Kinetics of the hydrodeoxygenation of cresol isomers over Ni2P/SiO2: Proposals of nature of deoxygenation active sites based on an experimental study

Gonçalves, Vinicius Ottonio O.; Souza, Priscilla M. de; Silva, Victor Teixeira da; Noronha, Fábio B.; Richard, Frédéric

doi:10.1016/j.apcatb.2016.12.051

Cited by 69 publications

(33 citation statements)

References 74 publications

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“…Considering the provided model results, it can be noted that the catalyst's ability to hydrogenate a benzene ring increases with annealing temperature from 0 to 600 • C by two orders of magnitude between Ru/C-Fe 2 O 3 and Ru/C-Fe 2 O 3 -300, 2.5-fold between being annealed at 300 and 500 • C, and 1.3-fold between being annealed at 500 and 600 • C, decreasing thereafter, as the catalyst annealed at 750 • C exhibited lower hydrogenation activity compared to other active catalysts, i.e. being between nonactive and annealed at 300 • C. Similarly, the increase of annealing temperature up to 600 • C facilitated deoxygenation of unsaturated and saturated intermediates (Ar-aromatics, Al-alkyl): Generally, deoxygenation of saturated compounds was more favoured compared to the unsaturated shown also by Goncalves and coworkers [36]. Further, hydrogenation is more favoured than deoxygenation over all tested catalysts being in an agreement with other kinetic studies [37,38].…”

Section: Modelling Resultsmentioning

confidence: 69%

Catalytic Hydrogenation, Hydrodeoxygenation, and Hydrocracking Processes of a Lignin Monomer Model Compound Eugenol over Magnetic Ru/C–Fe2O3 and Mechanistic Reaction Microkinetics

et al. 2018

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Conversion of waste lignocellulosic (LC) biomass, a widely-available low-cost feedstock, into value-added biobased chemicals (and biofuels) has been gaining much attention recently. Therefore, the present lignin valorisation study was aimed at developing magnetically-separable highly-active catalysts for hydrodeoxygenation (HDO), also proposing surface chemical kinetics. Five carbonaceous substrate-deposited Ru were synthesised and tested for the HDO of monomer moiety eugenol. Their annealing temperatures differed, specifically between 300 and 750 °C, while one was not subjected to calcination. Experiments revealed the substantial influence of annealing temperature on the product distribution. Namely, fresh nonannealed nanocomposites were not active for hydrogenolysis. By further pretreatment increase, hydrogenation and, exclusively, the deoxygenation of saturated cyclic species, were enhanced, these being more promoted considering rates and yields than commercial carbon-supported ruthenium. Over 80 mol% of 4-propyl-cylohexanol and propyl-cyclohexane could be formed over the samples, treated at 500 and 600 °C, for 100 and 125 min, respectively, under 275 °C and 5 MPa of reactor hydrogen pressure. Interestingly, a notable 4-propyl-phenol amount was produced upon 750 °C pretreating. The intrinsic microkinetic model, developed previously, was applied to determine relevant turnover parameters. Calculated modelling results indicated a 47- and 10-fold greater demethoxylation and dehydroxylation mechanism ability upon the reheatingpreheating at 600 °C in comparison to industrial (heterogeneous) Ru/C.

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Section: Modelling Resultsmentioning

confidence: 69%

Catalytic Hydrogenation, Hydrodeoxygenation, and Hydrocracking Processes of a Lignin Monomer Model Compound Eugenol over Magnetic Ru/C–Fe2O3 and Mechanistic Reaction Microkinetics

et al. 2018

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“…Transition metal phosphide such as Ni 2 P had also been applied in the HDO of lignin-derived feedstock recently [54][55][56][57]. The superiority of these transition metal Ni phosphide catalysts were high activity and low cost compared to noble metal catalysts.…”

Section: Monometallic Ni-based Catalysts For Hdo Of Ligninmentioning

confidence: 99%

“…Richard and co-workers studied the HDO of cresol isomers (i.e., m-cresol, p-cresol, o-cresol) over Ni 2 P/SiO 2 and found that the reactivity of cresols followed the order: m-cresol > p-cresol > o-cresol. This could be explained by the fact that the HDO route was more influenced by the position of the methyl group than HYD route [56]. Besides, the author proposed that Brønsted acidic sites (probably PO-H groups) as well as Lewis acidic sites (Ni δ+ species) were involved in dehydration and isomerization reactions, respectively [56].…”

Section: Monometallic Ni-based Catalysts For Hdo Of Ligninmentioning

confidence: 99%

“…This could be explained by the fact that the HDO route was more influenced by the position of the methyl group than HYD route [56]. Besides, the author proposed that Brønsted acidic sites (probably PO-H groups) as well as Lewis acidic sites (Ni δ+ species) were involved in dehydration and isomerization reactions, respectively [56]. Ni/ZnO-Al2O3-5 form ref [42].…”

Section: Monometallic Ni-based Catalysts For Hdo Of Ligninmentioning

confidence: 99%

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Lignin Valorizations with Ni Catalysts for Renewable Chemicals and Fuels Productions

Chen

Guan

Tsang³

et al. 2019

Catalysts

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Energy and fuels derived from biomass pose lesser impact on the environmental carbon footprint than those derived from fossil fuels. In order for the biomass-to-energy and biomass-to-chemicals processes to play their important role in the loop of the circular economy, highly active, selective, and stable catalysts and the related efficient chemical processes are urgently needed. Lignin is the most thermal stable fraction of biomass and a particularly important resource for the production of chemicals and fuels. This mini review mainly focuses on lignin valorizations for renewable chemicals and fuels production and summarizes the recent interest in the lignin valorization over Ni and relevant bimetallic metal catalysts on various supports. Particular attention will be paid to those strategies to convert lignin to chemicals and fuels components, such as pyrolysis, hydrodeoxygenation, and hydrogenolysis. The review is written in a simple and elaborated way in order to draw chemists and engineers' attention to Ni-based catalysts in lignin valorizations and guide them in designing innovative catalytic materials based on the lignin conversion reaction.Catalysts 2019, 9, 488 2 of 39 processes to play their important role in the loop of the circular economy, first, the process must be energy efficient itself [2]. Second, according to Anastas's second principle [3], atom economy should be maximized and excess starting materials which will not be contained in the final product should be avoided. Thus, developing highly active and selective catalysts and enzymes is an urgent need. Current technology for lignocellulosic valorization includes biochemical fermentation, chemical and thermochemical methods using enzymes and metal catalysts, respectively. Thermochemical methods, including combustion, pyrolysis, and gasification, and chemical methods, such as hydrodeoxygenation (HDO), hydrogenolysis, and oxidative cleavage, have the advantages of higher throughputs due to the short reaction time, and thus are more suitable for commercialized and industrialized scale-up.Woody and herbaceous biomasses are large polymeric networks consisting of ca. 35-50% cellulose, 25-30% hemicellulose (glucomannan and glucuronoxylan), and 15-30% of lignin (macromolecular polymer networks with interconnected phenylpropane and phenol units with various formula, e.g., (C 31 H 34 O 11 ) n ) by weight. Lignin is one of the most thermal stable fractions and a particularly important resource for the production of chemicals and fuels. With careful design of the metal catalysts, either aromatic platform molecules, or fuels components such as naphthenes, can be preferentially produced in high yields and with high selectivity.Over the past decade, numerous monometallic and bimetallic metal catalysts using both precious and base metal precursors on various supports have been reported to successfully convert lignin into valuable products. Transition metals such as Ni (price = US$ 12.628/kg as of April 2019) are much more economically viable than precious metals...

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“…Its crystal structure belongs to the P 62m space group with a = b = 5.859 Å and c = 3.382 Å [27]. The Ni 2 P is widely used for hydrodesulfurization [28] and hydrodenitrogenation [28][29][30] for fossil fuels, hydrodeoxygenation [31][32][33][34] for biomass conversion, and as a cathode catalyst in hydrogen evolution reactions [35,36]. The Ni 2 P can be regarded as a substitutional material for noble metals, such as Pt and Pd.…”

Section: Introductionmentioning

confidence: 99%

A new interpretation of the √7×√7 R19.1° structure for P adsorbed on a Ni(111) surface

Barrow

Seuser

Ariga-Miwa

et al. 2019

Science and Technology of Advanced Materials

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Kinetics of the hydrodeoxygenation of cresol isomers over Ni2P/SiO2: Proposals of nature of deoxygenation active sites based on an experimental study

Cited by 69 publications

References 74 publications

Catalytic Hydrogenation, Hydrodeoxygenation, and Hydrocracking Processes of a Lignin Monomer Model Compound Eugenol over Magnetic Ru/C–Fe2O3 and Mechanistic Reaction Microkinetics

Catalytic Hydrogenation, Hydrodeoxygenation, and Hydrocracking Processes of a Lignin Monomer Model Compound Eugenol over Magnetic Ru/C–Fe2O3 and Mechanistic Reaction Microkinetics

Lignin Valorizations with Ni Catalysts for Renewable Chemicals and Fuels Productions

A new interpretation of the √7×√7 R19.1° structure for P adsorbed on a Ni(111) surface

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