the interaction between RuO_x species and the support changed, and the hard-to-reduce RuO_x species was formed, leading to a significant decrease in catalyst activity. The developed in-situ H₂ reduction and moderate oxidation method eliminated the step of the non-in-situ reduction of catalyst outside the trickle bed reactor.

Keywords Ru/C catalyst in-situ H₂ reduction and moderate oxidation in-situ reduction non-in-situ reduction hydrogenation of 3,5-dimethylpyridine

Corresponding Author(s): Xiaoxun Ma

Online First Date: 09 November 2022 Issue Date: 19 December 2022

Cite this article:

Tao Lin,Xiaoxun Ma. Development of an in-situ H₂ reduction and moderate oxidation method for 3,5-dimethylpyridine hydrogenation in trickle bed reactor[J]. Front. Chem. Sci. Eng., 2022, 16(12): 1807-1817.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2243-2
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I12/1807

Fig.1 TBR for DPY hydrogenation.

Tab.1 Physico-chemical properties of the samples

Fig.2 N₂ adsorption-desorption isotherms and pore size distributions of the Ru/C catalysts.

Fig.3 H₂-TPR profiles of the samples: (a) carbon support, unreduced and Ru/C-y catalyst; (b) Ru/C-n, Ru/C-i0, Ru/C-i1 and Ru/C-i2 catalyst.

Fig.4 H₂-TPD profiles of the Ru/C catalysts.

Fig.5 X-ray diffraction patterns of the Ru/C catalysts.

Tab.2 Surface elements of the Ru/C catalysts

Fig.6 XPS spectra of Ru/C catalysts: (a) survey spectrum; (b) C 1s + Ru 3d; (c) Ru 3p.

Tab.3 Relatively abundance (%) of the components of the Ru 3p spectra

Fig.7 Raman spectra of the Ru/C catalysts.

Fig.8 (a) O₂ chemisorption and (b) O₂-TPD profiles of the Ru/C catalysts.

Fig.9 Effect of reaction temperature on DPY conversion over the Ru/C catalysts.

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