Primary alcohols as killers of Ni-based catalysts in transfer hydrogenation

doi:10.1016/S1872-2067(23)64606-6

Abstract

Abstract:

The effect of different types of alcohols used as hydrogen donors on the activity of a metal Ni-based catalyst in the hydrogenation of benzofuran as a model substrate under transfer hydrogenation conditions has been studied. The hydrogenation process of benzofuran using 2-PrOH as a hydrogen donor leads sequentially to dearomatization and then to deoxygenation of the substrates. At the same time, the use of primary alcohols such as MeOH, EtOH and 1-PrOH as hydrogen donors leads to irreversible deactivation of the Ni-containing catalyst. A clear mechanism of deactivation of Ni-based metal catalysts by primary alcohols has been established. The interaction of the catalyst with primary alcohols at a temperature of 250 °C leads to the formation of an inactive Ni₃C carbide phase, as well as sintering and segregation of metal particles on the surface of the alumina support.

Key words: Benzofuran, Transfer hydrogenation, Supercritical coprecipitation, Ni-catalysts, Alcohols

Nikolay Nesterov, Alexey Philippov, Vera Pakharukova, Evgeny Gerasimov, Stanislav Yakushkin, Oleg Martyanov. Primary alcohols as killers of Ni-based catalysts in transfer hydrogenation[J]. Chinese Journal of Catalysis, 2024, 58: 168-179.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64606-6

https://www.cjcatal.com/EN/Y2024/V58/I3/168

Figures/Tables 16

Table 1 Reaction conditions for the transfer hydrogenation of benzofuran.

Sample	Alcohol	Temperature, °C	Pressure, bar
Ni_Alum_2-Pr_250	2-PrOH	250	78‒81
Ni_Alum_2-Pr_300		300	117‒128
Ni_Alum_2-Pr_150		150	9‒11
Ni_Alum_2-Pr_82		82	1
—		250	54‒55
Ni_Alum_1-Pr_250	1-PrOH	250	42‒46
Ni_Alum_Et_250	EtOH	250	80‒82
Ni_Alum_Et_200		200	31‒33
Ni_Alum_Et_150		150	11‒12
Ni_Alum_Me_250	MeOH	250	94‒97
Ni_Alum_2-Pr-Et_250	2-PrOH + EtOH	250	72‒80

Fig. 1. Experimental XRD patterns for reduced Ni_Alum catalyst.

Fig. 2. HRTEM images of reduced Ni_Alum catalyst. (a,b) sample morphology; (c) HAADF-STEM image; (d) corresponding EDX mapping.

Fig. 3. Scheme of the transformations of benzofuran and intermediates over Ni_Alum catalyst (ki are the quasi-first order rate constants). BFN: 2,3-benzofuran; DBFN: 2,3-dihydrobenzofuran; OBFN: octahydrobenzofuran; 2-EPEL: 2-ethylphenol; 2-MPEL: 2-methylphenol; 2-ECHL: 2-ethylcyclohexanol; 2-ECHON: 2-ethylcyclohexanone; 2-MCHL: 2-methylcyclohexanol; 2-MCHON: 2-methylcyclohexanone; ECHN: ethylcyclohexane; MCHN: methylcyclohexane.

Fig. 4. Percentage composition of the reaction mixtures as functions of time. (a) m(Ni_Alum) = 0.42 g, 82 °C, 2-PrOH; (b) m(Ni_Alum) = 0.42 g, 150 °C, 2-PrOH; (c) m(Ni_Alum) = 0.12 g, 250 °C, 2-PrOH; (d) m(Ni_Alum) = 0.12 g, 275 °C, 2-PrOH; (e) m(Ni_Alum) = 0.12 g, 250 °C, 2-PrOH + EtOH. The points are experimental data and the lines are data calculated from the quasi-first order kinetic model.

Fig. 5. Experimental XRD patterns for Ni_Alum catalyst after transfer hydrogenation in 2-PrOH at different temperatures. (a) 82 °C; (b) 150 °C; (c) 250 °C; (d) 300 °C.

Table 2 XRD data of phase composition and structural features of crystalline phases in the catalyst before and after transfer hydrogenation in 2-PrOH at different temperatures. 2-Pr is 2-propanol, the number is the process temperature.

Sample	Phase	Lattice parameter, Å	D_XRD, nm
Ni_Alum_fresh	Ni⁰	a = 3.526(1)	5.0(5)
Ni_Alum_fresh	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_2-Pr_82	Ni⁰	a = 3.527(1)	5.5(5)
Ni_Alum_2-Pr_82	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_2-Pr_150	Ni⁰	a = 3.525(1)	5.5(5)
Ni_Alum_2-Pr_150	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_2-Pr_250	Ni⁰	a = 3.527(1)	6.0(5)
Ni_Alum_2-Pr_250	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_2-Pr_300	Ni⁰	a = 3.526(1)	5.5(5)
Ni_Alum_2-Pr_300	γ-Al₂O₃	a = 7.950(3)	3.0(5)

Fig. 6. Experimental XRD patterns for Ni_Alum catalyst after transfer hydrogenation at 250 °С in different media. (a) MeOH; (b) EtOH; (c) 1-PrOH; (d) mixture 2-PrOH-EtOH.

Table 3 XRD data of phase composition and structural features of crystalline phases in the catalyst after transfer hydrogenation in different primary alcohols and 2-PrOH-EtOH mixture.

Sample	Phase	Lattice parameter, Å	D_XRD, nm
Ni_Alum_Me_250	Ni⁰	a = 3.526(1)	19.0(5)
	Ni₃C	a = b = 4.582(1), c = 12.99(1)	18.5(5)
	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_Et_250	Ni⁰	a = 3.527(2)	12.0(5)
	Ni_1-_xC_x	a = 3.628(3)	4.0(5)
	Ni₃C	a = b = 4.582(2), c = 12.99(2)	29.5(5)
	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_1-Pr_250	Ni⁰	a = 3.524(2)	16.5(5)
	Ni_1-_xC_x	a = 3.626(3)	5.0(5)
	Ni₃C	-	-
	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_2-Pr-Et_250	Ni⁰	a = 3.528(3)	7.0(5)
	Ni_1-_xC_x	a = 3.610(3)	3.5(5)
	γ-Al₂O₃	a = 7.950(3)	3.0(5)

Fig. 7. HRTEM images of Ni_Alum_Me_250 catalyst. (a) sample morphology; (b) crystal structure of Ni3C and Ni0 crystallites; (c) HAADF-STEM image of catalyst; (d) corresponding EDX mapping.

Fig. 8. HRTEM images of Ni_Alum_1-Pr_250 catalyst: (a) sample morphology; (b) crystal structure of Ni3C and Ni1?xCx crystallites; (c) EDX mapping image of the catalyst; (d) particles of different carbides on the Al2O3 surface.

Fig. 9. An assumed scheme of Ni3C phase formation under transfer hydrogenation conditions in primary alcohols.

Fig. 10. Experimental XRD patterns for Ni_Alum catalyst after transfer hydrogenation in EtOH at different temperatures. (a) 150 °C; (b) 200 °C; (c) 250 °C.

Table 4 XRD data of phase composition and structural features of crystalline phases in the catalyst after transfer hydrogenation in EtOH at different temperatures.

Sample	Phase	Lattice parameter, Å	D_XRD, nm
Ni_Alum_Et_150	Ni⁰	a = 3.526(1)	6.0(5)
Ni_Alum_Et_150	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_Et_200	Ni⁰	a = 3.527(3)	7.5(5)
	Ni_1-_xC_x	a = 3.622(3)	5.0(5)
	γ-Al₂O₃	a = 7.950(3)	3.0(5)
Ni_Alum_Et_250	Ni⁰	a = 3.527(2)	12.0(5)
	Ni_1-_xC_x	a = 3.628(3)	4.0(5)
	Ni₃C	a = b = 4.582(3), c = 12.99(3)	29.5(5)
	γ-Al₂O₃	a = 7.950(3)	3.0(5)

Fig. 11. In situ FMR study of the Ni_Alum catalyst evolution in the presence of EtOH. (a) At 250 °C (the pressure during the experiment was in the range of 85?90 atmospheres): (i) 0 min, (ii) 20 min, (iii) 35 min, (iv) 60 min, (v) 90 min, (vi) 110 min and the result of the spectra simulation using the Lorentzian line shape. (b) The integral intensity of the spectrum components as a function on time. (c) The width of the spectra components as a function on time.

Fig. 12. Experimental XRD patterns for Ni_Alum catalyst after in situ FMR study.

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