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

Ramesh Kumar Chowdari, Shilpa Agarwal, Hero J. Heeres (Corresponding Author)

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Abstract

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 H 2 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 H 2 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 %).

Original languageEnglish
Pages (from-to)2044-2055
Number of pages12
JournalACS sustainable chemistry & engineering
Volume7
Issue number2
Early online date17 Dec 2018
DOIs
Publication statusPublished - 22 Jan 2019

Fingerprint

Lignin
Activated carbon
lignin
activated carbon
catalyst
Catalysts
Alkanes
Paraffins
alkane
Monomers
Kraft lignin
Physisorption
Biofuels
Aromatic compounds
Catalyst supports
Gas chromatography
biofuel
Catalyst activity
Oils
nuclear magnetic resonance

Keywords

  • UT-Hybrid-D
  • Depolymerization
  • Phosphided catalysts
  • Hydrotreatment
  • Biobased chemicals
  • Kraft lignin

Cite this

@article{43911678a55c41fe9016457be8191a87,
title = "Hydrotreatment of Kraft Lignin to Alkylphenolics and Aromatics using Ni, Mo and W Phosphides Supported on Activated Carbon",
abstract = "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 H 2 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 H 2 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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author = "Chowdari, {Ramesh Kumar} and Shilpa Agarwal and Heeres, {Hero J.}",
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Hydrotreatment of Kraft Lignin to Alkylphenolics and Aromatics using Ni, Mo and W Phosphides Supported on Activated Carbon. / Chowdari, Ramesh Kumar; Agarwal, Shilpa ; Heeres, Hero J. (Corresponding Author).

In: ACS sustainable chemistry & engineering, Vol. 7, No. 2, 22.01.2019, p. 2044-2055.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Hydrotreatment of Kraft Lignin to Alkylphenolics and Aromatics using Ni, Mo and W Phosphides Supported on Activated Carbon

AU - Chowdari, Ramesh Kumar

AU - Agarwal, Shilpa

AU - Heeres, Hero J.

N1 - ACS deal

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N2 - 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 H 2 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 H 2 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 %).

AB - 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 H 2 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 H 2 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 %).

KW - UT-Hybrid-D

KW - Depolymerization

KW - Phosphided catalysts

KW - Hydrotreatment

KW - Biobased chemicals

KW - Kraft lignin

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M3 - Article

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