Molybdenum Modified Nickel Phyllosilicates Catalyst for Maleic Anhydride Hydrogenation†

doi:10.7503/cjcu20190022

Abstract

Abstract:

A series of molybdenum-modified nickel phyllosilicates was synthesized by ammonia evaporation method. The effects of molybdenum content on the structure and catalytic performance of the catalyst for the liquid phase hydrogenation of maleic anhydride(MA) were investigated. The structure and morphology of the catalysts were characterized by N₂ adsorption-desorption, XRD, FTIR, TEM, H₂-TPR, NH₃-TPD, Py-IR and in situ XPS. The results displayed that the introduction of molybdenum has a remarkable influence on the morphology of the catalysts and its catalytic properties. The reduction degree of the active metal Ni and the sites of Ni⁰ on the surface of the catalysts were increased with the addition of Mo. Meanwhile, the hydrogen spillover was generated during the Ni reduction process. Such overflowing active hydrogen have super reduction ability, which can promote partial of MoO₃ to be reduced to MoO_x species that possesses Lewis acid properties. Due to the synergistic effect between the surface Ni⁰ and the Lewis acid sites induced from partially reduced Ni(Ni^σ⁺) and MoO_x, the catalytic performance of the catalyst was significantly improved for the hydrogenation of C≡C and C≡O groups in MA. The sample with the Mo doping content of 3% exhibits the highest activity. A 100% conversion of MA together with a γ-butyrolactone(GBL) selectivity of 27% was achieved within 3 h at 160 °C and the H₂ pressure of 5 MPa.

Key words: Molybdenum modified, Nickel phyllosilicate, Lewis acid, Maleic anhydride, Hydrogenation

CLC Number:

O643.38

TrendMD:

XIA Xiaoli,TAN Jingjing,WEI Caiyun,ZHAO Yongxiang. Molybdenum Modified Nickel Phyllosilicates Catalyst for Maleic Anhydride Hydrogenation^†[J]. Chem. J. Chinese Universities, 2019, 40(6): 1207.

Figures/Tables 12

Scheme 1 Process for maleic anhydride hydrogenation

Table 1 Textural properties of the catalysts

Catalyst	Mass fraction^a(%)		$S BET b$ /(m²·g^-1)	$V p b$ /(cm³·g^-1)	$D p b$ /nm	$d Ni c$ /nm	$n Ni d$ /(mmol·g^-1)	c^e/(μmol·g^-1)
Catalyst	Mo	Ni	$S BET b$ /(m²·g^-1)	$V p b$ /(cm³·g^-1)	$D p b$ /nm	$d Ni c$ /nm	$n Ni d$ /(mmol·g^-1)	c^e/(μmol·g^-1)
0MoNi-PS	0	31.50	347.09	0.61	7.66	3.8	0.80	1348.84
0.5MoNi-PS	0.29	31.21	302.18	0.65	5.79	3.9	0.83	1304.68
1MoNi-PS	1.21	29.97	270.20	0.51	5.39	4.0	0.88	1276.51
3MoNi-PS	2.97	29.05	213.98	0.32	5.0	4.5	0.96	1240.47
5MoNi-PS	5.18	26.25	182.02	0.26	4.74	4.7	0.57	836.38
7MoNi-PS	7.82	23.70	123.86	0.17	6.66	5.1	0.54	777.80

Table 1 Textural properties of the catalysts

Catalyst	Mass fraction^a(%)		$S BET b$ /(m²·g^-1)	$V p b$ /(cm³·g^-1)	$D p b$ /nm	$d Ni c$ /nm	$n Ni d$ /(mmol·g^-1)	c^e/(μmol·g^-1)
Catalyst	Mo	Ni	$S BET b$ /(m²·g^-1)	$V p b$ /(cm³·g^-1)	$D p b$ /nm	$d Ni c$ /nm	$n Ni d$ /(mmol·g^-1)	c^e/(μmol·g^-1)
0MoNi-PS	0	31.50	347.09	0.61	7.66	3.8	0.80	1348.84
0.5MoNi-PS	0.29	31.21	302.18	0.65	5.79	3.9	0.83	1304.68
1MoNi-PS	1.21	29.97	270.20	0.51	5.39	4.0	0.88	1276.51
3MoNi-PS	2.97	29.05	213.98	0.32	5.0	4.5	0.96	1240.47
5MoNi-PS	5.18	26.25	182.02	0.26	4.74	4.7	0.57	836.38
7MoNi-PS	7.82	23.70	123.86	0.17	6.66	5.1	0.54	777.80

Fig.1 XRD patterns of calcined(A) and reduced catalysts(B)

Fig.2 H2-TPR profiles of catalysts a. 0MoNi-PS; b. 0.5MoNi-PS; c. 1MoNi-PS; d. 3MoNi-PS; e. 5MoNi-PS; f. 7MoNi-PS.

Fig.3 TEM images(A—F) and corresponding size distributions(A'—F') of catalysts (A, A') 0MoNi-PS; (B, B') 0.5MoNi-PS; (C, C') 1MoNi-PS; (D, D') 3MoNi-PS; (E, E') 5MoNi-PS; (F, F') 7MoNi-PS.

Fig.4 NH3-TPD profiles of reduced catalysts a. 0MoNi-PS; b. 0.5MoNi-PS; c. 1MoNi-PS; d. 3MoNi-PS; e. 5MoNi-PS; f. 7MoNi-PS.

Table 2 Distribution of different acid strength and the total acid content for different catalysts

Catalyst	Acid content(%)			Total acid/(mmol NH₃·g^-1)
Catalyst	Weak acid, α	Medium strong acid, (β+γ)	Strong acid, η	Total acid/(mmol NH₃·g^-1)
0MoNi-PS	5.13	81.30	13.57	1.71
0.5MoNi-PS	5.55	78.35	16.10	1.69
1MoNi-PS	4.02	78.95	17.03	1.68
3MoNi-PS	14.44	66.03	19.53	1.66
5MoNi-PS	9.04	74.72	16.24	1.29
7MoNi-PS	25.51	49.62	24.87	0.69

Fig.5 Py-IR spectra of reduced catalysts a. 0MoNi-PS; b. 0.5MoNi-PS; c. 1MoNi-PS; d. 3MoNi-PS; e. 5MoNi-PS; f. 7MoNi-PS.

Fig.6 In situ XPS spectra of the catalysts (A) N i 2 p ; (B) M o 3 d . a. 0MoNi-PS; b. 0.5MoNi-PS; c. 1MoNi-PS; d. 3MoNi-PS; e. 5MoNi-PS; f. 7MoNi-PS.

Fig.7 Effect of Mo doping content on the yield of GBL and the Ni0(A) and Lewis acid sites(B) on the surface of the catalysts Reaction conditions: MA: 4.9 g; catalyst: 0.3 g; hydrogen pressure: 5 MPa; 40 mL THF as solvent; t=160 ℃; reaction time: 3 h. MA: maleic anhydride, GBL:γ-butyrolactone, THF: tetrahydrofuran.

Fig.8 Reaction mechanism for the maleic anhydride hydrogenation

Fig.9 Stability of 3MoNi-PS catalyst Reaction conditions: MA: 4.9 g; catalyst: 0.3 g; hydrogen pressure: 5 MPa; 40 mL THF as solvent; temperature: 160 ℃; reaction time: 3 h.

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