Continuous hydrocyclization of aqueous levulinic acid to γ-valerolactone over bi-functional Ru/NbOPO4/SBA-15 catalyst under mild conditions

Mariappan Mani; Mariyamuthu Mariyaselvakumar; Ajaikumar Samikannu; Asit Baran Panda; Lakhya Jyoti Konwar; Jyri Pekka Mikkola

doi:10.1016/j.apcata.2022.118744

Continuous hydrocyclization of aqueous levulinic acid to γ-valerolactone over bi-functional Ru/NbOPO₄/SBA-15 catalyst under mild conditions

Mariappan Mani
, Mariyamuthu Mariyaselvakumar
, Ajaikumar Samikannu
, Asit Baran Panda
, Lakhya Jyoti Konwar^*
, Jyri Pekka Mikkola

^*Corresponding author for this work

Laboratory of Industrial Chemistry and Reaction Engineering

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

15 Citations (Scopus)

Abstract

Herein, we demonstrate that surface acid-base properties have marked effect upon the performance (activity, selectivity and stability) of supported Ru catalysts upon tandem hydrocyclization (hydrogenation-dehydration) of aqueous levulinic acid. A mesoporous bi-functional Ru/NbOPO₄/SBA-15 catalyst incorporating highly dispersed Ru sites and well balanced strong Brønsted acidic sites (optimum B/L and M+S/W ratio) was identified, which outperformed the benchmark monofuncational (Ru/SBA-15, Ru/MCM-41) and physically blended bi-functional catalysts (Ru catalysts mixed with acid co-catalysts e.g. NbOPO₄/Amberlyst-15). Further, the catalyst also demonstrated remarkable stability in a fixed-bed reactor, maintaining steady activity and γ-valerolactone selectivity (72–86%) during ca. 300 h time on stream (10 bar, 90–100 °C), corroborating its industrial potential. The exceptional performance and durability of the bi-functional catalyst was attributed to the presence of well dispersed hydrothermally and chemically stable acid (NbOPO₄) and redox (Ru) sites.

Original language	English
Article number	118744
Number of pages	16
Journal	Applied Catalysis A: General
Volume	643
DOIs	https://doi.org/10.1016/j.apcata.2022.118744
Publication status	Published - 5 Aug 2022
MoE publication type	A1 Journal article-refereed

Funding

The PRIS registration number of this publication is CSIR-CSMCRI – 04/2022 . Financial support from SERB ( SRG/2020/000325 ) and MLP0028 from CSIR , New Delhi are gratefully acknowledged. The authors also thank the Analytical Division and Centralized Instrumental Facilities of this institute for analytical support. The PRIS registration number of this publication is CSIR-CSMCRI – 04/2022. Financial support from SERB (SRG/2020/000325) and MLP0028 from CSIR, New Delhi are gratefully acknowledged. The authors also thank the Analytical Division and Centralized Instrumental Facilities of this institute for analytical support.

Keywords

Bi-functional catalyst
Catalyst deactivation
Flow chemistry
Supported Ru-catalysts
Tandem hydrocyclization
γ-valerolactone

Access to Document

10.1016/j.apcata.2022.118744

Cite this

@article{e5510d94e2bc43dc9415f1621adb054d,

title = "Continuous hydrocyclization of aqueous levulinic acid to γ-valerolactone over bi-functional Ru/NbOPO4/SBA-15 catalyst under mild conditions",

abstract = "Herein, we demonstrate that surface acid-base properties have marked effect upon the performance (activity, selectivity and stability) of supported Ru catalysts upon tandem hydrocyclization (hydrogenation-dehydration) of aqueous levulinic acid. A mesoporous bi-functional Ru/NbOPO4/SBA-15 catalyst incorporating highly dispersed Ru sites and well balanced strong Br{\o}nsted acidic sites (optimum B/L and M+S/W ratio) was identified, which outperformed the benchmark monofuncational (Ru/SBA-15, Ru/MCM-41) and physically blended bi-functional catalysts (Ru catalysts mixed with acid co-catalysts e.g. NbOPO4/Amberlyst-15). Further, the catalyst also demonstrated remarkable stability in a fixed-bed reactor, maintaining steady activity and γ-valerolactone selectivity (72{\textendash}86\%) during ca. 300 h time on stream (10 bar, 90{\textendash}100 °C), corroborating its industrial potential. The exceptional performance and durability of the bi-functional catalyst was attributed to the presence of well dispersed hydrothermally and chemically stable acid (NbOPO4) and redox (Ru) sites.",

keywords = "Bi-functional catalyst, Catalyst deactivation, Flow chemistry, Supported Ru-catalysts, Tandem hydrocyclization, γ-valerolactone",

author = "Mariappan Mani and Mariyamuthu Mariyaselvakumar and Ajaikumar Samikannu and Panda, \{Asit Baran\} and Konwar, \{Lakhya Jyoti\} and Mikkola, \{Jyri Pekka\}",

note = "Funding Information: The PRIS registration number of this publication is CSIR-CSMCRI {\textendash} 04/2022 . Financial support from SERB ( SRG/2020/000325 ) and MLP0028 from CSIR , New Delhi are gratefully acknowledged. The authors also thank the Analytical Division and Centralized Instrumental Facilities of this institute for analytical support. Funding Information: The PRIS registration number of this publication is CSIR-CSMCRI {\textendash} 04/2022. Financial support from SERB (SRG/2020/000325) and MLP0028 from CSIR, New Delhi are gratefully acknowledged. The authors also thank the Analytical Division and Centralized Instrumental Facilities of this institute for analytical support. Publisher Copyright: {\textcopyright} 2022 Elsevier B.V.",

year = "2022",

month = aug,

day = "5",

doi = "10.1016/j.apcata.2022.118744",

language = "English",

volume = "643",

journal = "Applied Catalysis A: General",

issn = "0926-860X",

publisher = "Elsevier",

}

TY - JOUR

T1 - Continuous hydrocyclization of aqueous levulinic acid to γ-valerolactone over bi-functional Ru/NbOPO4/SBA-15 catalyst under mild conditions

AU - Mani, Mariappan

AU - Mariyaselvakumar, Mariyamuthu

AU - Samikannu, Ajaikumar

AU - Panda, Asit Baran

AU - Konwar, Lakhya Jyoti

AU - Mikkola, Jyri Pekka

N1 - Funding Information: The PRIS registration number of this publication is CSIR-CSMCRI – 04/2022 . Financial support from SERB ( SRG/2020/000325 ) and MLP0028 from CSIR , New Delhi are gratefully acknowledged. The authors also thank the Analytical Division and Centralized Instrumental Facilities of this institute for analytical support. Funding Information: The PRIS registration number of this publication is CSIR-CSMCRI – 04/2022. Financial support from SERB (SRG/2020/000325) and MLP0028 from CSIR, New Delhi are gratefully acknowledged. The authors also thank the Analytical Division and Centralized Instrumental Facilities of this institute for analytical support. Publisher Copyright: © 2022 Elsevier B.V.

PY - 2022/8/5

Y1 - 2022/8/5

N2 - Herein, we demonstrate that surface acid-base properties have marked effect upon the performance (activity, selectivity and stability) of supported Ru catalysts upon tandem hydrocyclization (hydrogenation-dehydration) of aqueous levulinic acid. A mesoporous bi-functional Ru/NbOPO4/SBA-15 catalyst incorporating highly dispersed Ru sites and well balanced strong Brønsted acidic sites (optimum B/L and M+S/W ratio) was identified, which outperformed the benchmark monofuncational (Ru/SBA-15, Ru/MCM-41) and physically blended bi-functional catalysts (Ru catalysts mixed with acid co-catalysts e.g. NbOPO4/Amberlyst-15). Further, the catalyst also demonstrated remarkable stability in a fixed-bed reactor, maintaining steady activity and γ-valerolactone selectivity (72–86%) during ca. 300 h time on stream (10 bar, 90–100 °C), corroborating its industrial potential. The exceptional performance and durability of the bi-functional catalyst was attributed to the presence of well dispersed hydrothermally and chemically stable acid (NbOPO4) and redox (Ru) sites.

AB - Herein, we demonstrate that surface acid-base properties have marked effect upon the performance (activity, selectivity and stability) of supported Ru catalysts upon tandem hydrocyclization (hydrogenation-dehydration) of aqueous levulinic acid. A mesoporous bi-functional Ru/NbOPO4/SBA-15 catalyst incorporating highly dispersed Ru sites and well balanced strong Brønsted acidic sites (optimum B/L and M+S/W ratio) was identified, which outperformed the benchmark monofuncational (Ru/SBA-15, Ru/MCM-41) and physically blended bi-functional catalysts (Ru catalysts mixed with acid co-catalysts e.g. NbOPO4/Amberlyst-15). Further, the catalyst also demonstrated remarkable stability in a fixed-bed reactor, maintaining steady activity and γ-valerolactone selectivity (72–86%) during ca. 300 h time on stream (10 bar, 90–100 °C), corroborating its industrial potential. The exceptional performance and durability of the bi-functional catalyst was attributed to the presence of well dispersed hydrothermally and chemically stable acid (NbOPO4) and redox (Ru) sites.

KW - Bi-functional catalyst

KW - Catalyst deactivation

KW - Flow chemistry

KW - Supported Ru-catalysts

KW - Tandem hydrocyclization

KW - γ-valerolactone

UR - https://www.scopus.com/pages/publications/85133252862

U2 - 10.1016/j.apcata.2022.118744

DO - 10.1016/j.apcata.2022.118744

M3 - Article

AN - SCOPUS:85133252862

SN - 0926-860X

VL - 643

JO - Applied Catalysis A: General

JF - Applied Catalysis A: General

M1 - 118744

ER -