Hydrodeoxygenation and hydrodenitrogenation of n-hexadecanamide over Pt catalysts : effect of the support

Emma Verkama; Sylvia Albersberger; Aitor Arandia; Kristoffer Meinander; Marja Tiitta; Reetta Karinen; Riikka L. Puurunen

doi:10.1039/d3cy01480k

Hydrodeoxygenation and hydrodenitrogenation of n-hexadecanamide over Pt catalysts : effect of the support

Emma Verkama^*, Sylvia Albersberger, Aitor Arandia, Kristoffer Meinander, Marja Tiitta, Reetta Karinen, Riikka L. Puurunen

^*Corresponding author for this work

Neste Corporation

Research output: Contribution to journal › Article › Scientific › peer-review

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Abstract

Efficient catalysts for simultaneous hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) are needed for the production of renewable fuels. In this study, Pt catalysts supported on SiO₂, γ-Al₂O₃, SiO₂-Al₂O₃, ZrO₂, CeO₂-ZrO₂, Nb₂O₅, and TiO₂ were studied for the hydrotreatment of n-hexadecanamide (C16 amide) to n-paraffins at 300 °C and 80 bar H₂. The catalysts favored HDO over HDN, and the initial differences in the nitrogen removal level were smaller than the differences in the oxygen removal level. The Lewis acid properties of the support influenced the initial C16 amide conversion route and HDO activity, which was reflected in the reaction network and condensation reaction selectivity of the catalysts. Pt/Nb₂O₅ and Pt/TiO₂, with intermediate strength Lewis acid sites, initially favored the HDO of C16 amide to nitrogen-containing compounds. In contrast, the other catalysts converted C16 amide to oxygen- and nitrogen-containing compounds with similar selectivity. The HDO of the oxygen-containing compounds proceeded more efficiently on the Pt catalysts supported on oxides with weak Lewis acid sites (Pt/ZrO₂, Pt/CeO₂-ZrO₂) than on the irreducible oxides with strong or no Lewis acid sites (Pt/γ-Al₂O₃, Pt/SiO₂-Al₂O₃, Pt/SiO₂). As the presence of oxygen-containing compounds suppressed HDN activity, the catalysts with the highest HDO activity eventually gave the highest paraffin yield, regardless of which oxygen removal pathway was favored.

Original language	English
Pages (from-to)	431-448
Journal	Catalysis Science and Technology
Volume	14
Issue number	2
Early online date	15 Dec 2023
DOIs	https://doi.org/10.1039/d3cy01480k
Publication status	Published - 21 Jan 2024
MoE publication type	A1 Journal article-refereed

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CHEM_Verkama_et_al_Hydrodeoxygenation_and_hydrodenitrogenation_2024_Catalysis_Science_and_TechnologyFinal published version, 2.29 MBLicence: CC BY-NC

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@article{970c1c8a61c54198b4f795a26a207aab,

title = "Hydrodeoxygenation and hydrodenitrogenation of n-hexadecanamide over Pt catalysts : effect of the support",

abstract = "Efficient catalysts for simultaneous hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) are needed for the production of renewable fuels. In this study, Pt catalysts supported on SiO2, γ-Al2O3, SiO2-Al2O3, ZrO2, CeO2-ZrO2, Nb2O5, and TiO2 were studied for the hydrotreatment of n-hexadecanamide (C16 amide) to n-paraffins at 300 °C and 80 bar H2. The catalysts favored HDO over HDN, and the initial differences in the nitrogen removal level were smaller than the differences in the oxygen removal level. The Lewis acid properties of the support influenced the initial C16 amide conversion route and HDO activity, which was reflected in the reaction network and condensation reaction selectivity of the catalysts. Pt/Nb2O5 and Pt/TiO2, with intermediate strength Lewis acid sites, initially favored the HDO of C16 amide to nitrogen-containing compounds. In contrast, the other catalysts converted C16 amide to oxygen- and nitrogen-containing compounds with similar selectivity. The HDO of the oxygen-containing compounds proceeded more efficiently on the Pt catalysts supported on oxides with weak Lewis acid sites (Pt/ZrO2, Pt/CeO2-ZrO2) than on the irreducible oxides with strong or no Lewis acid sites (Pt/γ-Al2O3, Pt/SiO2-Al2O3, Pt/SiO2). As the presence of oxygen-containing compounds suppressed HDN activity, the catalysts with the highest HDO activity eventually gave the highest paraffin yield, regardless of which oxygen removal pathway was favored.",

author = "Emma Verkama and Sylvia Albersberger and Aitor Arandia and Kristoffer Meinander and Marja Tiitta and Reetta Karinen and Puurunen, {Riikka L.}",

note = "Funding Information: Dr. Hua Jiang is acknowledged for the STEM images, and Ellen J{\"a}rvinen is acknowledged for assistance with the batch reactor experiments. Dr. Yingnan Zhao and the Research Analytics department of Neste Corporation are acknowledged for the guidance with the acid site characterization and for access to the equipment that was used for the pyridine FTIR measurements. All members of the Neste-Aalto HDN catalyst development project group are gratefully acknowledged for fruitful discussions. This study was funded by Neste Corporation (Neste-Aalto HDN catalyst development project). The Bioeconomy and Raw materials research infrastructures at Aalto University and the OtaNano Nanomicroscopy Center were used for the study. Publisher Copyright: {\textcopyright} 2024 The Royal Society of Chemistry.",

year = "2024",

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doi = "10.1039/d3cy01480k",

language = "English",

volume = "14",

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journal = "Catalysis Science and Technology ",

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publisher = "Royal Society of Chemistry",

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T1 - Hydrodeoxygenation and hydrodenitrogenation of n-hexadecanamide over Pt catalysts : effect of the support

AU - Verkama, Emma

AU - Albersberger, Sylvia

AU - Arandia, Aitor

AU - Meinander, Kristoffer

AU - Tiitta, Marja

AU - Karinen, Reetta

AU - Puurunen, Riikka L.

N1 - Funding Information: Dr. Hua Jiang is acknowledged for the STEM images, and Ellen Järvinen is acknowledged for assistance with the batch reactor experiments. Dr. Yingnan Zhao and the Research Analytics department of Neste Corporation are acknowledged for the guidance with the acid site characterization and for access to the equipment that was used for the pyridine FTIR measurements. All members of the Neste-Aalto HDN catalyst development project group are gratefully acknowledged for fruitful discussions. This study was funded by Neste Corporation (Neste-Aalto HDN catalyst development project). The Bioeconomy and Raw materials research infrastructures at Aalto University and the OtaNano Nanomicroscopy Center were used for the study. Publisher Copyright: © 2024 The Royal Society of Chemistry.

PY - 2024/1/21

Y1 - 2024/1/21

N2 - Efficient catalysts for simultaneous hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) are needed for the production of renewable fuels. In this study, Pt catalysts supported on SiO2, γ-Al2O3, SiO2-Al2O3, ZrO2, CeO2-ZrO2, Nb2O5, and TiO2 were studied for the hydrotreatment of n-hexadecanamide (C16 amide) to n-paraffins at 300 °C and 80 bar H2. The catalysts favored HDO over HDN, and the initial differences in the nitrogen removal level were smaller than the differences in the oxygen removal level. The Lewis acid properties of the support influenced the initial C16 amide conversion route and HDO activity, which was reflected in the reaction network and condensation reaction selectivity of the catalysts. Pt/Nb2O5 and Pt/TiO2, with intermediate strength Lewis acid sites, initially favored the HDO of C16 amide to nitrogen-containing compounds. In contrast, the other catalysts converted C16 amide to oxygen- and nitrogen-containing compounds with similar selectivity. The HDO of the oxygen-containing compounds proceeded more efficiently on the Pt catalysts supported on oxides with weak Lewis acid sites (Pt/ZrO2, Pt/CeO2-ZrO2) than on the irreducible oxides with strong or no Lewis acid sites (Pt/γ-Al2O3, Pt/SiO2-Al2O3, Pt/SiO2). As the presence of oxygen-containing compounds suppressed HDN activity, the catalysts with the highest HDO activity eventually gave the highest paraffin yield, regardless of which oxygen removal pathway was favored.

AB - Efficient catalysts for simultaneous hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) are needed for the production of renewable fuels. In this study, Pt catalysts supported on SiO2, γ-Al2O3, SiO2-Al2O3, ZrO2, CeO2-ZrO2, Nb2O5, and TiO2 were studied for the hydrotreatment of n-hexadecanamide (C16 amide) to n-paraffins at 300 °C and 80 bar H2. The catalysts favored HDO over HDN, and the initial differences in the nitrogen removal level were smaller than the differences in the oxygen removal level. The Lewis acid properties of the support influenced the initial C16 amide conversion route and HDO activity, which was reflected in the reaction network and condensation reaction selectivity of the catalysts. Pt/Nb2O5 and Pt/TiO2, with intermediate strength Lewis acid sites, initially favored the HDO of C16 amide to nitrogen-containing compounds. In contrast, the other catalysts converted C16 amide to oxygen- and nitrogen-containing compounds with similar selectivity. The HDO of the oxygen-containing compounds proceeded more efficiently on the Pt catalysts supported on oxides with weak Lewis acid sites (Pt/ZrO2, Pt/CeO2-ZrO2) than on the irreducible oxides with strong or no Lewis acid sites (Pt/γ-Al2O3, Pt/SiO2-Al2O3, Pt/SiO2). As the presence of oxygen-containing compounds suppressed HDN activity, the catalysts with the highest HDO activity eventually gave the highest paraffin yield, regardless of which oxygen removal pathway was favored.

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DO - 10.1039/d3cy01480k

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VL - 14

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JO - Catalysis Science and Technology

JF - Catalysis Science and Technology

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ER -

Hydrodeoxygenation and hydrodenitrogenation of n-hexadecanamide over Pt catalysts : effect of the support

Abstract

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Neste-Aalto HDN Catalyst Development

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Findings from Aalto University Yields New Data on Chemicals and Chemistry (Hydrodeoxygenation and Hydrodenitrogenation of n -hexadecanamide Over Pt Catalysts: Effect of the Support)

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Hydrodeoxygenation and hydrodenitrogenation of n-hexadecanamide over Pt catalysts : effect of the support

Abstract

UN SDGs

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Neste-Aalto HDN Catalyst Development

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Bioeconomy Research Infrastructure

OtaNano

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Findings from Aalto University Yields New Data on Chemicals and Chemistry (Hydrodeoxygenation and Hydrodenitrogenation of n -hexadecanamide Over Pt Catalysts: Effect of the Support)

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