RESUMEN

The retro-aldol fragmentation of glucose is a complex reaction of industrial relevance, which provides a potentially sustainable route for the production of α-hydroxyester compounds of relevance to the green polymer industry, such as methyl lactate and methyl vinyl glycolate. Although the zeolite catalyst, Sn-Beta, has shown itself to be a promising catalyst for this process, important information concerning the stability of the catalyst during continuous operation is not yet known, and improvements to its yield of retro-aldol products are also essential. Here, we perform detailed spectroscopic studies of a selection of Sn-Beta catalysts and evaluate their performances for the retro-aldol fragmentation of glucose under continuous processing conditions, with the dual aims of developing new structure-activity-lifetime relationships for the reaction and maximizing the productivity and selectivity of the process. Kinetic studies are performed under both established reaction conditions and in the presence of additional promoters, including water and alkali salts. Generally, this study demonstrates that the reaction conditions and choice of catalyst cannot be optimized in isolation, since each catalyst explored in this study responds differently to each particular process perturbation. However, by evaluating each type of the Sn-Beta catalyst under each set of reaction conditions, we reveal that postsynthetic Sn-Beta catalysts exhibit the best levels of performance when activity, selectivity, and stability are taken into account. Specifically, the best levels of performance are obtained with a postsynthetic Sn-Beta catalyst that is preactivated in a flow of methanol prior to reaction, which provides α-hydroxyester yields over 90% at the early stages of continuous operation and operates at high yield and selectivity for over 60 h on stream. Space-time-yields over two orders of magnitude higher than any previously reported for this reaction are achieved, setting a new benchmark in terms of the retro-aldol fragmentation of glucose.

RESUMEN

The direct and quantitative identification of active sites is crucial for the development of zeolite catalysts and their implementation in industry. Herein we report on the application of one-dimensional 119Sn direct polarization (DP) and rotational echo double-resonance (REDOR) and two-dimensional 119Sn magic-angle tuning (MAT) NMR spectroscopy for the identification of different Sn sites in fully dehydrated Sn-BEA zeolite. It is demonstrated that 119Sn magic-angle spinning (MAS) NMR techniques, modified by Carr-Purcell-Meiboom-Gill (CPMG) echo-train acquisition allow to resolve three groups of NMR signals, which can be attributed to three groups of nonequivalent T-sites based on the existing theoretical predictions: (I) T9, T4, and T3; (II) T2, T1, and T8; and (III) T7, T5, and T6. Results suggest that the sites attributed to group III are the most populated in Sn-BEA samples obtained via the fluoride route. The attribution of NMR lines to different T-sites in the structure of BEA allows for the establishment of structure-reactivity relationship and therefore for further improvement of Sn-BEA catalysts.

RESUMEN

Alkali-metal ions have recently been shown to strongly influence the catalytic behavior of stannosilicates in the conversion of carbohydrates. An effect of having alkali-metal ions present is a pronounced increase in selectivity towards methyl lactate. Mechanistic details of this effect have remained obscure and are herein addressed experimentally through kinetic experiments and isotope tracking. The presence of alkali-metal ions has a differential effect in competing reaction pathways and promotes the rate of carbon-carbon bond breakage of carbohydrate substrates, but decreases the rates of competing dehydration pathways. Further addition of alkali-metal ions inhibits the activity of Sn-Beta in all major reaction pathways. The alkali-metal effects on product distribution and on the rate of product formation are similar, thus pointing to a kinetic reaction control and to irreversible reaction steps in the main pathways. Additionally, an effect of the accompanying basic anions is shown, supposedly facilitating the cation exchange and eliciting a different concentration-dependent effect to that of neutral alkali-metal salts.

RESUMEN

The future role of biomass-derived chemicals relies on the formation of diverse functional monomers in high yields from carbohydrates. Recently, it has become clear that a series of α-hydroxy acids, esters, and lactones can be formed from carbohydrates in alcohol and water solvents using tin-containing catalysts such as Sn-Beta. These compounds are potential building blocks for polyesters bearing additional olefin and alcohol functionalities. An NMR approach was used to identify, quantify, and optimize the formation of these building blocks in the Sn-Beta-catalyzed transformation of abundant carbohydrates. Record yields of the target molecules can be achieved by obstructing competing reactions through solvent selection.

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RESUMEN

A highly selective self-condensation of glycolaldehyde to different C4 molecules has been achieved using Lewis acidic stannosilicate catalysts in water at moderate temperatures (40-100 °C). The medium-sized zeolite pores (10-membered ring framework) in Sn-MFI facilitate the formation of tetrose sugars while hindering consecutive aldol reactions leading to hexose sugars. High yields of tetrose sugars (74 %) with minor amounts of vinyl glycolic acid (VGA), an α-hydroxyacid, are obtained using Sn-MFI with selectivities towards C4 products reaching 97 %. Tin catalysts having large pores or no pore structure (Sn-Beta, Sn-MCM-41, Sn-SBA-15, tin chloride) led to lower selectivities for C4 sugars due to formation of hexose sugars. In the case of Sn-Beta, VGA is the main product (30 %), illustrating differences in selectivity of the Sn sites in the different frameworks. Under optimized conditions, GA can undergo further conversion, leading to yields of up to 44 % of VGA using Sn-MFI in water. The use of Sn-MFI offers multiple possibilities for valorization of biomass-derived GA in water under mild conditions selectively producing C4 molecules.

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RESUMEN

(119)Sn CPMG MAS NMR is demonstrated to be a fast and efficient method for characterization of Sn-sites in Sn-containing zeolites. Tuning of the CPMG echo-train sequence decreases the experimental time by a factor of 5-40 in the case of as-synthesized and hydrated Sn-BEA samples and by 3 orders of magnitude in the case of dehydrated Sn-BEA samples as compared to conventional methods. In the latter case, the reconstruction of the quantitative spectrum without the loss of sensitivity is shown to be possible. The method proposed allows obtaining (119)Sn MAS NMR spectra with improved resolution for Sn-BEA zeolites with natural (119)Sn isotope abundance using conventional MAS NMR equipment.

RESUMEN

This study focuses on increasing the selectivity to methyl lactate from sugars using stannosilicates as heterogeneous catalyst. All group I ions are found to have a promoting effect on the resulting methyl lactate yield. Besides, the alkali ions can be added both during the preparation of the catalyst or directly to the solvent mixture to achieve the highest reported yield of methyl lactate (ca. 75 %) from sucrose at 170 °C in methanol. The beneficial effect of adding alkali to the reaction media applies not only to highly defect-free Sn-Beta prepared through the fluoride route, but also to materials prepared by post-treatment of dealuminated commercial Beta zeolites, as well as ordered mesoporous stannosilicates, in this case Sn-MCM-41 and Sn-SBA-15. These findings open the door to the possibility of using other preparation methods or different Sn-containing silicates with equally high methyl lactate yields as Sn-Beta.

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