1708-43-6

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InChI:InChI=1/C8H10O4/c9-6-4-11-8(12-5-6)7-2-1-3-10-7/h1-3,6,8-9H,4-5H2

Upstream product

• 98-01-1 furfural 
• 56-81-5 glycerol 

Relevant academic research and scientific papers

Modified boehmite: A choice of catalyst for the selective conversion of glycerol to five-membered dioxolane

The choice of the active site and support matrix decides the activity of a catalyst. Any modifications on these will have a significant impact on the reactivity and selectivity of the catalyst. Here, we have synthesised WO3-loaded boehmite and applied it for the acetalization of a biomass-derived bulk chemical, glycerol. The well-characterized acid catalyst exhibits a selective acetalization of glycerol with good conversions into a five-membered dioxolane product. The cyclability of the catalyst up to six times along with the retention of the catalytic activity ensures the heterogeneity of the material.

Structure–Activity Relationships of WOx-Promoted TiO2–ZrO2 Solid Acid Catalyst for Acetalization and Ketalization of Glycerol towards Biofuel Additives

Abstract: WOx-promoted TiO2–ZrO2 solid acid catalyst was prepared and applied in the catalytic acetalization and ketalization of glycerol with carbonyl compounds to produce biofuel additives. The presence of WOx promoter and TiO2 remarkably improved the catalytic activity of ZrO2. Approximately, 100% glycerol conversion was evidenced with non-bulky aliphatic aldehydes and ketones like, propanol and cyclohexanone. The physical characterization of WOx-promoted TiO2–ZrO2, revealed a higher formation of tetragonal crystalline phase of ZrO2, over monoclinic. The total surface acidity and the ratio of Br?nsted to Lewis acidic site concentrations were determined by NH3-TPD and pyridine-chemisorbed FTIR spectroscopy, respectively. A considerably higher concentration of Lewis acidic sites, ~ 213.29?μmol/gm, was evidenced on the WOx-promoted TiO2–ZrO2 catalyst surface. Catalytic activity study revealed a direct correlation between the surface Lewis acidic site concentration and the activity of catalyst. This significant observation indicated the key role of Lewis acidic sites in this catalytic process. The WOx-promoted TiO2–ZrO2 catalyst was also considerably stable and showed good performance in the acetalization/ketalization of glycerol with other substituted carbonyl compounds. Graphic Abstract: The WOx-promoted TiO2–ZrO2 solid acid catalyst exhibits superior catalytic performance for acetalization and ketalization of glycerol with carbonyl compounds to produce biofuel additives. [Figure not available: see fulltext.].

Low temperature synthesis of bio-fuel additives via valorisation of glycerol with benzaldehyde as well as furfural over a novel sustainable catalyst, 12-tungstosilicic acid anchored to ordered cubic nano-porous MCM-48

The present article demonstrates designing of novel catalyst, 12-tungstosilicic acid (TSA) anchored to ordered nano-porous MCM-48 (nMCM-48); TSA/nMCM-48, characterization and evaluation for synthesis of bio-fuel additives via glycerol valorisation with aromatic aldehydes. The nanopores of support were confirmed by BET and TEM while the interaction between TSA and nMCM-48 was confirmed by decrease in the surface area and pore volume of the catalysts. Assessment of vital reaction parameters (% loading of active species, mole ratio of reactants, catalyst amount, temperature and time) were performed to achieve maximum conversion of glycerol. The catalyst showed noteworthy performance at 30 °C towards conversion (>85 %) and thermodynamically stable dioxane derivative (>60 %) with remarkable TON (5945 for benzaldehyde and 7355 for furfural). The catalyst was regenerated and used for successive four catalytic runs with almost same activity. The superiority of novel catalyst is because of its geometry and nano porosity.

Graphene-promoted acetalisation of glycerol under acid-free conditions

Serendipity led us to unveil unexpected and uncovered properties of graphene for the acetalisation of glycerol with both aldehydes and ketones, furnishing an acid-free process for fuel bio-additive candidates. Mechanistic studies ruled out the intervention of residual acidic species or metallic cations at the surface of graphene, and therefore, the peculiar electronic properties of graphene are most probably responsible for this unforeseen reactivity. Recycling studies revealed the robustness of graphene under the experimental conditions since only a marginal erosion of the reaction yield was observed after six cycles.

Clay catalysed rapid valorization of glycerol towards cyclic acetals and ketals

Biodiesel production usually results in a huge amount of glycerol, raising a critical need to transform it into high value products. The present study highlights that solvent-free, conventional thermal activation, and non-conventional microwave/ultrasonic activation in the liquid phase are able to selectively transform glycerol into cyclic acetals and ketals using an optimised acid activated clay catalyst. Several parameters for the acid activation of bentonite clay were optimized under mild reaction conditions with a high concentration of clay (6%) and varying the acid concentration in the range of 6 to 15 N. The acid-activated clay samples were characterized by XRD, FT-IR, BET, and XRF analysis. The active sites of the catalyst were examined by volumetric titration and confirmed by pyridine adsorbed FT-IR and advanced NH3-TPD analyses. The activation performed at relatively mild conditions, i.e.; 6 N H2SO4 and 6% w/v clay, reproducibly resulted in an improved surface area (180 m2 g-1) and surface acidity (23 mg KOH g-1), with superior quantitative Br?nsted and Lewis acidic sites. Moreover, the eco-friendly process involving a catalyst, microwave, or ultra-sonication were successfully utilized to achieve a commercially valuable hyacinth fragrance, in addition to furan-based fuel additive precursors exhibiting a high conversion of glycerol and excellent selectivity within much less activation time (2 min).

Eco-friendly synthesis of bio-additive fuels from renewable glycerol using nanocrystalline SnO2-based solid acids

The present work has been undertaken with an aim to synthesize valuable bio-additive fuels from glycerol acetalization using SnO2-based solid acids. Various promoters, namely SO42-, MoO3 and WO3 were incorporated to the SnO2 using a wet-impregnation method. An extensive physicochemical characterization has been achieved by means of XRD, BET surface area, BJH analysis, FT-IR, pyridine adsorbed FT-IR, NH3-TPD, ICP-OES and XPS techniques. The BET surface area of SnO2 is significantly improved from 11 to 32, 56 and 41 m2 g-1 after the addition of the WO3, MoO 3, and SO42- promoters, respectively. The XPS studies revealed that Sn is present in the +4 oxidation state, whereas Mo, W and S are in the +6 oxidation state in the prepared samples. In addition, the SO42-/SnO2 sample contained super acidic sites, along with strong- and medium-acidic sites. The amount of acidic sites was found to be 46.47, 61.81, 81.45 and 186.98 μmol g-1 for the SnO2, WO3/SnO2, MoO3/SnO 2, and SO42-/SnO2 samples, respectively. The pyridine adsorbed FT-IR studies revealed the existence of a superior quantity of Bronsted acidic sites than Lewis acidic sites in the synthesized catalysts. Promoted SnO2 catalysts exhibited a promising catalytic performance for glycerol acetalization with acetone and furfural, and the activity of the catalysts was found to increase in the following order: SnO2 3/SnO2 3/ SnO2 42-/SnO2. The outstanding performance of the SO42-/SnO2 catalyst is mainly due to the existence of a large amount of acidic sites associated with the super acidic sites. The achieved optimum glycerol conversions with acetone and furfural were ~98 and 99% over the SO 42-/SnO2 catalyst, respectively.

Conversion of platform chemical glycerol to cyclic acetals promoted by acidic ionic liquids

The condensation of glycerol, a platform chemical from renewable materials, with benzaldehyde to generate cyclic acetals was investigated using acidic ionic liquid as catalyst. Evidence was presented that the product mixture of 4-hydroxymethyl-2-phenyl-1,3-dioxolane and 5-hydroxyl-2-phenyl-1,3-dioxane, with cis and trans two stereo-isomers for each one identified by 1H NMR were obtained. Further modification of reaction conditions promoted by N-butyl-pyridinium bisulfate ([BPy]HSO4) led to the totally cyclic acetals with 99.8% yield at room temperature. A micro water-removal reactor constituted by ionic liquids was proposed, which favourably shifted the condensation equilibrium to the product side by transferring the produced water out of the organic phase in time, so that the water-carrying agent or reactive distillation was avoided. Moreover, the product separation made this methodology more accessible to sustainable green biomass chemistry.

Al-SBA-15 catalysed cross-esterification and acetalisation of biomass-derived platform chemicals

Al-SBA-15 exhibited excellent catalytic activities in acid-catalysed glycerol transformation including esterification and acetalisation reactions. Quantitative conversion and good selectivities to mono- and diacetylglycerides could be obtained in the esterification of glycerol with levulinic acid. The catalyst also proved to be very effective in the acetalisation of glycerol with aldehydes and acetone, with an interesting selectivity switch from the 6-membered acetal (using paraformaldehyde as an aldehyde source) to a 5-membered acetal (when benzaldehyde or furfural was employed). Al-SBA-15 materials were also proved to be highly stable and reusable in most glycerol transformations under the investigated reaction conditions.

Selective glycerol transformations to high value-added products catalysed by aluminosilicate-supported iron oxide nanoparticles

Conversion of glycerol to cyclic acetals (with paraformaldehyde, benzaldehyde, furfural and acetone) and to mono-, di- and triacetylglycerides (with levulinic acid) was investigated using a supported iron oxide nanoparticle system of a mesoporous aluminosilicate heterogeneous catalyst (Fe/Al-SBA-15). The effect of various parameters on the reaction, temperature, mol% of catalyst or ratio of glycerol:substrate were studied. An optimization of the reaction conditions carried out with glycerol by means of experimental design methodology showed that a very high glycerol conversion (99%) and high combined selectivity toward di- and triacetylglycerides could be obtained under optimized conditions. All of the acetalisation reactions carried out at 100 °C also gave good to excellent conversions and selectivities to target products, illustrating the potential of Fe/Al-SBA-15 as a highly active, stable and reusable heterogeneous catalyst in glycerol acid-catalysed transformations.

Design of highly efficient Mo and W-promoted SnO2 solid acids for heterogeneous catalysis: Acetalization of bio-glycerol

Development of highly promising solid acids is one of the key technologies to meet the essential challenges of economical and environmental concerns. Thus, novel molybdenum and tungsten promoted SnO2 solid acids (wet-impregnation) and pure SnO2 (fusion method) were prepared. The synthesized catalysts were systematically analyzed using various techniques, namely, XRD, BET surface area, pore size distribution, XPS, FTIR, FTIR of adsorbed pyridine, Raman, NH3-TPD, and H2-TPR. XRD results suggested formation of nanocrystalline SnO2 solid solutions due to the incorporation of molybdenum and tungsten cations into the SnO2 lattice. All the materials exhibited smaller crystallite size, remarkable porosity, and high specific surface area. Raman measurements suggested the formation of more oxygen vacancy defects in the doped catalysts, and the TPR results confirmed facile reduction of the doped SnO2. NH 3-TPD studies revealed the beneficial role of molybdenum and tungsten oxides on the acidic properties of the SnO2. FTIR studies of adsorbed pyridine showed the existence of a larger number of Bronsted acidic sites compared to Lewis acidic sites in the prepared catalysts. The resulting catalysts are found to be efficient solid acids for acetalization of glycerol with acetone, furfural, and its derivatives under solvent-free and ambient temperature conditions. Particularly, the Mo6+-doped SnO 2 catalyst exhibited excellent catalytic performance in terms of both glycerol conversion and selectivity of the products. The increased presence of acidic sites and enhanced specific surface area, accompanied by notable redox properties and superior lattice defects are found to be the decisive factors for better catalytic activity of the Mo6+-doped SnO2 sample. The investigated SnO2 solid acids represent a novel class of heterogeneous catalysts useful for the transformation of glycerol to value-added products in an eco-friendly manner.