Preparation of Ni 2 P/Al-SBA-15 catalyst and its performance for benzofuran hydrodeoxygenation

Zhu, Tianhan; Song, Hua; Dai, Xueya; Song, Hualin

doi:10.1016/j.cjche.2017.03.027

Cited by 20 publications

(14 citation statements)

References 36 publications

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“…The incorporation of Al into the SBA-15 support not only increases the acid strength, but also promotes the formation of highly dispersed Ni 2 P particles on the surface. Al also contributes to suppress the enrichment of P, and consequently increases Ni dispersion [123].…”

Section: Support Types and Influence On Reactivitymentioning

confidence: 99%

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

2019

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Recently, catalysts based on transition metal phosphides (TMPs) have attracted increasing interest for their use in hydrodeoxygenation (HDO) processes destined to synthesize biofuels (green or renewable diesel) from waste vegetable oils and fats (known as hydrotreated vegetable oils (HVO)), or from bio-oils. This fossil-free diesel product is produced completely from renewable raw materials with exceptional quality. These efficient HDO catalysts present electronic properties similar to noble metals, are cost-efficient, and are more stable and resistant to the presence of water than other classical catalytic formulations used for hydrotreatment reactions based on transition metal sulfides, but they do not require the continuous supply of a sulfide source. TMPs develop a bifunctional character (metallic and acidic) and present tunable catalytic properties related to the metal type, phosphorous-metal ratio, support nature, texture properties, and so on. Here, the recent progress in TMP-based catalysts for HDO of waste oils is reviewed. First, the use of TMPs in catalysis is addressed; then, the general aspects of green diesel (from bio-oils or from waste vegetable oils and fats) production by HDO of nonedible oil compounds are presented; and, finally, we attempt to describe the main advances in the development of catalysts based on TMPs for HDO, with an emphasis on the influence of the nature of active phases and effects of phosphorous, promoters, and preparation methods on reactivity.

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Section: Support Types and Influence On Reactivitymentioning

confidence: 99%

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

2019

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“…It was obvious that the decomposition temperature of NH 4 H 2 PO 2 to produce PH 3 was in the range of 230−320 °C, which was lower than that of NaH 2 PO 2 (330− 340 °C) reported by Liu et al 42 When PH 3 was generated, it would react with Ni to form Ni 2 P at lower temperatures. 43 In our previous work, 40 it was found that Ni 2 P reduction from a precursor synthesized by Ni(NO 3 ) 2 •6H 2 O and (NH 4 ) 2 •HPO 4 did not occur until the temperature was higher than 600 °C, which was ascribed to the strong thermodynamic stability of the P−O bond. The remarkable decrease (at least 300 °C) in the reduction temperature of Ni 2 P/Al 2 O 3 precursors was mainly attributed to the low valence of P species in NH 4 H 2 PO 2 , which was prone to be reduced at lower temperatures.…”

Section: Introductionmentioning

confidence: 93%

“…Figure2b, except the precursor of the Cat-5 catalyst (Cat-5pre), Cat-10-pre, Cat-15-pre, and Cat-20-pre all mainly showed two H 2 consumption peaks, which were attributed to Ni 2+ reduction to Ni or the reduction of P species. It was consistent with the H 2 -TPR analysis of Ni 2 P/SBA-15 catalysts reported by Zhu et al43 In our previous work,40 it was found that Ni 2 P reduction from a precursor synthesized by Ni(NO 3 ) 2 •6H 2 O and (NH 4 ) 2 •HPO 4 did not occur until the temperature was higher than 600 °C, which was ascribed to the strong thermodynamic stability of the P−O bond. The remarkable decrease (at least 300 °C) in the reduction temperature of Ni 2 P/Al 2 O 3 precursors was mainly attributed to the low valence of P species in NH 4 H 2 PO 2 , which was prone to be reduced at lower temperatures.…”

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confidence: 95%

Naphthalene Hydrogenation Saturation over Ni₂P/Al₂O₃ Catalysts Synthesized by Thermal Decomposition of Hypophosphite

et al. 2020

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A series of Ni 2 P/Al 2 O 3 catalysts with different Ni 2 P loadings were synthesized via thermal decomposition of hypophosphite and employed for naphthalene hydrogenation saturation. Results showed that Ni 2 P loading greatly affected Ni 2 P particle size and the number of active sites of the as-synthesized catalysts, which was derived from the variable interaction between POx and Al 2 O 3 . When the hydrogenation saturation reaction was performed at 300 °C, 4 MPa, a H 2 /oil volume ratio of 600, and a liquid hourly space velocity (LHSV) of 3 h −1 , 98% naphthalene conversion and 98% selectivity to decalin were achieved over Ni 2 P/Al 2 O 3 catalysts with 10 wt % Ni 2 P. The superior naphthalene hydrogenation saturation performance was ascribed to the large specific surface area (169 m 2 •g −1 ), small Ni 2 P particle size (3.8 nm), and the high number of exposed active sites (CO sorption 30 μmol•g −1 ), which were beneficial to the adsorption and diffusion of the reactant molecules on the catalyst.

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“…The content of decarbonylated products (Ph, B, MB, MCH) was neglected because their selectivities were low, which indicates the slow rate of correlative reactions. Based on our previous study [32,33], the proposed reaction network in the HDO of BF over Ni 5 Cu 5 /γ-Al 2 O 3 catalyst is shown in Scheme 1. The 2,3-DHBF was formed initially by hydrogenation and followed by ring opening via C-O bonding cleavage, which was reported to be the key step [34].…”

Section: Hydrodeoxygenation (Hdo) Performance Of Bimetallic Ni X Cu (mentioning

confidence: 99%

Hydrodeoxygenation of Benzofuran over Bimetallic Ni-Cu/γ-Al2O3 Catalysts

Zhu

Song

et al. 2020

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Bimetallic NixCu(10−x)/γ-Al2O3 catalysts (where x is the mass fraction of Ni) with different Ni/Cu mass ratios were prepared. The catalysts were characterized by X-ray diffractometry, N2 adsorption–desorption, inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy, H2-temperature programmed reduction, and transmission electron microscopy. The effect of Ni/Cu mass ratio on benzofuran hydrodeoxygenation was investigated in a fixed-flow reactor. Cu addition improved the NiO reducibility. The strong interaction of Ni and Cu led to the formation of smaller and highly dispersed CuO and NiO species over γ-Al2O3, which favors an improvement in catalytic activity. Among the as-prepared catalysts, the Ni5Cu5/γ-Al2O3 showed the highest deoxygenated product yield (79.9%) with an acceptable benzofuran conversion of 95.2%, which increased by 18.3% and 16.9% compared with that of the monometallic Ni/γ-Al2O3 catalyst. A possible reaction network was proposed, which would provide insight into benzofuran hydrodeoxygenation over the Ni5Cu5/γ-Al2O3 catalyst.

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Preparation of Ni 2 P/Al-SBA-15 catalyst and its performance for benzofuran hydrodeoxygenation

Cited by 20 publications

References 36 publications

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

Naphthalene Hydrogenation Saturation over Ni₂P/Al₂O₃ Catalysts Synthesized by Thermal Decomposition of Hypophosphite

Hydrodeoxygenation of Benzofuran over Bimetallic Ni-Cu/γ-Al2O3 Catalysts

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Preparation of Ni 2 P/Al-SBA-15 catalyst and its performance for benzofuran hydrodeoxygenation

Cited by 20 publications

References 36 publications

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

Naphthalene Hydrogenation Saturation over Ni2P/Al2O3 Catalysts Synthesized by Thermal Decomposition of Hypophosphite

Hydrodeoxygenation of Benzofuran over Bimetallic Ni-Cu/γ-Al2O3 Catalysts

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Naphthalene Hydrogenation Saturation over Ni₂P/Al₂O₃ Catalysts Synthesized by Thermal Decomposition of Hypophosphite