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. 2022 May 20;15(10):e202200375.
doi: 10.1002/cssc.202200375. Epub 2022 Apr 1.

Efficient Production of Adipic Acid by a Two-Step Catalytic Reaction of Biomass-Derived 2,5-Furandicarboxylic Acid

Anh Vy Tran  1 , Seok-Kyu Park  2 , Hye Jin Lee  1 , Tae Yong Kim  3 , Younhwa Kim  4 , Young-Woong Suh  5 , Kwan-Young Lee  2 , Yong Jin Kim  1   6 , Jayeon Baek  1
Affiliations

Efficient Production of Adipic Acid by a Two-Step Catalytic Reaction of Biomass-Derived 2,5-Furandicarboxylic Acid

Anh Vy Tran et al. ChemSusChem. .

Abstract

Efficient catalytic ring-opening coupled with hydrogenation is a promising but challenging reaction for producing adipic acid (AA) from 2,5-furan dicarboxylic acid (FDCA). In this study, AA synthesis is carried out in two steps from FDCA via tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) over a recyclable Ru/Al2 O3 and an ionic liquid, [MIM(CH2 )4 SO3 H]I (MIM=methylimidazolium) to deliver 99 % overall yield of AA. Ru/Al2 O3 is found to be an efficient catalyst for hydrogenation and hydrogenolysis of FDCA to deliver THFDCA and 2-hydroxyadipic acid (HAA), respectively, where ruthenium is more economically viable than well-known palladium or rhodium hydrogenation catalysts. H2 chemisorption shows that the alumina phase strongly affects the interaction between Ru nanoparticles (NPs) and supports, resulting in materials with high dispersion and small size of Ru NPs, which in turn are responsible for the high conversion of FDCA. An ionic liquid system, [MIM(CH2 )4 SO3 H]I is applied to the hydrogenolysis of THFDCA for AA production. The [MIM(CH2 )4 SO3 H]I exhibits superior activity, enables simple product isolation with high purity, and reduces the severe corrosion problems caused by the conventional hydroiodic acid catalytic system.

Keywords: biomass valorization; carboxylic acids, heterogeneous catalysis; hydrodeoxygenation; ruthenium.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
a) Conventional process and b) biomass‐derived chemicals process for the formation of AA (dashed outline represents this study).
Figure 1
Figure 1
The conversion of FDCA into THFDCA over different kinds of Ru/metal oxide catalysts as a function of reaction temperatures of a) 30 °C, c) 50 °C, and e) 80 °C. ICP analysis of supernatant of different Ru/metal oxides after centrifugation of the reaction solutions at b) 30 °C, d) 50 °C, and f) 80 °C. Conditions: 1.0 wt% FDCA (0.202 g), Cat. Ru/support (0.1635 g), solvent=H2O (20 mL), P(H2)=3.1 MPa, t=4 h, T=30 °C, 50 °C, 80 °C.
Scheme 2
Scheme 2
Possible products from the conversion of FDCA into AA including hydrogenation and ring‐opening processes.
Figure 2
Figure 2
a) Effect of alumina support phase on the conversion of FDCA. Conditions: 1.0 wt% FDCA (0.202 g), Cat. Ru/alumina (0.1635 g), solvent=H2O (20 mL), P(H2)=3.1 MPa, t=4 h, T=50 °C. b) XRD spectra of different alumina‐supported Ru species.
Figure 3
Figure 3
a) H2 temperature‐programmed reduction on different Ru/alumina catalysts. b) Strong Ru‐alumina interaction. c) Medium Ru‐alumina interaction. d) Weak Ru‐alumina interaction.
Figure 4
Figure 4
Reusability test of Ru/(AlOOH+γ‐Al2O3) on the formation of THFDCA. Conditions: 1 wt% FDCA (0.202 g), Cat. Ru/(AlOOH+γ‐Al2O3) (0.1635 g), H2O (20 mL), H2 (3.1 MPa), T=50 °C, 4 h.
Figure 5
Figure 5
Correlation between catalytic activity and Brønsted acidity.
Scheme 3
Scheme 3
Possible pathways from FDCA into AA include hydrogenation and ring‐opening reactions with THFDCA and HAA as intermediates.
Figure 6
Figure 6
Effect of H2 pressure on the formation of AA over [MIM(CH2)4SO3H]I. Conditions: THFDCA (0.165 g, 0.958 mmol); Cat. [[MIM(CH2)4SO3H]I] (1.55 g), t=2 h, P=3.4 MPa, T=180 °C.
Scheme 4
Scheme 4
Proposed mechanism of the production of THFDCA over [MIM(CH2)4SO3H]I.
Figure 7
Figure 7
Reusability test of [MIM(CH2)4SO3H]I. Conditions: THFDCA (0.165 g, 93 %), n(Sub/Cat.)=0.22, H2=3.4 MPa, T=180 °C, t=2 h.
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