An investigation on the influence of support type for Ni catalysed vapour phase hydrogenation of aqueous levulinic acid to γ-valerolactone

Kumar, Velisoju Vijay; Gutta, Naresh; Sudhakar, M.; Chatla, Anjaneyulu; Bhargava, Suresh K.; Tardio, James; Reddy, Vanga Karnakar; Padmasri, A.H.; Venugopal, A.

doi:10.1039/c5ra24199e

Cited by 106 publications

(85 citation statements)

References 37 publications

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“…Thus, the higher catalytic conversion and selectivity of Ni−Al‐Ti is possibly due to the high number of active Ni metal surface sites and high LAS/BAS ratio. The Brønsted acidity is not suitable for the metal for GVL selectivity in LA hydrogenation …”

Section: Resultsmentioning

confidence: 99%

Ni‐Al‐Ti Hydrotalcite Based Catalyst for the Selective Hydrogenation of Biomass‐Derived Levulinic Acid to γ‐Valerolactone

et al. 2019

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NiÀ Al-Ti mixed oxide derived from NiÀ Al-Ti hydrotalcite precursor is identified as an efficient catalyst for the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). This catalyst showed high active surface Ni sites due to a higher synergy in the mixed oxide formed from the hydrotalcite precursor. These results are further supported by X-ray diffraction analysis (XRD), electron spin resonance spectroscopy (ESR) and scanning electron microscopy (SEM) results. The higher activity of NiÀ Al-Ti compared to NiÀ Al, NiÀ Ti catalysts was attributed to a high ratio of Lewis to Brønsted acid sites (LAS/BAS) observed from pyridine adsorption -DRIFTS results along with high surface Ni sites on the catalyst surface measured from CO-chemisorption studies. This contributed to the enhanced selectivity of the desired product, GVL over NiÀ Al-Ti catalyst as compared to its individual counter parts, NiÀ Ti and NiÀ Al catalysts.[a] R.

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Section: Resultsmentioning

confidence: 99%

Ni‐Al‐Ti Hydrotalcite Based Catalyst for the Selective Hydrogenation of Biomass‐Derived Levulinic Acid to γ‐Valerolactone

et al. 2019

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“…HPA is highly reactive and readily undergoes dehydration to GVL . Alternatively, dehydration of LA (step (VIII)) on acid sites generates α‐angelica lactone (AGL) that undergoes reduction to GVL (step (IX)) . The HPA or AGL intermediates were not isolated in the product mixture.…”

Section: Resultsmentioning

confidence: 99%

Continuous gas phase catalytic transformation of levulinic acid to γ‐valerolactone over supported Au catalysts

Mustafin

Cárdenas‐Lizana

Keane

2017

J of Chemical Tech & Biotech

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BACKGROUND: -Valerolactone (GVL) is a high value chemical obtained from hydrogenation of bio-derived levulinic acid (LA). Work to date has focused on batch pressurised catalytic systems where high GVL yield is challenging. In this work, the role of support redox and acidity properties is examined in the continuous gas phase hydrogenation of aqueous LA at ambient pressure over gold on Al 2 O 3 , CeO 2 and TiO 2 ; Pd/Al 2 O 3 served as a benchmark in catalyst tests. RESULTS: 100% GVL yield was achieved under stoichiometric conditions (inlet H2 /LA = 1) over supported Au (mean size = 3.0-4.3 nm). Greater catalytic activity was recorded for Au on reducible TiO 2 and CeO 2 . Under the same reaction conditions, Pd/Al 2 O 3 delivered higher LA consumption rates but promoted formation of pentanoic acid. CONCLUSIONS: GVL formation proceeds via 4-hydroxypentanoic as reactive intermediate. Surface oxygen vacancies (confirmed by O 2 titration) formed during temperature programmed reduction of reducible oxides activate LA for reaction. Greater GVL productivity (with full hydrogen utilisation) is demonstrated in this work relative to state-of-the art supported Pd and Ru catalysts. EXPERIMENTAL Catalyst preparation and activationThe oxide carriers ( -Al 2 O 3 (Puralox, Condea Vista Co.), CeO 2 (Grace Davison) and TiO 2 (P25, Degussa)) were used as received. Supported (1.0-3.0% wt.) Au catalysts were prepared by deposition-precipitation. Urea (100-fold excess, Riedel-de Haën, 99%), used as basification agent, was added to an aqueous solution of HAuCl 4 (4 × 10 −5 -5 × 10 −3 M; 20-50 cm 3 , Sigma-Aldrich,99%) containing the support (5-30 g). The wileyonlinelibrary.com/jctb

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“…[14][15][16] Similarly, it has been postulated that acidic moieties surrounding the catalytically active surface could be beneficial to reduce the extent of deactivation. [17][18][19][20] Alternative active phases to Ru, such as Cu, 21 Pt, 22 Ni, 23 , Pd, 24 Ir, 24 and Au 25 , are much less selective, yielding 2-methyltetrahydrofuran and 1,4-pentandiol, and/or require harsher reaction condition to reach the same conversion level. Applications of nanostructured hybrid materials in catalysis are continuously expanding due to the unique properties that can arise from the interaction of the organic and inorganic components.…”

Section: Introductionmentioning

confidence: 99%

Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Albani

Vilé

et al. 2017

Green Chem.

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a Gamma-valerolactone (GVL), a versatile renewable compound listed among the top 10 most promising platform chemical by the US Department of Energy, is produced via hydrogenation of levulinic acid (LA). The traditional high-loading ruthenium-on-carbon catalyst (5 wt.% Ru) employed for this transformation suffers from low metal utilisation and poor resistance to deactivation due to the formation of RuO x species. Aiming at an improved catalyst design, we have prepared ruthenium nanoparticles modified with the water-soluble hydroxyethyl-dimethyl ammonium dihydrogen phosphate (HHDMA) ligand and supported on TiSi 2 O 6 . The hybrid catalyst has been characterised by ICP-OES, elemental analysis, TGA, DRIFTS, H 2 -TPR, STEM, EDX, 31 P and 13 C MAS-NMR, and XPS. When evaluated in the continuous-flow hydrogenation of LA, the Ru-HHDMA/TiSi 2 O 6 catalyst (0.24 wt.% Ru) displays a fourfold higher reaction rate than the stateof-the-art Ru/C catalyst, while maintaining a 100% selectivity to GVL and no sign of deactivation after 15 hours on stream. An in-depth molecular analysis by Density Functional Theory demonstrates that the intrinsic acidic properties of the ligand-metal interface under reaction conditions ensure that the less energy demanding path is followed. The reaction does not obey the expected cascade mechanism and intercalates hydrogenation steps, hydroxyl/water eliminations, and ring closings to ensure high selectivity. Moreover, the interfacial acidity increases the robustness of the material against ruthenium oxide formation. These results provide valuable improvements for the sustainable production of GLV and insights for the rationalisation of the exceptional selectivity of Ru-based catalysts.

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An investigation on the influence of support type for Ni catalysed vapour phase hydrogenation of aqueous levulinic acid to γ-valerolactone

Abstract: Product distribution is dependent on the nature and strength of the acid site in the vapour phase hydrogenation of levulinic acid.

Cited by 106 publications

References 37 publications

Ni‐Al‐Ti Hydrotalcite Based Catalyst for the Selective Hydrogenation of Biomass‐Derived Levulinic Acid to γ‐Valerolactone

Ni‐Al‐Ti Hydrotalcite Based Catalyst for the Selective Hydrogenation of Biomass‐Derived Levulinic Acid to γ‐Valerolactone

Continuous gas phase catalytic transformation of levulinic acid to γ‐valerolactone over supported Au catalysts

Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

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