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Synergistic NiCo-BTC Catalysts for the Catalytic Transfer Hydrogenation of Furfural to γ-Valerolactone: Insights from Monometallic Cu-, Ni-, and Co-BTC Comparison
(2026-10-01)
Thansirisunthorn, Sudarat
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Teerawatananond, Thapong
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Shoosri, Tanyarat
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Rungtaweevoranit, Bunyarat
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Miyake, Takanori
A series of monometallic Cu-BTC, Ni-BTC, and Co-BTC catalysts was successfully synthesized via the solvothermal method to evaluate their performance in the catalytic transfer hydrogenation of furfural (FF) to γ-valerolactone (GVL). The Co-BTC and Ni-BTC catalysts exhibited higher FF conversion, selectivity, and GVL yield than Cu-BTC due to favorable redox properties of Co2+ and Ni2+ and stronger acidity that enhance substrate activation and key ring-opening and lactonization steps. To further enhance performance, bimetallic NiCo-BTC catalysts with different Ni/Co mole ratios (0.25, 0.50, 0.75, 1.00) were developed. All bimetallic NiCo-BTC catalysts outperformed the monometallic counterparts, with 0.50NiCo-BTC achieving complete FF conversion and the highest GVL selectivity and yield of 89% at 200 °C after 24 h. TEM, XPS, XANES, and NH<inf>3</inf>-TPD analyses indicated that the enhanced catalytic activity and selectivity arise from synergistic Ni-Co interactions and increased surface acidity. Time-resolved product analysis confirmed a sequential pathway with furfuryl alcohol (FA) as a key intermediate. Moreover, the 0.50NiCo-BTC catalyst exhibited good reusability over three cycles with minimal activity loss, demonstrating structural stability under reaction conditions. These results highlighted the importance of metal synergy and acid site tuning in designing highly efficient metal organic framework catalysts for biomass upgrading via catalytic transfer hydrogenation.
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Energy analysis and life cycle assessment of furfural and 5-hydroxymethylfurfural integrated biorefinery processes with heat pump-assisted reactive distillation
(2025-03-15)
Wiranarongkorn, Kunlanan
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Im-Orb, Karittha
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Saebea, Dang
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Patcharavorachot, Yaneeporn
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Arpornwichanop, Amornchai
Bio-based products, such as biochemicals and bioenergy, have received considerable attention in efforts to mitigate the effects of climate change. In this study, an integrated biorefinery process for the production of furfural and 5-hydroxymethylfurfural (HMF) using sugarcane bagasse is proposed. Three process scenarios were compared: the integrated process of HMF and furfural production using (i) conventional reactive distillation (RD), (2) heat pump-assisted RD, and (3) heat pump-assisted RD with heat integration. The comparison focused on energy efficiency and life cycle analysis. The simulation results revealed that the overall energy efficiency of the proposed process could increase by 14.5 % with the additional heat pump to the RD column at a pressure ratio of 1.4 due to a reduction of external energy consumption. This improvement reduced the environmental impact of natural gas combustion for utility production. Specifically, the global warming potential of processes involving heat pump-assisted RD without and with heat integration decreased by 16.66 % and 80.08 %, respectively, compared to conventional RD. These results indicate that incorporating heat pump-assisted RD and implementing effective heat management within the integrated biorefinery process significantly decreased external energy consumption, leading to substantial environmental benefits.
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Role of Copper Species in Copper Phyllosilicate Catalysts for the Catalytic Transfer Hydrogenation of Furfural to γ-Valerolactone
(2025-02-17)
Shoosri, Tanyarat
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Thongratkaew, Sutarat
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Rungtaweevoranit, Bunyarat
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Kraithong, Wasawat
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Faungnawakij, Kajornsak
Copper phyllosilicate (CuPS) catalysts were synthesized and evaluated for the catalytic transfer hydrogenation of furfural to γ-valerolactone (GVL). Various copper loadings (10–30 wt.%) were studied to elucidate the impact of copper species on catalytic performance. Notably, a high dispersion of copper (%D<inf>Cu</inf> ≈ 70%) and a substantial BET surface area (620 m2/g) were achieved, even at the maximum copper loading of 30 wt.%. TR-XANEs and XPS analyses identified the two geometric structures of Cu2⁺ on the CuPS catalysts; square planar and octahedral alongside Cu⁺/Cu⁰ species were formed upon reduction at temperatures exceeding 200 °C. The reduced 30% CuPS-R catalyst, enriched in metallic Cu⁰, achieved complete conversion of furfural, but exhibited low GVL selectivity (22%). Conversely, the as-synthesized 30% CuPS, predominantly composed of Cu2⁺, showed a lower furfural conversion (14%) but higher selectivity for GVL (37%). The physical mixing of 30% CuPS-R and 30% CuPS in a 50:50 ratio yielded the best catalytic performance, resulting in 100% furfural conversion and 86% GVL selectivity. The findings suggest that metallic Cu⁰ is essential for initiating the conversion of furfural, while Cu2⁺ plays a critical role in GVL formation. An optimal Lewis/Brønsted acidity (L/B) ratio of 5.7 is proposed for the mixed catalysts. The proposed reaction mechanism underscores the complex interplay between different copper species and acid sites, emphasizing the need for optimizing both metal and acid functionalities in catalyst design.
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Comparative techno-economic and energy analyses of integrated biorefinery processes of furfural and 5-hydroxymethylfurfural from biomass residue
(2023-04-01)
Wiranarongkorn, K.
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Im-orb, K.
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Patcharavorachot, Y.
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Maréchal, F.
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Arpornwichanop, A.
For efficient feedstock and energy utilization, integrated biorefinery processes are applied to furfural production from bagasse to convert furfural residue into 5-hydroxymethylfurfural (HMF)—an important intermediate building block for the production of various biochemicals. Here, a techno-economic analysis of the integrated processes of furfural and HMF production combined with electricity generation under different scenarios was performed to identify the most suitable process design. Simulations revealed that using the whole bagasse in the biorefinery plant and recycling 50% waste from the HMF production to recover unreacted sugar (scenario 2) achieved the maximum furfural and HMF production with minimum CO<inf>2</inf> emission, compared with integrated processes without sugar recycling (scenario 1), with 80% (scenario 3) and 60% biomass (scenario 4) bypassed to the biorefinery, and with a standalone combined heat and power system (scenario 5). Moreover, heat integration improved the efficiency of biorefinery plant (scenario 2), with an energy recovery potential of 71%, leading to the maximum profit at 11% internal rate of return. However, the high operating cost associated with the requirement of solvents and catalysts for HMF production represents the largest cost distribution in the proposed integrated processes. Sensitivity analysis revealed that solvent cost was the most important parameter for economic benefit. In addition, improving technological efficiency in the pretreatment and HMF production phases can enhance product yield, thereby benefiting the profitability of this process.
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Development of bimetallic Ni-Cu/SiO2 catalysts for liquid phase selective hydrogenation of furfural to furfuryl alcohol
(2021-01-15)
Weerachawanasak, Patcharaporn
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Krawmanee, Pacharaporn
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Inkamhaeng, Weerachat
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Cadete Santos Aires, Francisco J.
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Sooknoi, Tawan
Bimetallic Ni-Cu/SiO<inf>2</inf> catalysts with different Cu loading (2–5 wt%) were developed for liquid phase selective hydrogenation of furfural to furfuryl alcohol. Among these, bimetallic 2%Ni-X%Cu/SiO<inf>2</inf> (X = 2, 5) catalysts exhibited better catalytic performances than monometallic 2%Ni/SiO<inf>2</inf> and 2%Cu/SiO<inf>2</inf>. Moreover, the bimetallic 2%Ni-5%Cu/SiO<inf>2</inf> catalyst showed the best catalytic performance with 94% of furfural conversion and 64% of furfuryl alcohol selectivity. The synergetic effect of NiCu alloy particles that are present on bimetallic Ni-Cu/SiO<inf>2</inf> catalysts change the adsorption configuration of furfural on the catalyst surface resulting in high catalytic performance in liquid phase selective hydrogenation of furfural to furfuryl alcohol.
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Flame spray-synthesized Pt-Co/TiO2 catalysts for the selective hydrogenation of furfural to furfuryl alcohol
(2021-01-15)
Tolek, Weerachon
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Khruechao, Kitima
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Pongthawornsakun, Boontida
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Mekasuwandumrong, Okorn
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Cadete Santos Aires, Francisco José
Flame spray-synthesized Pt/TiO<inf>2</inf> and PtCo/TiO<inf>2</inf> catalysts with 0.7 wt% Pt and 0–0.4 wt% Co were studied in the hydrogenation of furfural to furfuryl alcohol (FA) at 50 °C and 2 MPa H<inf>2</inf>. Particle formation under high temperature flame facilitated high Pt dispersion and formation of Pt-TiO<inf>x</inf> interface sites, which were beneficial for furfural conversion to FA. Modifying with Co accelerated rutile phase TiO<inf>2</inf> formation, which strongly diminished hydrogenation activity on the (FSP)-PtCo/TiO<inf>2</inf>. On the other hand, (I)-PtCo/TiO<inf>2</inf> prepared by conventional impregnation, anatase phase TiO<inf>2</inf> was preserved (> 85%) and both furfural conversion and FA selectivity increased upon increasing Co loading.

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