Search Results (26)

The industrial processes used to produce paper and cellulose generate many lignocellulosic residues. These residues are usually burned to produce heat to supply the energy demands of other processes, increasing greenhouse gas emissions and resulting in a high environmental impact. Instead of burning these lignocellulosic residues, they can be converted into saccharides, which are feedstock for high-value products and biofuels. Keggin heteropolyacids are efficient catalysts for obtaining saccharides from cellulose and hemicellulose and converting them into bioproducts or biofuel. Furfural, 5-hydroxymethylfurfural, levulinic acid, and alkyl levulinates are important platform molecules obtained from saccharides and raw materials in the biorefinery processes used to produce fine chemicals and biofuels. This review discusses the significant progress achieved in the development of the processes based on heteropolyacid-catalyzed reactions to convert biomass and their residues into furfural, 5-hydroxymethylfurfural, levulinic acid, and alkyl levulinates in homogeneous and heterogeneous reaction conditions. The different modifications that can be performed to a Keggin HPA structure, such as the replacement of the central atom (P or Si) with B or Al, the doping of the heteropolyanion with metal cations, and a proton exchange with metal or organic cations, as well as their impact on the catalytic activity of HPAs, are detailed and discussed herein. Full article

We examined the effectiveness of metal-exchanged phosphomolybdic acid salts in converting levulinic acid, derived from biomass, into valuable products (alkyl levulinate). We prepared salts of phosphomolybdic acid using different metals (Fe³⁺, Al³⁺, Zn²⁺, Cu²⁺, Mn²⁺, Ni²⁺, and Co²⁺). The influence of metal cations on the conversion and selectivity of the reactions was assessed. We found that the salts prepared with iron and aluminum phosphomolybdate were the most effective catalysts for the esterification of levulinic acid with methanol, with the conversion and selectivity tending towards 100% after 6 h of reaction at a temperature of 323 K. The effect of catalyst loading and its recovery and reuse was evaluated; the results from the reaction using aluminum phosphomolybdate remained similar for four cycles of use. The influence of temperature on conversion and selectivity was investigated between 298 and 353 K. The reactivity of different alcohols with a carbon chain size of C1-C4 was assessed and conversions above 65% were obtained for all alcohols tested under the conditions evaluated, except for tert-butyl alcohol. These catalysts are a promising alternative to the traditional soluble and corrosive Brønsted acid catalysts. The superior performance of these catalysts was ascribed to the higher pH decline triggered by the hydrolysis of these metal cations. Full article

In the present study, a green and readily effective route is presented, using for the first time, methanesulfonic acid (MSA) as a catalyst to produce alkyl levulinates (ALs) via the addition of alcohols to α-angelica lactone (α-AL). A smooth procedure was developed that resulted in the production of high-purity ALs, with complete conversions and high yields (99.1–99.8%), within 20 to 60 min of reaction in the presence of 0.5 mol% MSA. The reactions were carried out solvent-free, at room temperature, and in atmospheric air. Reaction conditions were optimized, and equimolar amounts of alcohol reagent were used. This work presents the main advantages of the use of a catalyst (MSA) that is low cost, easily biodegradable, and does not release toxic gases into the environment, but has an acidic strength comparable to that of other mineral acids. Therefore, this study proves the remarkable efficiency of MSA as a catalyst in the synthesis of ALs through an economically and environmentally favorable route. Full article

This work developed an efficient route to produce fuel bioadditive alkyl levulinates. Special attention was paid to butyl levulinate, which is a bioadditive with an adequate carbon chain size to be blended with liquid fuels such as diesel or gasoline. In this process, levulinic acid was esterified with butyl alcohol using cheap and commercially affordable metal nitrates as catalysts, producing bioadditives at more competitive costs. Iron (III) nitrate was the most active and selective catalyst toward butyl levulinate among the salts evaluated. In solvent-free conditions, with a low molar ratio and catalyst load (1:6 acid to alcohol, 3 mol% of Fe (NO₃)₃), conversion and selectivity greater than 90% after an 8 h reaction was achieved. A comparison of the iron (III) nitrate with other metal salts demonstrated that its superior performance can be assigned to the highest Lewis acidity of Fe³⁺ cations. Measurements of pH allow the conclusion that a cation with high Lewis acidity led to a greater H⁺ release, which results in a higher conversion. Butyl levulinate and pseudobuty levulinate were always the primary and secondary products, respectively. The consecutive character of reactions between butyl alcohol and levulinic acid (formation of the pseudobutyl levulinate and its conversion to butyl levulinate) was verified by assessing the reactions at different temperatures and conversion rates. A variation in Fe(NO₃)₃ catalyst load impacted the conversion much more than reaction selectivity. The same effect was verified when the reactions were carried out at different temperatures. The reactivity of alcohols with different structures depended more on steric hindrance on the hydroxyl group than the size of the carbon chain. A positive aspect of this work is the use of a commercial iron nitrate salt as the catalyst, which has advantages over traditional mineral acids such as sulfuric and hydrochloric acids. This solid catalyst is not corrosive and avoids neutralization steps after reactions, minimizing the generation of residues and effluents. Full article

A series of activated carbons (YMBC) obtained from yerba mate twig residue (YMT) were prepared by chemical (H₃PO₄) and thermal activation. Five materials were synthesized, varying the carbonization temperature (400–600 °C under N₂ atmosphere) and H₃PO₄:YMT ratio (60–80 wt%). They were physicochemically and texturally characterized by SEM-EDX, BET, FT-IR, and ³¹P MAS-NMR. Potentiometric titration with the n-butylamine technique was used to evaluate their acidic properties. The materials exhibited a high specific surface area (572 m² g⁻¹ < S_BET < 1031 m² g⁻¹) and mesoporosity (67% < S_meso/S_BET < 93%). The results showed that the acid strength and the number of acid sites increased with the H₃PO₄:YMT ratio and decreased with the calcination temperature increment. The FT-IR and ³¹P characterization revealed the presence of H_n+2P_nO_3n+1 species firmly (via P-O-C linkages) and loosely attached (by electrostatic interaction). The latter were successfully removed by refluxing the material in water or n-propanol. The optimal reaction conditions were applied to the synthesis of other levulinic acid esters using YMBC-500-70_NP as a catalyst. Furthermore, the effective separation of the product combined with the use of a recyclable catalyst resulted in a clean and environmentally friendly strategy for the synthesis of alkyl levulinates, bioproducts of relevance to the biorefinery industry, which can be applied as fragrances, flavoring agents, as well as fuel additives. Full article

This study presents the synthesis and characterization of mesoporous silica using biobased silica recovered from rice husks (RHs) as an excellent example of the circular economy. Distinct hydrothermal methods were used, namely, the autoclave hydrothermal method and microwave irradiation. Furthermore, the microwave-synthesized SBA-15 material was subjected to post-functionalization with –SO₃H groups using the organosilane 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane (CSPTMS). The structural and chemical properties of the prepared materials were rigorously characterized through several techniques, thereby confirming the successful preparation of this functionalized material. Subsequently, the functionalized SBA-15 (CSPTMS@SBA-15) was employed as a catalyst in the synthesis of ethyl levulinate (EL) from 5-hydroxymethylfurfural (5-HMF) using different methodologies: typical high-pressure batch reactor, conventional heating, and microwave irradiation. This investigation aimed to elucidate the influence of microwave and non-microwave heating methods on the efficient conversion of 5-HMF into EL. The findings revealed that the microwave reactor exhibited superior conversion rates and selectivity when compared to the non-microwave heating methods. The study also explored the effects of temperature and utilization of various alcohols as both solvents and reagents. The results demonstrated that higher temperatures favored the production of alkyl levulinate and that complete conversion of 5-HMF was attainable for all the alcohols employed. Specifically, for methanol and ethanol a 100% yield of alkyl levulinates was achieved, while for 1-propanol and butanol a reduction in the yield of alkyl levulinates was observed. These outcomes underscore the feasibility of achieving significant yields of various alkyl levulinates through the utilization of CSPTMS@SBA-15 as a catalyst. Full article

Diphenolic acid, or 4,4-bis(4-hydroxyphenyl)pentanoic acid, represents one of the potentially most interesting bio-products obtainable from the levulinic acid supply-chain. It represents a valuable candidate for the replacement of bisphenol A, which is strongly questioned for its toxicological issues. Diphenolic acid synthesis involves the condensation reaction between phenol and levulinic acid and requires the presence of a Brønsted acid as a catalyst. In this review, the state of the art related to the catalytic issues of its synthesis have been critically discussed, with particular attention to the heterogeneous systems, the reference benchmark being represented by the homogeneous acids. The main opportunities in the field of heterogeneous catalysis are deeply discussed, as well as the bottlenecks to be overcome to facilitate diphenolic acid production on an industrial scale. The regioselectivity of the reaction is a critical point because only the p,p′-isomer is of industrial interest; thus, several strategies aiming at the improvement of the selectivity towards this isomer are considered. The future potential of adopting alkyl levulinates, instead of levulinic acid, as starting materials for the synthesis of new classes of biopolymers, such as new epoxy and phenolic resins and polycarbonates, is also briefly considered. Full article

Alkyl levulinates are promising and versatile biomass-derived chemicals, which are utilized as fuel additives, flavoring agents, fragrances, solvents, and precursors for synthesizing valuable γ-valerolactone. A method for synthesizing alkyl levulinates involves the esterification of levulinic acid with the corresponding alkyl alcohols in the presence of solid acid catalysts that have abundant Brønsted acid sites. Alkyl levulinates can also be synthesized from other biomass-derived molecules such as furfuryl alcohol and furfural via alcoholysis and one-pot conversion, respectively. Thus far, various heterogeneous catalysts have been developed for the conversion of the biomass-derived molecules (levulinic acid, furfuryl alcohol, and furfural) into alkyl levulinates. To obtain the target products in high yields, numerous strategies have been employed including increasing Brønsted acidity, dispersing and incorporating Brønsted acid sites, inducing the formation of mesopores, and inducing a synergistic effect of metal–Brønsted acid sites that are present on a catalyst surface. Here, we summarily reviewed the performances of the heterogeneous catalysts in the conversions, describing the design and development of the heterogeneous catalysts that ensured the excellent yield of alkyl levulinates. Full article

This work reports a straightforward and high-yielding synthesis of alkyl levulinates (ALs), a class of promising biofuel, renewable solvent, and chemical feedstock of renewable origin. ALs were prepared by the acid-catalyzed esterification of levulinic acid (LA) and by the alcoholysis of carbohydrate-derived chemical platforms, such as furfuryl alcohol (FAL) and α-angelica lactone (α-AGL). Phosphotungstic acid (PTA) was chosen as the solid acid catalyst for the transformation, which was heterogenized on humin-derived activated carbon (HAC) for superior recyclability. Using HAC as catalyst support expands the scope of valorizing humin, a complex furanic resin produced inevitably as a side product (often considered waste) during the acid-catalyzed hydrolysis/dehydration of sugars and polymeric carbohydrates. Under optimized conditions (150 °C, 7 h, 25 wt.% of 20%PTA/HAC-600 catalyst), ethyl levulinate (EL) was obtained in an 85% isolated yield starting from FAL. Using the general synthetic protocol, EL was isolated in 88% and 84% yields from LA and α-AGL, respectively. The 20%PTA/HAC-600 catalyst was successfully recovered from the reaction mixture and recycled for five cycles. A marginal loss in the yield of ALs was observed in consecutive catalytic cycles due to partial leaching of PTA from the HAC support. Full article

γ-valerolactone can be a game-changer in the chemical industry because it could substitute fossil feedstocks in different fields. Its production is from the hydrogenation of levulinic acid or alkyl levulinates and can present some risk of thermal runaway. To the best of our knowledge, no studies evaluate the thermal stability of this production in a continuous reactor. We simulated the thermal behavior of the hydrogenation of butyl levulinate over Ru/C in a continuous stirred-tank reactor and performed a sensitivity analysis. The kinetic and thermodynamic constants from Wang et al.’s articles were used. We found that the risk of thermal stability is low for this chemical system. Full article

In this research, ethyl levulinate, methyl levulinate, and 2-methyltetrahydrofuran as bio-derived hemicellulose-based solvents were applied as green alternatives in palladium-catalyzed aminocarbonylation reactions. Iodobenzene and morpholine were used in optimization reactions under different conditions, such as temperatures, pressures, and ligands. It was shown that the XantPhos ligand had a great influence on conversion (98%) and chemoselectivity (100% carboxamide), compared with the monodentate PPh₃. Following this study, the optimized conditions were used to extend the scope of substrates with nineteen candidates (various para-, ortho-, and meta-substituted iodobenzene derivatives and iodo-heteroarenes), as well as eight different amine nucleophiles. Full article

The Menshutkin reaction represents the alkylation of tertiary amines by alkyl halide where the reactants are neutral and the products, quaternary ammonium salts, are two ions with opposite signs. The most commonly used organic solvents in quaternization reactions are volatile organic solvents (VOSs), namely acetone, anhydrous benzene, dry dichloromethane (DCM), dimethylformamide (DMF) and acetonitrile (ACN). The purpose of this work was to examine eutectic solvents as a “greener” alternative to conventional solvents so that quaternization reactions take place in accordance with the principles of green chemistry. Herein, sixteen eutectic solvents were used as replacements for volatile organic ones in quaternization reactions of isonicotinamide with substituted phenacyl bromides. The reactions were carried out at 80 °C by three synthetic approaches: conventional (4–6 h), microwave (20 min) and ultrasound (3 h). Microwave-assisted organic reactions produced the highest yields, where in several reactions, the yield was almost quantitative. The most suitable eutectic solvents were based on choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and glycerol, oxalic or levulinic acid as hydrogen bond donors (HBDs). The benefits of these three deep eutectic solvents (DESs) as a medium for quaternization reactions are the simplicity of their preparation for large-scale production, with inexpensive, available and nontoxic starting materials, as well as their biodegradability. Full article

In recent years, functionalized metal oxides have been gaining popularity for biomass conversion to fuels and chemicals due to the global energy crisis. This study reports a novel catalyst based on noble metal immobilization on functionalized zirconia that has been successfully used in the production of biofuel alkyl levulinates (ALs) from lignocellulosic biomass-derived levulinic acid (LA) under vapor-phase. The wet impregnation method was used to immobilize Pt-metal nanoparticles on zirconia-based supports (silicotungstic acid zirconia, STA-ZrO₂; sulfated zirconia, S-ZrO₂; and tetragonal zirconia, t-ZrO₂). A variety of physicochemical techniques were used to characterize the prepared catalysts, and these were tested under atmospheric pressure in continuous flow esterification of LA. The order of catalytic activity followed when ethyl levulinate was produced from levulinic acid via esterification: Pt/STA-ZrO₂ ≫ Pt/S-ZrO₂ ≫ Pt/t-ZrO₂. Moreover, it was found that ALs synthesis from LA with different alcohols utilizing Pt/STA-ZrO₂ catalyst followed the order ethyl levulinate ≫ methyl levulinate ≫ propyl levulinate≫ butyl levulinate. This work outlines an excellent approach to designing efficient catalysts for biofuels and value-added compounds made from biomass. Full article

Levulinic acid (LA) is one of the top twelve chemicals listed by the US Department of Energy that can be derived from biomass. It serves as a building block and platform chemical for producing a variety of chemicals, fuels and materials which are currently produced in fossil based refineries. LA is a key strategic chemical, as fuel grade chemicals and plastic substitutes can be produced by its catalytic conversion. LA derivatisation to various product streams, such as alkyl levulinates via esterification, γ-valerolactone via hydrogenation and N-substituted pyrrolidones via reductive amination and many other transformations of commercial utility are possible owing to the two oxygen functionalities, namely, carbonyl and carboxyl groups, present within the same substrate. Various biomass feedstock, such as agricultural wastes, marine macroalgae, and fresh water microalgae were successfully converted to LA in high yields. Finding a substitute to mineral acid catalysts for the conversion of biomass to LA is a challenge. The use of an ultrasound technique facilitated the production of promising nano-solid acid catalysts including Ga salt of molybophosphoric acid and Ga deposited mordenite zeolite, with optimum amounts of Lewis and Bronsted acidities needed for the conversion of glucose to LA in high yields, being 56 and 59.9 wt.% respectively. Microwave irradiation technology was successfully utilized for the accelerated production of LA (53 wt.%) from glucose in a short duration of 6 min, making use of the unique synergistic catalytic activity of ZnBr₂ and HCl. Full article

Organosulfonic acid-functionalized mesoporous silica is a class of heterogeneous acid catalysts used in esterification processes due to its high surface area, shape-selective properties, and strongly acidic sites. Since water is generated as a by-product of esterification, the surface of mesostructured silica is modified to enhance hydrophobicity and catalytic performance. In this study, a series of propylsulfonic acid-functionalized nanocomposites based on natural rubber and hexagonal mesoporous silica (NRHMS-SO₃H) with different acidities were prepared via an in situ sol-gel process using tetraethyl orthosilicate as the silica source, dodecylamine as the nonionic templating agent, and (3-mercaptopropyl)trimethoxysilane as the acid-functional group precursor. Compared with conventional propylsulfonic acid-functionalized hexagonal mesoporous silica (HMS-SO₃H), NRHMS-SO₃H provided higher hydrophobicity, while retaining mesoporosity and high surface area. The catalytic activity of synthesized solid acids was then evaluated via batch esterification of levulinic acid (LA) with alcohols (ethanol, n-propanol, and n-butanol) to produce alkyl levulinate esters. NRHMS-SO₃H exhibited higher catalytic activity than HMS-SO₃H and ultra-stable Y (HUSY) zeolite owing to the synergistic effect between the strongly acidic-functional group and surface hydrophobicity. The activation energy of the reaction over the NRHMS-SO₃H surface was lower than that of HUSY and HMS-SO₃H, suggesting that tuning the hydrophobicity and acidity on a nanocomposite surface is a compelling strategy for energy reduction to promote catalysis. Full article