Hydroxyalkylation/alkylation of 2-methylfuran and furfural over niobic acid catalysts for the synthesis of high carbon transport fuel precursors

Raguindin, Reibelle Q.; Gebresillase, Mahlet N.; Han, Seung Ju; Seo, Jeong Gil

doi:10.1039/d0se00267d

Cited by 23 publications

(8 citation statements)

References 40 publications

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“…The hydroxyalkylation/alkylation reaction mechanism has been reported to be initiated by a relatively strong Bronsted acid site via protonation of the carbonyl group of acetone and the creation of a carbocation intermediate. − Nucleophilic attack of 2MF to this carbocation forms the hydroxyalkyation product, which then interacts with a second 2MF molecule to form the alkylation product, BMFP, upon dehydration. Yields of BMFP observed over the solid acid catalysts generally increase with increasing BAS density (ranging from 0.12 to 0.76 mmol/g), as expected.…”

Section: Resultsmentioning

confidence: 99%

“…In terms of acid site strength (rigorously defined by deprotonation energy), the catalysts are ranked as follows: Nafion NR50 > PE-SiO 2 ≈ PE-Betas > H-Betas . Yet, despite the fact that stronger Bronsted acid sites increase the rate of the slow hydroxyalkylation step, both PE-Betas and H-Beta_100 achieve higher TONs compared to PE-SiO 2 and Nafion NR50. These results show that confinement within the micropores of zeolite materials is beneficial for executing this reaction, and has a significant contribution to TON.…”

Section: Resultsmentioning

confidence: 99%

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Sulfonic Acid-Functionalized Zeolite Beta: Bronsted Acid Catalysts for Reactions Involving Liquid Water

Lusardi

Davis

2021

ACS Sustainable Chem. Eng.

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The utility of zeolites in biomass upgrading reactions can be limited in cases where stronger Bronsted acidity and/or hydrophobicity are required for effective catalysis. While sulfonated solids/sulfonic acid catalysts can be used in such cases, they forego the advantageous effects of confinement that are afforded by zeolites. Here, acidity, hydrophobicity, and confinement are integrated into a solid material by functionalizing the intrapore voids of zeolite Beta with phenethyl-sulfonic acid sites (PE-Betas). These PE-Betas, along with conventional H-Betas, mesoporous phenethyl-sulfonic acidfunctionalized SiO 2 gel (PE-SiO 2 ), and commercial sulfonic acid catalysts (para-toluenesulfonic acid, Nafion NR50) are evaluated in the hydroxyalkylation/alkylation reaction of 2-methylfuran with acetone. The PE-Betas show superior turnover numbers (TON) due to the combination of high acid site strength and hydrophobicity that arises from the confined PE groups. Further, the hydrophobicity and TON over PE-Betas are invariant with acid site density, showing that these materials effectively decouple the active site density−hydrophilicity relationship that is a fundamental limitation of conventional zeolites. These sulfonic acidfunctionalized zeolites represent a distinct class of water-tolerant, strong Bronsted acid catalysts that may be well suited for a wide range of biomass upgrading reactions that generate stoichiometric amounts of liquid water.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Sulfonic Acid-Functionalized Zeolite Beta: Bronsted Acid Catalysts for Reactions Involving Liquid Water

Lusardi

Davis

2021

ACS Sustainable Chem. Eng.

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“…[3,24] Li, Zhang, and co-workers [25,26] prepared a panel of diesel precursors via the HAA reaction from various biomass-derived aldehydes and 2-MF over solid acids such as Amberlyst-15, Nafion-212. Apart from that, niobium oxides, [27,28] acid functionalized hydrogen coke, [29] lignosulfonate-based acidic resin, [30] the protonated titanate nanotube (PTNT) [31] were also used in HAA reactions with high reactivities. Saha and co-workers reported the HAA reaction through the improved graphene oxide (IGO) catalysts, [32] and further developed the hydrodeoxygenation (HDO) reactions over Ir-ReO x /SiO 2 catalysts to afford the alkanes.…”

Section: Introductionmentioning

confidence: 99%

Rapid Synthesis of Diesel Precursors from Biomass‐Derived Furanics Over Aluminum‐Doped Mesoporous Silica Sphere Catalysts

et al. 2023

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The condensation of biomass-derived molecules has been increasingly utilized as a sustainable strategy for the preparation of high-carbon precursors for high-density fuels, thus stimulating the demand for more efficient catalysts. This study concerns the synthesis of an aluminum-doped mesoporous silica sphere (Al-MSS) catalyst for the conversion of biobased furfural and 2-methylfuran into a C 15 diesel precursor through a hydroxyalkylation/alkylation (HAA) reaction. A series of Al-MSS catalysts with different Si/Al ratios and calcination temperatures is prepared and extensively characterized, among which Al-MSS20-450 (Si/Al = 20 : 1, calcined at 450 °C) exhibits unprecedentedly high reaction efficiency in catalyzing HAA reaction, offering a 94 % product yield at 140 °C in 20 min. The catalyst also gives high product yields across a broad temperature range from 80 °C to 140 °C with varied reaction time. Reaction kinetics reveal that both competitive substrate adsorption and temperature-dependent system viscosity affect the reaction efficiencies. Correlations between the catalytic activity and surface acid sites disclose that moderate and strong acid sites are primarily responsible for catalysis. Brønsted and Lewis acid sites are found by poisoning assays to work synergistically to catalyze the reaction, with the former being the primary sites. Finally, the catalyst displays good recycling performance, which further highlights its potential for industrial application.

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“…Production of chemicals with more than six carbon atoms from biomass-derived cellulose and hemicellulose is a challenging task. Significant work has been done to produce C5 and C6 sugar monomers by the acid hydrolysis of cellulose and hemicellulose. − These monomers can be converted into C5 and C6 platform furanic compounds (furfural and 5-hydroxymethylfurfural (HMF)), which can act as building blocks for future biorefineries, via an acid-catalyzed dehydration reaction. − Therefore, to sustain the petrochemical supply chain, production of biomass-derived furan derivatives has been attracting the attention of researchers and scientists in the last few years. , The most attractive and efficient strategies to increase the biomass-derived furanic compounds’ carbon chain length are the carbon–carbon (C–C) coupling reactions through aldol condensation, hydroxyalkylation, etherification, esterification, and acetalization. − …”

Section: Introductionmentioning

confidence: 99%

Pd-Decorated CePO₄ Catalyst for the One-Pot, Two-Step Cascade Reaction to Transform Biomass-Derived Furanic Aldehydes into Fuel Intermediates

2021

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Production of fuel range chemicals from biomass-derived carbonyls is a viable strategy to overcome the dependency on nonrenewable fossil fuels. Acid–base catalytic processes play a vital role in producing liquid fuel range chemicals and intermediates derived from renewable biomass. Aldol condensation is one of the simplest ways to convert biomass-derived carbonyls to C8–C15 range fuels. Herein, CePO4 possessing acidic and basic sites is synthesized under basic pH and used as catalyst support to decorate Pd nanoparticles to fabricate a Pd/CePO4 catalyst. Pd/CePO4 facilitates aldol condensation to form a highly selective α,β-unsaturated methyl ketone in the first step, followed by the selective reduction of CC to form a C–C coupled hydrogenated product containing a CO functional group in a one-pot cascade protocol. Many biomass and non-biomass-derived aldehydes are reacted with acetone and methyl isobutyl ketone (MIBK) for the selective production of fuel precursors. Pyridine Fourier transform infrared (FT-IR) and NH3/CO2 temperature-programmed desorption (TPD) measurements are employed to probe the acidity and basicity of the catalyst. The influence of different Pd loadings on the reducibility of these catalysts is studied by H2 temperature-programmed reduction (TPR) analysis. The activation energy (E a) for aldol condensation between furfural and acetone is estimated to be 55.3 kJ/mol. The present catalytic system offers a higher furfural conversion (99.0%) with a higher selectivity (93.6%) of the desired hydrogenated product. Production of furan-based higher-carbon-containing compounds having carbonyl functionality using a simple and robust metal phosphate-based catalyst would be highly interesting from industrial and academic perspectives for fuel/chemical production.

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Hydroxyalkylation/alkylation of 2-methylfuran and furfural over niobic acid catalysts for the synthesis of high carbon transport fuel precursors

Abstract: In producing high-grade transport fuel from lignocellulosic biomass, carbon–carbon (C–C) coupling reactions are one of the most available and efficient strategies for increasing the carbon chain length and thereby producing fuel precursors.

Cited by 23 publications

References 40 publications

Sulfonic Acid-Functionalized Zeolite Beta: Bronsted Acid Catalysts for Reactions Involving Liquid Water

Sulfonic Acid-Functionalized Zeolite Beta: Bronsted Acid Catalysts for Reactions Involving Liquid Water

Rapid Synthesis of Diesel Precursors from Biomass‐Derived Furanics Over Aluminum‐Doped Mesoporous Silica Sphere Catalysts

Pd-Decorated CePO₄ Catalyst for the One-Pot, Two-Step Cascade Reaction to Transform Biomass-Derived Furanic Aldehydes into Fuel Intermediates

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Hydroxyalkylation/alkylation of 2-methylfuran and furfural over niobic acid catalysts for the synthesis of high carbon transport fuel precursors

Abstract: In producing high-grade transport fuel from lignocellulosic biomass, carbon–carbon (C–C) coupling reactions are one of the most available and efficient strategies for increasing the carbon chain length and thereby producing fuel precursors.

Cited by 23 publications

References 40 publications

Sulfonic Acid-Functionalized Zeolite Beta: Bronsted Acid Catalysts for Reactions Involving Liquid Water

Sulfonic Acid-Functionalized Zeolite Beta: Bronsted Acid Catalysts for Reactions Involving Liquid Water

Rapid Synthesis of Diesel Precursors from Biomass‐Derived Furanics Over Aluminum‐Doped Mesoporous Silica Sphere Catalysts

Pd-Decorated CePO4 Catalyst for the One-Pot, Two-Step Cascade Reaction to Transform Biomass-Derived Furanic Aldehydes into Fuel Intermediates

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Product

Resources

About

Pd-Decorated CePO₄ Catalyst for the One-Pot, Two-Step Cascade Reaction to Transform Biomass-Derived Furanic Aldehydes into Fuel Intermediates