Effect of Yttrium and Citric Acid on the Hydrodesulfurization Performance of Unsupported Nickel Phosphide†

doi:10.7503/cjcu20150923

Abstract

Abstract:

The Yttrium(Y), citric acid(CA) and combined Y and CA modified bulk nickel phosphide(Ni-P) catalysts were prepared by temperature programmed reduction(TPR) method. The catalysts were characterized by means of X-ray diffraction(XRD), N₂-adsorption specific surface area measurements(BET), CO chemisorption uptake measurements, X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM). The effects of Y and CA on catalyst activity for dibenzothiophene(DBT) hydrodesulfurization(HDS) were studied. The results indicated that both Y and CA can promote the transformation from Ni_xP_yO_z amorphous phase to nickel phosphide active phase, suppress the formation of Ni₅P₄ phase and therefore promote the formation of Ni₂P active phase. Addition of Y or CA can increase the surface area and suppress the enrichment of phosphorus on surface, leading to a smaller and highly dispersed active phase particles. The Y, CA and combined Y and CA modified nickel phosphide catalysts were proved to possess higher HDS activity than Ni-P sample. The DBT conversions of catalysts followed the order: Y-Ni-P-CA>Ni-P-CA>Y-Ni-P>Ni-P. At the conditions of 340 ℃, 3.0 MPa, WHSV of 1.5 h^-1 and H₂/oil volume ratio of 700, the DBT conversion of the Y-Ni-P-CA catalyst reached 97%, which is an increase of 35% when compared with that found for bulk Ni-P sample.

Key words: Hydrodesulfurization, Nickel phosphide, Yttrium, Citric acid, Dibenzothiophene

CLC Number:

TrendMD:

SONG Hua,YU Qi,XU Xiaowei,SONG Hualin,JIANG Nan,LI Feng,CHEN Yanguang. Effect of Yttrium and Citric Acid on the Hydrodesulfurization Performance of Unsupported Nickel Phosphide^†[J]. Chem. J. Chinese Universities, 2016, 37(8): 1528.

Figures/Tables 7

Fig.1 XRD patterns of the Ni-P(a), Y-Ni-P(b), Ni-P-CA(c) and Y-Ni-P-CA(d) catalysts

Table 1 Structural data of the Ni-P, Y-Ni-P, Ni-P-CA and Y-Ni-P-CA catalysts

Catalyst	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	D/nm	CO uptake/(μmol·g^-1)	10³ TOF/s^-1
Ni-P	6.1	0.025	16.2	171	8.5
Y-Ni-P	12.9	0.070	21.8	287	7.4
Ni-P-CA	56.5	0.192	13.3	328	6.8
Y-Ni-P-CA	42.5	0.164	15.2	343	6.5

Table 2 Spectral parameters obtained by XPS analysis

Sample	E_b/eV						Superficial molar ratio
Sample	Ni^δ⁺	Ni²⁺	Satellite	P^δ^-	P⁵⁺	P(complexing)	$N i δ + / ∑ Ni$	P/Ni
Ni-P	852.7	856.7	861.2	128.8	134.8		0.041	3.0
Y-Ni-P	852.5	856.1	860.8	129.0	134.5		0.048	2.7
Ni-P-CA	851.9	855.0	859.8	129.2	133.4	136.8	0.343	2.4
Y-Ni-P-CA	852.6	855.9	861.0	130.4	134.9	136.2	0.320	2.3

Table 2 Spectral parameters obtained by XPS analysis

Sample	E_b/eV						Superficial molar ratio
Sample	Ni^δ⁺	Ni²⁺	Satellite	P^δ^-	P⁵⁺	P(complexing)	$N i δ + / ∑ Ni$	P/Ni
Ni-P	852.7	856.7	861.2	128.8	134.8		0.041	3.0
Y-Ni-P	852.5	856.1	860.8	129.0	134.5		0.048	2.7
Ni-P-CA	851.9	855.0	859.8	129.2	133.4	136.8	0.343	2.4
Y-Ni-P-CA	852.6	855.9	861.0	130.4	134.9	136.2	0.320	2.3

Fig.2 XPS spectra of the Ni-P(a), Y-Ni-P(b), Ni-P-CA(c) and Y-Ni-P-CA(d) catalysts (A) Ni2p core level of spectra; (B) P2p core level of spectra.

Fig.3 TEM images of the Ni-P(A, A'), Y-Ni-P(B, B'), Ni-P-CA(C, C') and Y-Ni-P-CA(D, D') catalysts

Fig.4 HDS activity of the Ni-P, Y-Ni-P, Ni-P-CA and Y-Ni-P-CA catalyst 340 ℃; 3.0 MPa; V(H2)/V(oil)=700; WHSV=1.5 h-1.

Fig.5 HDS selectivity of the Ni-P, Y-Ni-P, Ni-P-CA and Y-Ni-P-CA catalysts Conditions: 340 ℃, 3.0 MPa, V(H2)/V(oil)=700, WHSV=1.5 h-1.

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