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Heterogeneously catalyzed lignin depolymerisation in continuous flow : assessing feedstock pretreatment and catalyst deactivation

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Abstract
Due to the large-scale production of lignin, continuous flow reactors are preferred for its further valorization through depolymerization. However, there is limited literature on their use in lignin depolymerization, especially concerning feedstock pretreatments and catalyst deactivation. Therefore, in this study, the impact of a batch solvolysis pretreatment on the mild reductive catalytic depolymerization of Soda lignin, with and without a Pd catalyst, is evaluated and catalyst deactivation is systematically assessed. The Pd catalyst substantially enhances Mw reductions, e.g., without feedstock pretreatment, it increases the Mw reduction from approximately 70 % to 90 % at low time-on-streams (T.O.S.). It also yields products with more functionalities from the untreated feedstock, i.e., at low T.O.S., the phenolic and aliphatic OH content increases from 4.21 to 4.89 mmol/g and 2.30 to 3.72 mmol/g, respectively. The differences are less pronounced with the pretreated feedstock due to condensation of the lignin structure. Furthermore, the high space–time that can be achieved at a short residence time negates the need for a pretreatment. Regarding deactivation, no significant Pd leaching or poisoning by S or Na was observed. The Pd nanoparticles grew from about 8 nm to 20 nm (pretreated feed) and 17 nm (untreated feed), which is likely due to the phase change from PdO to metallic Pd rather than deactivation through sintering. The support material changed from γ-Al2O3 to boehmite, leading to the loss of acid sites and morphological changes. While some indications for small amounts of coke deposits were observed, they could not be differentiated from interstitial water within the boehmite structure. Thus, the main cause for deactivation of the Pd catalyst was identified to be the hydrothermal instability of the alumina support.
Keywords
Lignin, Depolymerization, Bio-aromatics, Continuous flow reactor, Heterogeneous catalysis, Feedstock pretreatment, Catalyst deactivation, HYDROTHERMAL STABILITY, GAMMA-ALUMINA, POLYMERS, TRANSFORMATION, PALLADIUM, OXIDATION, MONOMERS, ETHANOL, EUGENOL, ETHER

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MLA
De Saegher, Tibo, et al. “Heterogeneously Catalyzed Lignin Depolymerisation in Continuous Flow : Assessing Feedstock Pretreatment and Catalyst Deactivation.” CHEMICAL ENGINEERING JOURNAL, vol. 503, 2025, doi:10.1016/j.cej.2024.158216.
APA
De Saegher, T., Elmroth Nordlander, J., Hallböök, F., Atanasova, B., Vermeir, P., Van Geem, K., … Lauwaert, J. (2025). Heterogeneously catalyzed lignin depolymerisation in continuous flow : assessing feedstock pretreatment and catalyst deactivation. CHEMICAL ENGINEERING JOURNAL, 503. https://doi.org/10.1016/j.cej.2024.158216
Chicago author-date
De Saegher, Tibo, Jonas Elmroth Nordlander, Filip Hallböök, Boyana Atanasova, Pieter Vermeir, Kevin Van Geem, Jeriffa De Clercq, An Verberckmoes, Christian Hulteberg, and Jeroen Lauwaert. 2025. “Heterogeneously Catalyzed Lignin Depolymerisation in Continuous Flow : Assessing Feedstock Pretreatment and Catalyst Deactivation.” CHEMICAL ENGINEERING JOURNAL 503. https://doi.org/10.1016/j.cej.2024.158216.
Chicago author-date (all authors)
De Saegher, Tibo, Jonas Elmroth Nordlander, Filip Hallböök, Boyana Atanasova, Pieter Vermeir, Kevin Van Geem, Jeriffa De Clercq, An Verberckmoes, Christian Hulteberg, and Jeroen Lauwaert. 2025. “Heterogeneously Catalyzed Lignin Depolymerisation in Continuous Flow : Assessing Feedstock Pretreatment and Catalyst Deactivation.” CHEMICAL ENGINEERING JOURNAL 503. doi:10.1016/j.cej.2024.158216.
Vancouver
1.
De Saegher T, Elmroth Nordlander J, Hallböök F, Atanasova B, Vermeir P, Van Geem K, et al. Heterogeneously catalyzed lignin depolymerisation in continuous flow : assessing feedstock pretreatment and catalyst deactivation. CHEMICAL ENGINEERING JOURNAL. 2025;503.
IEEE
[1]
T. De Saegher et al., “Heterogeneously catalyzed lignin depolymerisation in continuous flow : assessing feedstock pretreatment and catalyst deactivation,” CHEMICAL ENGINEERING JOURNAL, vol. 503, 2025.
@article{01JEV1SZ18D6BP4NR5MXTJRTA7,
  abstract     = {{Due to the large-scale production of lignin, continuous flow reactors are preferred for its further valorization through depolymerization. However, there is limited literature on their use in lignin depolymerization, especially concerning feedstock pretreatments and catalyst deactivation. Therefore, in this study, the impact of a batch solvolysis pretreatment on the mild reductive catalytic depolymerization of Soda lignin, with and without a Pd catalyst, is evaluated and catalyst deactivation is systematically assessed. The Pd catalyst substantially enhances Mw reductions, e.g., without feedstock pretreatment, it increases the Mw reduction from approximately 70 % to 90 % at low time-on-streams (T.O.S.). It also yields products with more functionalities from the untreated feedstock, i.e., at low T.O.S., the phenolic and aliphatic OH content increases from 4.21 to 4.89 mmol/g and 2.30 to 3.72 mmol/g, respectively. The differences are less pronounced with the pretreated feedstock due to condensation of the lignin structure. Furthermore, the high space–time that can be achieved at a short residence time negates the need for a pretreatment. Regarding deactivation, no significant Pd leaching or poisoning by S or Na was observed. The Pd nanoparticles grew from about 8 nm to 20 nm (pretreated feed) and 17 nm (untreated feed), which is likely due to the phase change from PdO to metallic Pd rather than deactivation through sintering. The support material changed from γ-Al2O3 to boehmite, leading to the loss of acid sites and morphological changes. While some indications for small amounts of coke deposits were observed, they could not be differentiated from interstitial water within the boehmite structure. Thus, the main cause for deactivation of the Pd catalyst was identified to be the hydrothermal instability of the alumina support.}},
  articleno    = {{158216}},
  author       = {{De Saegher, Tibo and Elmroth Nordlander, Jonas and Hallböök, Filip and Atanasova, Boyana and Vermeir, Pieter and Van Geem, Kevin and De Clercq, Jeriffa and Verberckmoes, An and Hulteberg, Christian and Lauwaert, Jeroen}},
  issn         = {{1385-8947}},
  journal      = {{CHEMICAL ENGINEERING JOURNAL}},
  keywords     = {{Lignin,Depolymerization,Bio-aromatics,Continuous flow reactor,Heterogeneous catalysis,Feedstock pretreatment,Catalyst deactivation,HYDROTHERMAL STABILITY,GAMMA-ALUMINA,POLYMERS,TRANSFORMATION,PALLADIUM,OXIDATION,MONOMERS,ETHANOL,EUGENOL,ETHER}},
  language     = {{eng}},
  pages        = {{13}},
  title        = {{Heterogeneously catalyzed lignin depolymerisation in continuous flow : assessing feedstock pretreatment and catalyst deactivation}},
  url          = {{http://doi.org/10.1016/j.cej.2024.158216}},
  volume       = {{503}},
  year         = {{2025}},
}

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