Catalytic hydrodeoxygenation of anisole over nickel supported on plasma treated alumina–silica mixed oxides

Taghvaei, Hamed; Rahimpour, Mohammad Reza; Bruggeman, Peter

doi:10.1039/c7ra02594g

Cited by 30 publications

(8 citation statements)

References 44 publications

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“…The TOF for 0.16 wt % Pt/Al‐SBA‐15 was 67740 h −1 per Pt site or 621 h −1 per H + , which compares favorably with 10 700 h −1 for Pd/USY (200 °C and 52 bar H 2 ), approximately 10 000 h −1 for 0.5 wt % Pt/HY(2.6) (250 °C and 40 bar H 2 ) and 424 h −1 for Ni 2 P/SiO 2 (300 °C and 15 bar H 2 ) . Such promotion may either reflect a new (facile) reaction pathway for anisole, such as transalkylation, demethylation or hydrolysis, or the suppression of the poisoning of Pt active sites by reaction intermediates formed over Pt/SBA‐15. As the same products are observed for Pt/Al‐SBA‐15 and Pt/SBA‐15 (methoxycyclohexane, cyclohexane and benzene), we can infer that the former scenario is improbable, whereas experimental and theoretical studies on model Pt catalysts suggest that anisole is indeed prone to decomposition to strongly chemisorbed species (consistent with the latter scenario) .…”

Section: Resultsmentioning

confidence: 90%

Metal–Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al‐SBA‐15

et al. 2020

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Hydrodeoxygenation (HDO) is a promising technology to upgrade fast pyrolysis bio‐oils but it requires active and selective catalysts. Here we explore the synergy between the metal and acid sites in the HDO of anisole, a model pyrolysis bio‐oil compound, over mono‐ and bi‐functional Pt/(Al)‐SBA‐15 catalysts. Ring hydrogenation of anisole to methoxycyclohexane occurs over metal sites and is structure sensitive; it is favored over small (4 nm) Pt nanoparticles, which confer a turnover frequency (TOF) of approximately 2000 h−1 and a methoxycyclohexane selectivity of approximately 90 % at 200 °C and 20 bar H2; in contrast, the formation of benzene and the desired cyclohexane product appears to be structure insensitive. The introduction of acidity to the SBA‐15 support promotes the demethyoxylation of the methoxycyclohexane intermediate, which increases the selectivity to cyclohexane from 15 to 92 % and the cyclohexane productivity by two orders of magnitude (from 15 to 6500 mmol gPt−1 h−1). Optimization of the metal–acid synergy confers an 865‐fold increase in the cyclohexane production per gram of Pt and a 28‐fold reduction in precious metal loading. These findings demonstrate that tuning the metal–acid synergy provides a strategy to direct complex catalytic reaction networks and minimize precious metal use in the production of bio‐fuels.

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Section: Resultsmentioning

confidence: 90%

Metal–Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al‐SBA‐15

et al. 2020

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“…This bifunctionality in the catalytic system is often achieved upon combining a transition-metal hydrogenating catalyst with an acidic support. For example, Rh/Al 2 O 3 , Ni/NaY, Ni/Al 2 O 3 –SiO 2 , Pd/ZrO 2 , and Pd/Fe 2 O 3 are used to perform HDO reactions of biomass-derived platform chemicals, such as glycerol, sorbitol, phenolics, etc. In an alternate strategy, to synthesize an effective HDO catalyst, instead of using an acidic support, an oxophilic metal is alloyed with the hydrogenating metal.…”

Section: Introductionmentioning

confidence: 99%

Synergistic Effect of Zn in a Bimetallic PdZn Catalyst: Elucidating the Role of Undercoordinated Sites in the Hydrodeoxygenation Reactions of Biorenewable Platforms

Gupta

Khan

Saha

et al. 2019

Ind. Eng. Chem. Res.

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The promotional role of Zn in hydrodeoxygenation (HDO) reactions of 5-hydroxymethyl furfural (HMF) to produce 2,5-dimethyl furan (DMF) over the Pd catalyst was studied using plane-wave density functional theory (DFT) calculations. HMF is first hydrogenated to form bis(hydroxymethyl) furan (BHMF), which undergoes HDO to form DMF. In order to provide a mechanistic explanation to the experimental observation, DFT calculations focusing on the energetics of the HDO reaction steps for BHMF conversion to DMF were performed on three different surfaces: Pd(111), Pd(211), and PdZn(211). Zn was assumed to preferentially substitute the defect sites of the bimetallic catalyst in reduced metallic state. Calculated values of activation energies for C–O dissociations steps were significantly reduced on the PdZn(211) surface, compared to the Pd(111) and Pd(211) surfaces. Therefore, theoretical results provided a clue to the reactivity of the Zn-decorated step sites for the HDO reaction.

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“…The utilized reaction system for the catalytic HDO experiments was Microactivity-reference, PID Eng & Tech. The apparatus and the experimental procedure is well introduced in the previously published works [39,41,51,52,[61][62][63][64][65]. In summary, the apparatus involves an upstream pre-evaporator, mixing chamber, a one-way stainless-steel tube (30.5 cm length and 0.9 cm diameter) employed as the fixed catalyst bed, an electric heating jacket, a downstream catalyst fines filter (10 μm), a pressure transducer, and control valve.…”

Section: Catalytic Hdo Of Cyclohexanonementioning

confidence: 99%

Converting Cyclohexanone to Liquid Fuel-Grade Products: A Characterization and Comparison Study of Hydrotreating Molybdenum Catalysts

et al. 2021

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Developing biomass-based strategies for liquid bio-fuels production is promising for the reduction of the aftereffects of fossil fuels. The conversion of lignin-derived intermediates such as cyclohexanone is currently of a great deal of interest. The current study aims to evaluate the molybdenum-based hydrotreating catalysts for the conversion of cyclohexanone in the presence of hydrogen. Catalytic experiments at 400 °C, 15 bar, and a range of WHSV were developed. The experiments reveal that catalyst type and reaction WHSV affect the cyclohexanone conversion, product distribution, deoxygenation efficiency, total hydrocarbon production capacity, and heating value of the product blend. The main products include C 6 cyclic and aromatic hydrocarbons and oxygenates. Cyclohexane, cyclohexene, benzene, cyclohexanol, and phenol are major products. Small quantities of methylcyclopentane and bicyclic hydrocarbons and oxygenates are also reported in some cases. Increasing WHSV reduced the cyclohexanone conversion. Cyclohexanone conversions up to 89% were observed at the lowest WHSVs over a cobalt-molybdenum sample. The highest hydrocarbon production capacity (99.53%) was managed at WHSV = 5.240 g cyclohexanone /g cat h over a cobalt-molybdenum sample, while the highest deoxygenation efficiency, i.e. 81.29% degree of deoxygenation and 5.35 C/O ratio enhancement were achieved at WHSV = 0.262 g cyclohexanone /g cat h by a nickel-molybdenum sample. The heating values would be enhanced by up to 22.7% when cyclohexanone is converted over the utilized catalysts. The larger heating value (44.90 MJ/kg, 22.7% enhancement) was obtained over a nickel-molybdenum catalyst, which is comparable to the energy density of the conventional fuels. The results reveal that the catalysts are efficient in the conversion of cyclohexanone to liquid bio-fuels.

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Catalytic hydrodeoxygenation of anisole over nickel supported on plasma treated alumina–silica mixed oxides

Abstract: Hydrodeoxygenation (HDO) of anisole, a representative of lignin-derived bio oil, was investigated on plasma treated SiO2–Al2O3 supported Ni nanocatalyst at low hydrogen pressure.

Cited by 30 publications

References 44 publications

Metal–Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al‐SBA‐15

Metal–Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al‐SBA‐15

Synergistic Effect of Zn in a Bimetallic PdZn Catalyst: Elucidating the Role of Undercoordinated Sites in the Hydrodeoxygenation Reactions of Biorenewable Platforms

Converting Cyclohexanone to Liquid Fuel-Grade Products: A Characterization and Comparison Study of Hydrotreating Molybdenum Catalysts

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