Hydrodeoxygenation of Lignin-Derived Phenols: From Fundamental Studies towards Industrial Applications

Mäki‐Arvela, Päivi; Murzin, Dmitry Yu.

doi:10.3390/catal7090265

Cited by 98 publications

(62 citation statements)

References 84 publications

(363 reference statements)

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“…Initially absent of toluene, the 2-step upgraded oil was composed of 0.017 g of toluene. It was previously reported that it is among the plausible products of guaiacol conversion [62,63], in agreement with the lower guaiacol concentration in the upgraded products in comparison to the feed. The concentration of benzene also increased in the UOP 2 nd ,Ni-Cr,325 • C from 0.006 g to 0.0181 g. Another six compounds belonging to the benzene group were observed in the 2-step upgraded oil with 1-methyl-naphtalene, the heterocyclic aromatic compound with the highest concentration (0.038 g), as evidence of aromatic condensation taking place.…”

Section: Characterization Of Upgraded Liquid Products and Feedstocks supporting

confidence: 82%

Evaluation of High-Loaded Ni-Based Catalysts for Upgrading Fast Pyrolysis Bio-Oil

et al. 2019

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The catalytic activity of high-loaded Ni-based catalysts for beech wood fast-pyrolysis bio-oil hydrotreatment is compared to Ru/C. The influence of promoter, temperature, reaction time, and consecutive upgrading is investigated. The catalytic activity is addressed in terms of elemental composition, pH value, H2 consumption, and water content, while the selectivity is based on the GC-MS/FID results. The catalysts showed similar deoxygenation activity, while the highest hydrogenation activity and the highest upgraded oil yields were obtained with Ni-based catalysts. The elemental composition of upgraded oils was comparable for 2 and 4 h of reaction, and the temperature showed a positive effect for reactions with Ni–Cr and Ru/C. Ni–Cr showed superior activity for the conversion of organic acids, sugars and ketones, being selected for the 2-step upgrading reaction. The highest activity correlates to the strength of the acid sites promoted by Cr2O3. Consecutive upgrading reduced the content of oxygen by 64.8% and the water content by 90%, whereas the higher heating value increased by 90.1%. While more than 96% of the organic acid content was converted, the discrepancy of aromatic compounds quantified by 1H-NMR and GC-MS/FID may indicate polymerization of aromatics taking place during the second upgrading step.

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Section: Characterization Of Upgraded Liquid Products and Feedstocks supporting

confidence: 82%

Evaluation of High-Loaded Ni-Based Catalysts for Upgrading Fast Pyrolysis Bio-Oil

et al. 2019

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“…The latter is undesirable as alkanes are less valuable than aromatics and typically only have fuel value. In addition, methoxy removal by hydrogenolysis reactions may also occur, as shown by model component studies, 58,59 leading to the formation of methanol. The latter is likely not inert under the prevailing reaction conditions and may be converted to gas-phase components.…”

Section: Results and Discussionmentioning

confidence: 98%

Hydrotreatment of Kraft Lignin to Alkylphenolics and Aromatics Using Ni, Mo, and W Phosphides Supported on Activated Carbon

Chowdari

Agarwal

Heeres

2018

ACS Sustainable Chem. Eng.

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The conversion of lignin to biofuels and biobased chemicals is currently attracting a lot of attention. We here report on the valorization of Kraft lignin by a catalytic hydrotreatment using Ni, Mo, and W phosphide catalysts supported on activated carbon in the absence of an external solvent. Experiments were carried out in a batch setup in the temperature range of 400–500 °C and 100 bar initial H2 pressure. The synthesized catalysts were characterized by X-ray diffraction, nitrogen physisorption, and transmission electron microscopy. The lignin oils were analyzed extensively by different techniques such as GPC, GC-MS-FID, 13C NMR, and elemental analysis. Two-dimensional gas chromatography (GC×GC-FID) was applied to identify and quantify distinct groups of compounds (aromatics, alkylphenolics, alkanes, etc.). Mo-based catalysts displayed higher activity compared to the W-containing catalysts. The reaction parameters such as the effect of reaction temperature, reaction time, and catalyst loading were studied for two catalysts (15MoP/AC and 20NiMoP/AC), and optimized reaction conditions regarding yields of monomeric components were identified (400 °C, 100 bar H2 at RT, 10 wt % catalyst loading on lignin intake). The highest monomer yield (45.7 wt % on lignin) was obtained for the 20NiMoP/AC (Ni 5.6 wt %, Mo 9.1 wt %, P 5.9 wt %) catalyst, which includes 25% alkylphenolics, 8.7% aromatics, and 9.9% alkanes. Our results clearly reveal that the phosphide catalysts are highly efficient catalyst to depolymerize the Kraft lignin to valuable biobased chemicals and outperform sulfided NiMo catalysts (monomer yield on lignin < 30 wt %).

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“…Hydrogenation and hydrodeoxygenation (HDO) of bio-oils is currently a significant research undertaking [1,2] and a wide range of conditions and catalysts have been investigated [3]. In this paper we will report on the liquid-phase hydrogenation and HDO of anisole, phenol and 4-methoxyphenol.…”

Section: Introductionmentioning

confidence: 99%

Low temperature hydrogenation and hydrodeoxygenation of oxygen-substituted aromatics over Rh/silica: part 1: phenol, anisole and 4-methoxyphenol

Alshehri

Feral

Kirkwood

et al. 2019

Reac Kinet Mech Cat

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The hydrogenation and competitive hydrogenation of anisole, phenol and 4-methoxyphenol was studied in the liquid phase over a Rh/silica catalyst at 323 K and 3 barg hydrogen pressure. The rate of conversion of the reactants to products gave an order of anisole ≫ phenol > 4-methoxyphenol with hydrogenation and hydrodeoxygenation products being produced. Anisole, the most reactive substrate, was rapidly converted to methoxycyclohexane, cyclohexane, cyclohexanone and cyclohexanol, while phenol was hydrogenated to cyclohexanone, cyclohexanol and cyclohexane. In both cases cyclohexanol was produced as a secondary product from cyclohexanone hydrogenation. The yield of cyclohexane, the hydrodeoxygenation (HDO) product was > 20% from both reactants and was formed as a primary product from the aromatic species. Hydrogenation of 4-methoxyphenol was selective to 4-methoxycyclohexanone with no alcohol formation, while the hydrogenolysis products revealed that the catalyst was more active for demethoxylation than dehydroxylation. A comparative strength of adsorption was determined from competitive hydrogenation and gave an order of anisole > phenol > 4-methoxyphenol. Competitive, pair hydrogenation inhibited HDO and stopped cyclohexane from being produced from phenol and 4-methoxyphenol, although it was still produced from anisole. An increased rate of hydrogenation for 4-methoxyphenol was observed for competitive reactions with phenol and anisole but not when all three reactants were present. In contrast to the pair reactions, when all three reactants were present HDO occurred with all aromatics producing cyclohexane. Replacing hydrogen with deuterium revealed an inverse kinetic isotope effect for ring hydrogenation of 4-methoxyphenol but not phenol or anisole, which both had a positive KIE.

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Hydrodeoxygenation of Lignin-Derived Phenols: From Fundamental Studies towards Industrial Applications

Cited by 98 publications

References 84 publications

Evaluation of High-Loaded Ni-Based Catalysts for Upgrading Fast Pyrolysis Bio-Oil

Evaluation of High-Loaded Ni-Based Catalysts for Upgrading Fast Pyrolysis Bio-Oil

Hydrotreatment of Kraft Lignin to Alkylphenolics and Aromatics Using Ni, Mo, and W Phosphides Supported on Activated Carbon

Low temperature hydrogenation and hydrodeoxygenation of oxygen-substituted aromatics over Rh/silica: part 1: phenol, anisole and 4-methoxyphenol

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