Tuning of the active phase structure and hydrofining performance of alumina-supported tri-metallic WMoNi catalysts via phosphorus incorporation

doi:10.1007/s11705-017-1686-3

Front. Chem. Sci. Eng.

2018, Vol. 12

Issue (1) : 59-69 https://doi.org/10.1007/s11705-017-1686-3

RESEARCH ARTICLE

Tuning of the active phase structure and hydrofining performance of alumina-supported tri-metallic WMoNi catalysts via phosphorus incorporation

Shufeng Shan¹, Haiyan Liu¹(

), Gang Shi¹, Xiaojun Bao²

¹. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
². State Key Laboratory of Energy & Environmental Photocatalysis, Fuzhou University, Fuzhou 350116, China

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Abstract

The effects of phosphorus on the structure and hydrofining performance of tri-metallic WMoNi/Al₂O₃ catalysts prepared with W/Mo-based hybrid precursor nanocrystals were investigated. The incorporation of phosphorus weakened the metal-support interactions (MSIs) and facilitated the formation of more synergetic NiWMoS phases with higher stacks. Catalytic tests using a fluid catalytic cracking diesel fuel showed that the changes in the MSIs and the morphology of the active phases had a more positive effect on the hydrodenitrogenation activity than on the hydrodesulfurization activity. In contrast, when phosphorus was incorporated into a tri-metallic WMoNiP/Al₂O₃ catalyst prepared by a conventional incipient impregnation method, the MSIs decreased causing aggregation of the metal species which resulted in poorer hydrofining performance of the catalyst. These results show that incorporating phosphorus into a WMoNi/Al₂O₃ catalyst can finely tune the structure of the active phase to enhance the hydrogenation and hydrodenitrogenation activity of the resulting tri-metallic catalyst.

Keywords fluid catalytic cracking diesel hydrofining performance WMoNiP/Al₂O₃ synergetic effect and structure of NiWMoS phases

Corresponding Author(s): Haiyan Liu,Xiaojun Bao

Just Accepted Date: 25 September 2017 Online First Date: 05 January 2018 Issue Date: 26 February 2018

Cite this article:

Shufeng Shan,Haiyan Liu,Gang Shi, et al. Tuning of the active phase structure and hydrofining performance of alumina-supported tri-metallic WMoNi catalysts via phosphorus incorporation[J]. Front. Chem. Sci. Eng., 2018, 12(1): 59-69.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1686-3
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I1/59

Fig.1 (A) XRD patterns of (a) WMoNi-HHD, (b) WMo-HHD-PNi and (c) WMo-IM-PNi; (B) DRS UV-vis spectra of (a) WMoNi-HHD, (b) WMo-HHD-PNi and (c) WMo-IM-PNi after subtracting the spectra of γ-Al₂O₃; and (C) E_g values of (a) WMoNi-HHD, (b) WMo-HHD-PNi and (c) WMo-IM-PNi

Tab.1 Textural properties of Al₂O₃, WMoNi-HHD, WMo-HHD-PNi and WMo-IM-PNi

Fig.2 NH₃-TPD profiles of WMoNi-HHD, WMo-HHD-PNi and WMo-IM-PNi

Fig.3 TPR spectra of WMoNi-HHD, WMo-HHD-PNi and WMo-IM-PNi

Sample	Surface atomic ratios and sulfidation degrees /%						MS₂ morphology parameters
Sample	W/Al^a)	Mo/Al^a)	Ni/Al^a)	Ni/(Ni+W+Mo)^a)	W_sulfidation	Mo_sulfidation	$L ‾$ ^b)	$N ‾$ ^b)	f_M^c)
WMoNi-HHD	0.048	0.036	0.045	0.350	42.6	60.1	3.9	2.4	0.29
WMo-HHD-PNi	0.042	0.033	0.041	0.354	56.1	88.7	4.1	2.7	0.28
WMo-IM-PNi	0.031	0.020	0.027	0.346	48.0	83.8	6.5	2.8	0.15

Tab.2 XPS and HRTEM results of the sulfided WMoNi-HHD, WMo-HHD-PNi and WMo-IM-PNi

Fig.4 (A) Mo3d and (B) W4f XPS spectra of the sulfided WMoNi-HHD; (C) Mo3d and (D) W4f XPS spectra of the sulfided WMo-HHD-PNi, (E) Mo3d and (F) W4f XPS spectra of the sulfided WMo-IM-PNi

Fig.5 HRTEM images of the sulfided (A) WMoNi-HHD, (B) WMo-HHD-PNi and (C) WMo-IM-PNi

Fig.6 Distributions of (A) lengths and (B) number of layered MS₂ (M= W or Mo) slabs on sulfided WMoNi-HHD, WMo-HHD-PNi and WMo-IM-PNi

Tab.3 Properties of FCC diesel fuel before and after hydrofining over WMoNi-HHD, WMo-HHD-PNi and WMo-IM-PNi

Fig.7 (A) HDS and (B) HDN activity of WMoNi-HHD, WMo-HHD-PNi and WMo-IM-PNi using FCC diesel fuel

Fig.8 Schematic representation of the composition and morphology of the sulfide phases in (A) WMoNi-HHD, (B) WMo-HHD-PNi and (C) WMo-IM-PNi

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