Synthesis Of GVL Research Articles

Recent advances on bifunctional catalysts for one-pot conversion of furfural to γ-valerolactone

γ-Valerolactone (GVL) is one of the most valuable compounds derived from furfural (FAL), which has been industrially produced from agricultural byproducts like corn cobs. It is extremely challenging to synthesize GVL from FAL efficiently via a one-pot cascade reaction due to the need for multiple active sites in a single pot. By focusing on the aspects of one-pot synthesis of GVL from FAL, the authors aim to shed light on the rational design and utilization of environmentally friendly bifunctional catalysts with high efficiency in this reaction. Perspectives regarding future research opportunities in bi- or multi-functional catalysts for one-pot GVL synthesis are also discussed.

Effective one‐pot tandem synthesis of γ‐valerolactone from biogenic furfural over zirconium phosphate catalyst

Abstractγ‐Valerolactone (GVL) is a renowned starting material in production of bio‐fuels, valuable chemicals and polymers. The one‐pot tandem synthesis of GVL from furfural without a cumbersome intermediate separation/purification process is highly desired, yet the transformation remains challenging owing to the complicated reaction routes. Zirconium phosphate (ZrPO), a cheap and easily prepared solid catalyst with Lewis–Brønsted dual acidity, is herein discovered to enable one‐pot tandem transformation of furfural into GVL with using 2‐propanol as H‐donor/solvent to proceed smoothly. In addition, ZrPO prepared by hydrothermal method exhibits superior catalytic performance in comparison with the counterpart prepared by co‐precipitation method, giving a 42.7% yield of GVL at 180 °C. The difference in catalytic activity between ZrPO materials prepared by hydrothermal method and co‐precipitation method is linked with their morphology and acid sites density. Furthermore, the as‐prepared ZrPO catalyst works in a heterogeneous manner and can be reused for multiple times without significant deactivation. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd

Cascade Upgrading of Biomass-Derived Furfural to γ-Valerolactone Over Zr/Hf-Based Catalysts.

Biomass feedstocks are promising candidates of renewable clean energy. The development and utilization of biological energy is in line with the concept of sustainable development and circular economy. As an important platform chemical, γ-valerolactone (GVL) is often used as green solvent and biofuel additive. Regarding this, the efficient synthesis of GVL from biomass derivative furfural (FF) has attracted wide attention recently, However, suitable catalyst with appropriate acid-base sites is required due to the complex reaction progress. In this Mini Review, the research progress of catalytic synthesis of GVL from furfural by Zr/Hf-based catalysts was reviewed. The different effects of Lewis acid-base and Brønsted acid sites in the catalysts on each steps in the reaction process were discussed firstly. Then the effects of regulation of acid-base sites in the catalysts was also studied. Finally, the advantages and challenges of Zr/Hf-based catalysts in FF converted to GVL system were proposed.

Noble Metal-Free Hierarchical ZrY Zeolite Efficient for Hydrogenation of Biomass-Derived Levulinic Acid.

Developing a low-cost and robust catalyst for efficient transformation of biomass-derived platform chemicals plays a crucial role in the synthesis of future transportation fuels. Herein, a post-synthetic strategy was employed to develop a noble metal-free and robust ZrY zeolite catalyst, which is efficient for the hydrogenation of biomass-derived levulinic acid (LA) into biofuel γ-valerolactone (GVL), whereas over 95% yield of GVL was achieved in 10 h at 220°C. The effects of acidic properties from ZrY catalysts and various reaction parameters on the catalytic performance were then discussed in detail. Subsequently, different characterization tools were used to compare the difference and relationship of structure activity between the fresh and spent ZrY catalysts. It was found that acidity and the metal–support interaction were important for the direct synthesis of GVL. This work provides a guideline to design a noble metal-free catalyst for high-value utilization of biomass-derived sources.

Aqueous-phase hydrogenation of levulinic acid over carbon layer protected silica-supported cobalt-ruthenium catalysts

The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) by using water as solvent is a crucial process in the production of fine chemicals from biomass. An ultrathin carbon layer coating CoRu bimetallic catalyst supported on silica ([email protected]/SiO2) is prepared by using tannis-ligated cobalt-ruthenium complex on silica as precursors, and applied for catalyzed synthesis of GVL from LA. Because of the synergistic effect between cobalt and ruthenium, the addition of small amounts of Ru to Co catalysts can increase the catalytic activity in the aqueous hydrogenation of LA. The ultrathin carbon layer covered on the CoRu bimetallic catalyst can greatly reduce the leaching of active metals. The [email protected]/SiO2 catalyst achieves high stability and is reused up to 5 runs without significant loss of performance in aqueous hydrogenation of levulinic acid.

Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ-Valerolactone Over Ni Supported on Equilibrium Fluid-Catalytic-Cracking Catalysts

Nickel supported on equilibrium fluid-catalytic-cracking catalysts (Ni/E-cats) were prepared by a simple grinding-pyrolysis method and employed for the transfer hydrogenation of ethyl levulinate (EL) to γ-valerolactone (GVL). 96.2% selectivity of GVL and 90.3% conversion of EL were obtained at 180 °C for 6 h over 30-Ni/E-cat. Through XRD, N2 adsorption–desorption, NH3-TPD and SEM analysis, the high activity of the 30-Ni/E-cat catalyst was attributed to its dispersed Ni metal active centers and available acidic sites. Catalytic probe test revealed that metal and acid sites of Ni/E-cat played a synergistic catalytic role in the synthesis of GVL in 2-propanol, where Ni metal sites contribute to the hydrogenation of ketone group in EL, and acid sites of E-cat promoted the lactonization of intermediate ethyl- or isopropyl 4-hydroxyvalerate. Two reaction pathways and synergistic mechanism were proposed in this catalytic system. Moreover, Ni/E-cat catalyst exhibited good stability up to four cycles without obvious loss of catalytic activity.

Heterogeneous Catalytic Hydrogenation of Levulinic Acid to γ-Valerolactone with Formic Acid as Internal Hydrogen Source.

As one of the most promising biomass-based platform molecules, γ-valerolactone (GVL) can be synthesized from a variety of lignocellulosic feedstocks through different hydrogen supply pathways. Among these transformation routes, the hydrogenation of levulinic acid (LA) to GVL by using formic acid (FA) as the internal hydrogen source is regarded as a critical path for the sustainable development of renewable energy systems. Although a large number of studies on the synthesis of GVL have been reported, the FA/LA catalytic system has not been interpreted as thoroughly as it should be. In this Minireview, core concerns are focused on key issues and their effects in this FA/LA catalytic system. The catalytic mechanism, together with competitive adsorption behavior between FA and LA on heterogeneous catalysts, is presented. The effects of active metal species and catalyst supports on the overall catalytic performance are summarized, and the influences of key condition parameters, including the time, temperature, FA/LA molar ratios, and aqueous solvent, are discussed. In particular, impacts and improvements of coke deposition and metal leaching, which could greatly affect the catalyst stability, are analyzed in detail. Additionally, several feasible suggestions for the enhancement of the catalytic efficiency and stability are also proposed.

ZrO2-SBA-15 catalysts for the one-pot cascade synthesis of GVL from furfural

Controlling the zirconia coating thickness in ZrO2-SBA-15 materials allows tuning their catalytic performance in the one-pot transformation of furfural into GVL.

Novel synthesis of Ru/OMS catalyst by solvent-free method: Selective hydrogenation of levulinic acid to γ-valerolactone in aqueous medium and kinetic modelling

γ-Valerolactone (GVL) is an important bio-derived molecule that could be used for the sustainable production of value-added chemicals and fuels. It is mainly synthesized by hydrogenation of levulinic acid by using supported ruthenium catalyst. Here we are reporting the synthesis of ruthenium supported on manganese oxide octahedral molecular sieve (OMS-2) catalyst prepared by different methods. Three different methods, i.e. reflux, hydrothermal and solventless protocols were used for the preparation of OMS-2. The prepared catalysts were used for the selective hydrogenation of biomass-derived levulinic acid (LA) to GVL using molecular hydrogen in water. Solventless synthesized OMS (OMS-2S) is energy efficient, rapid and economical way of synthesis. Among three different catalysts, Ru supported on solventless OMS-2 i.e. 1 wt% Ru/OMS-2S catalyst showed LA conversion of 99.9% and yield of 99.8% towards GVL in 1 h with the overall turnover frequency of 0.95 s−1 at mild conditions (100 °C, 30 atm H2). Different OMS-2 supported Ru catalysts showed a very high turnover frequency in comparison with those reported in literature for the synthesis of GVL. The specific textural and chemical properties of catalysts were characterized by various techniques. Moreover, 1 wt% Ru/OMS-2S catalyst was reusable up to four times without significant loss of activity and was very stable. By studying the effects of different process parameters, a kinetic model was developed based on LHHW type of mechanism. The apparent activation energy for LA hydrogenation to GVL is 11.75 kcal/mol.

Porous Ti/Zr Microspheres for Efficient Transfer Hydrogenation of Biobased Ethyl Levulinate to γ-Valerolactone.

γ-Valerolactone (GVL) is one of the versatile platform molecules and biofuel additives derived from the lignocellulosic biomass. Herein, the efficient synthesis of GVL from biobased ethyl levulinate (EL) using alcohol as both H-donor and solvent without an external hydrogen source has been achieved over porous Ti/Zr microspheres. The catalysts (TixZry) with different Ti/Zr molar ratios were synthesized using hexadecylamine (HDA) as a structure-directing agent via a sol–gel process combined with solvothermal treatment and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, thermal gravimetric analysis, NH3/CO2-TPD, N2 adsorption–desorption, and pyridine-IR. A high GVL yield of 90.1% at 100% EL conversion was obtained at 180 °C for 6 h over Ti2Zr8 in 2-propanol. The microspheric and porous structure, enhanced surface areas, and acid/base contents by the proper introduction of Ti species into Zr oxide were demonstrated to be responsible for the pronounced performance. The microspheric Ti2Zr8 porous catalyst could be reused at least six times with no decrease in catalytic activity.

Continuous Synthesis of γ-Valerolactone in a Trickle-Bed Reactor over Supported Nickel Catalysts

Various Ni-based catalysts were tested in the continuous liquid phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) in a trickle-bed reactor using water as solvent with the aim to develop an economic and environmentally friendly way for the GVL synthesis. For this purpose, various synthesis methods were used to prepare Ni-based catalysts, which were first screened in batch reactors. Characterization by X-ray diffraction, temperature-programmed reduction, electron microscopy, hydrogen chemisorption, and X-ray absorption spectroscopy showed that slow precipitation using urea resulted in a good Ni dispersion. The dispersion also improved at lower Ni loading, and smaller Ni particles mostly showed an enhanced catalytic performance for the synthesis of GVL. 5 wt % Ni/Al2O3 prepared by wet impregnation showed the highest specific activity for the hydrogenation of LA to GVL (90% LA conversion and 75% GVL yield) featuring an average Ni particle size of 6 nm. Some deactivation of the catalysts was ...

Catalytic Transfer Hydrogenation of Biomass-Derived Levulinic Acid and Its Esters to γ-Valerolactone over Sulfonic Acid-Functionalized UiO-66

Production of γ-valerolactone (GVL) from biomass-derived levulinic acid and its esters via a catalytic transfer hydrogenation (CTH) process over sulfonic acid-functionalized UiO-66, a microporous zirconium-based metal–organic framework (Zr-MOF), is reported herein. On the basis of comprehensive structural analyses by means of XRD, N2 physisorption, IR, TG, and Zr K-edge XAFS, we show that free sulfonic acid (−SO3H) groups can uniformly be tethered on a UiO-66 framework without affecting the coordination state of Zr atoms, while crystallinity and surface area decrease along with the functionalization. As a consequence, UiO-66 bearing a 60 mol % fraction of sulfonic acid-containing benzene dicarboxylate (BDC) linker and retaining a high surface area exhibits the highest catalytic activity in the CTH reaction of levulinic acid and its esters to give GVL with the maximum GVL yield of up to 85% at 140 °C. Comparative experiments, together with characterization results, reveal that the high catalytic activity is provided by the cooperative effect between Lewis-basic Zr6O4(OH)4 clusters and Brönsted-acidic −SO3H sites arranged in a confined nanospace adjacently with each other, which catalyze the CTH reaction of levulinic acid and its esters and facilitate successive intramolecular dealcoholization to afford GVL, respectively. The catalyst is reusable during repeated cycles without appreciable loss of activity and selectivity, shows broad scopes toward substrates and alcohols, and also allows direct synthesis of GVL from furfural, making this material a promising candidate for efficient GVL production from biomass resources.

ChemInform Abstract: Synthesis of γ‐Valerolactone from Carbohydrates and Its Applications

AbstractReview: 88 refs.

Synthesis of γ‐Valerolactone from Carbohydrates and its Applications

γ-Valerolactone (GVL) is a valuable chemical intermediate that can be obtained by catalytic reduction of levulinic acid (LA) or alkyl levulinates (AL). There are many reports on the synthesis of GVL from LA or AL. However, the demand for the large-scale synthesis of GVL requires more environmentally friendly and cost-effective production processes. This article focuses on the recent advance in the synthesis of GVL from carbohydrates or lignocellulosic biomass. In addition, application of GVL as the reaction solvents, fuel additives, and as precursor for the synthesis of jet fuel and polymer monomers is also discussed.

Direct Catalytic Transformation of Biomass Derivatives into Biofuel Component γ-Valerolactone with Magnetic Nickel-Zirconium Nanoparticles.

A series of mixed oxide nanoparticles were prepared by a coprecipitation method and characterized by many techniques. Nickel-zirconium oxide catalysts and their partially reduced magnetic counterparts were highly efficient in the direct transformation of biomass derivatives, including ethyl levulinate, fructose, glucose, cellobiose, and carboxymethyl cellulose, into γ-valerolactone (GVL) without the use of an external hydrogen source, producing a maximum GVL yield of 95.2 % at 200 °C for 3 h with hydrogen-reduced magnetic Zr5 Ni5 nanoparticles (<20 nm). The acid-base bifunctionality of these nanocatalysts plays a synergic role in the synthesis of GVL in alcohols, whereas appropriate control of the nickel/zirconium molar ratio is able to improve the selectivity towards GVL (≈98 %), along with high formation rates (up to 54.9 mmol g-1 h-1 ). Moreover, the magnetic Zr5 Ni5 nanoparticles were conveniently recovered by means of a magnet for five cycles with almost constant activity.

An integrated strategy for the conversion of cellulosic biomass into γ-valerolactone

A new integrated strategy for the synthesis of GVL from beechwood based on the use of 2-MeTHF and RANEY® Ni is presented.

Combined dehydration/(transfer)-hydrogenation of C6-sugars (D-glucose and D-fructose) to γ-valerolactone using ruthenium catalysts

γ-Valerolactone (GVL) is considered a very interesting green, bio-based platform chemical with high application potential. We here describe research activities on the one-pot catalytic synthesis of GVL from C6-sugar sources (D-glucose, D-fructose, sucrose and cellulose) using an acid catalyst in combination with a hydrogenation catalyst (Ru/C) and either molecular hydrogen or formic acid as the hydrogen donor. When using formic acid, the highest yield of GVL (52 mol%) was obtained at 180 °C, 16 h reaction time and D-fructose as the C6-sugar source. The major by-products were insoluble solids, known as humins, formed during the acid catalysed conversion of D-fructose to the intermediate levulinic acid (LA). When using molecular hydrogen as the hydrogen source, the highest yield of GVL (62 mol%) was obtained using D-fructose in combination with TFA and Ru/C in water (180 °C, 94 bar H2, 8 h). Complete conversion of D-fructose was observed at these conditions. The major by-products were formic acid and insoluble solid materials (humins). The use of a pre-formed homogeneous water soluble ruthenium catalysts from RuCl3 and tris(3-sulfonatophenyl)phosphane (TPPTS) in combination with TFA gave quantitative C6-sugar conversions but a lower GVL yield (23 mol%) compared to the heterogeneous Ru catalyst.