Zirconia-Supported Pt, Pd, Rh, Ru, and Ni Catalysts in the Hydrotreatment of Fatty Amides and Amines

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

doi:10.1021/acs.energyfuels.3c04372

Zirconia-Supported Pt, Pd, Rh, Ru, and Ni Catalysts in the Hydrotreatment of Fatty Amides and Amines

Emma Verkama^*
, Sylvia Albersberger
, 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

14 Citations (Scopus)

181 Downloads (Pure)

Abstract

Active catalysts for simultaneous hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) enable the production of fuels from renewable feedstocks. In this work, zirconia-supported nickel, ruthenium, rhodium, palladium, and platinum catalysts were evaluated in the HDO and HDN of n-hexadecanamide (C16 amide). The HDN of 1-hexadecylamine (C16 amine) was studied separately to assess the HDN activity and the preference between C-C and C-N bond cleavage routes without the interference of HDO. The differences in the catalytic activity were mainly attributed to the metal identity. Pt/ZrO₂ and Ru/ZrO₂ exhibited the highest activity toward the conversion of both model compounds. The C16 amide was converted more efficiently than the C16 amine over the studied catalysts, and a high HDO activity did not translate to a high activity in HDN, which was particularly evident in the case of Rh/ZrO₂. The active metal strongly influenced the preferred reaction routes, as observed from differences in the yields of C15 and C16 n-paraffins and C32 condensation products. Ni/ZrO₂ and Pd/ZrO₂ exhibited the lowest activity and paraffin selectivity in the hydrotreatment of both model compounds. Ru/ZrO₂ and Rh/ZrO₂ favored the formation of n-pentadecane from both the C16 amine and C16 amide, whereas Pt/ZrO₂ produced n-hexadecane and high intermediate yields of the C32 condensation products.

Original language	English
Pages (from-to)	4464-4479
Number of pages	16
Journal	Energy & Fuels
Volume	38
Issue number	5
DOIs	https://doi.org/10.1021/acs.energyfuels.3c04372
Publication status	Published - 7 Mar 2024
MoE publication type	A1 Journal article-refereed

Funding

Henni Kuokka is acknowledged for assistance with the batch reactor experiments. Dr. Hua Jiang and the facilities of the OtaNano Nanomicroscopy center are acknowledged for the STEM images. Dr. Yingnan Zhao and the Research Analytics department of Neste Corporation are acknowledged for the guidance and equipment support related to the pyridine FTIR measurements. This work used the Bioeconomy and Raw materials research infrastructures at Aalto University. This work was funded by Neste Corporation as a part of the Neste-Aalto HDN catalyst development project.

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10.1021/acs.energyfuels.3c04372Licence: CC BY

CHEM_Verkama_et_al_Zirconia-supported_2024_Energy_and_FuelsFinal published version, 3.19 MBLicence: CC BY

Cite this

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title = "Zirconia-Supported Pt, Pd, Rh, Ru, and Ni Catalysts in the Hydrotreatment of Fatty Amides and Amines",

abstract = "Active catalysts for simultaneous hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) enable the production of fuels from renewable feedstocks. In this work, zirconia-supported nickel, ruthenium, rhodium, palladium, and platinum catalysts were evaluated in the HDO and HDN of n-hexadecanamide (C16 amide). The HDN of 1-hexadecylamine (C16 amine) was studied separately to assess the HDN activity and the preference between C-C and C-N bond cleavage routes without the interference of HDO. The differences in the catalytic activity were mainly attributed to the metal identity. Pt/ZrO2 and Ru/ZrO2 exhibited the highest activity toward the conversion of both model compounds. The C16 amide was converted more efficiently than the C16 amine over the studied catalysts, and a high HDO activity did not translate to a high activity in HDN, which was particularly evident in the case of Rh/ZrO2. The active metal strongly influenced the preferred reaction routes, as observed from differences in the yields of C15 and C16 n-paraffins and C32 condensation products. Ni/ZrO2 and Pd/ZrO2 exhibited the lowest activity and paraffin selectivity in the hydrotreatment of both model compounds. Ru/ZrO2 and Rh/ZrO2 favored the formation of n-pentadecane from both the C16 amine and C16 amide, whereas Pt/ZrO2 produced n-hexadecane and high intermediate yields of the C32 condensation products.",

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

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T1 - Zirconia-Supported Pt, Pd, Rh, Ru, and Ni Catalysts in the Hydrotreatment of Fatty Amides and Amines

AU - Verkama, Emma

AU - Albersberger, Sylvia

AU - Meinander, Kristoffer

AU - Tiitta, Marja

AU - Karinen, Reetta

AU - Puurunen, Riikka L.

PY - 2024/3/7

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N2 - Active catalysts for simultaneous hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) enable the production of fuels from renewable feedstocks. In this work, zirconia-supported nickel, ruthenium, rhodium, palladium, and platinum catalysts were evaluated in the HDO and HDN of n-hexadecanamide (C16 amide). The HDN of 1-hexadecylamine (C16 amine) was studied separately to assess the HDN activity and the preference between C-C and C-N bond cleavage routes without the interference of HDO. The differences in the catalytic activity were mainly attributed to the metal identity. Pt/ZrO2 and Ru/ZrO2 exhibited the highest activity toward the conversion of both model compounds. The C16 amide was converted more efficiently than the C16 amine over the studied catalysts, and a high HDO activity did not translate to a high activity in HDN, which was particularly evident in the case of Rh/ZrO2. The active metal strongly influenced the preferred reaction routes, as observed from differences in the yields of C15 and C16 n-paraffins and C32 condensation products. Ni/ZrO2 and Pd/ZrO2 exhibited the lowest activity and paraffin selectivity in the hydrotreatment of both model compounds. Ru/ZrO2 and Rh/ZrO2 favored the formation of n-pentadecane from both the C16 amine and C16 amide, whereas Pt/ZrO2 produced n-hexadecane and high intermediate yields of the C32 condensation products.

AB - Active catalysts for simultaneous hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) enable the production of fuels from renewable feedstocks. In this work, zirconia-supported nickel, ruthenium, rhodium, palladium, and platinum catalysts were evaluated in the HDO and HDN of n-hexadecanamide (C16 amide). The HDN of 1-hexadecylamine (C16 amine) was studied separately to assess the HDN activity and the preference between C-C and C-N bond cleavage routes without the interference of HDO. The differences in the catalytic activity were mainly attributed to the metal identity. Pt/ZrO2 and Ru/ZrO2 exhibited the highest activity toward the conversion of both model compounds. The C16 amide was converted more efficiently than the C16 amine over the studied catalysts, and a high HDO activity did not translate to a high activity in HDN, which was particularly evident in the case of Rh/ZrO2. The active metal strongly influenced the preferred reaction routes, as observed from differences in the yields of C15 and C16 n-paraffins and C32 condensation products. Ni/ZrO2 and Pd/ZrO2 exhibited the lowest activity and paraffin selectivity in the hydrotreatment of both model compounds. Ru/ZrO2 and Rh/ZrO2 favored the formation of n-pentadecane from both the C16 amine and C16 amide, whereas Pt/ZrO2 produced n-hexadecane and high intermediate yields of the C32 condensation products.

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Zirconia-Supported Pt, Pd, Rh, Ru, and Ni Catalysts in the Hydrotreatment of Fatty Amides and Amines

Abstract

Funding

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Fingerprint

Neste-Aalto HDN Catalyst Development

Bioeconomy Research Infrastructure

OtaNano

OtaNano - Nanomicroscopy Center

Cite this

Zirconia-Supported Pt, Pd, Rh, Ru, and Ni Catalysts in the Hydrotreatment of Fatty Amides and Amines

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Projects

Neste-Aalto HDN Catalyst Development

Equipment

Bioeconomy Research Infrastructure

OtaNano

OtaNano - Nanomicroscopy Center

Cite this