Renewable Resources Robert-Jan van Putten,†,‡ Jan C. van der Waal,† Ed de Jong,*,† Carolus B. Rasrendra,‡,⊥ Hero J. Heeres,*,‡ and Johannes G. de Vries* †Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam, the Netherlands ‡Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands DSM Innovative Synthesis BV, P.O. Box 18, 6160 MD Geleen, the Netherlands Department of Chemical Engineering, Institut Teknologi Bandung, Ganesha 10, Bandung 40132, Indonesia

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources

Great attention has been given to metal–organic frameworks (MOFs)-derived solid bases because of their attractive structure and catalytic performance in various organic reactions. The extraordinary skeleton structure of MOFs provides many possibilities for incorporation of diverse basic functionalities, which is unachievable for conventional solid bases. The past decade has witnessed remarkable advances in this vibrant research area; however, MOFs for heterogeneous basic catalysis have never been reviewed until now. Therefore, a review summarizing MOFs-derived base catalysts is highly expected. In this review, we present an overview of the recent progress in MOFs-derived solid bases covering preparation, characterization, and catalytic applications. In the preparation section, the solid bases are divided into two categories, namely, MOFs with intrinsic basicity and MOFs with modified basicity. The basicity can originate from either metal sites or organic ligands. Different approaches used for generation o...

Metal-Organic Frameworks for Heterogeneous Basic Catalysis.

http://www.chtf.stuba.sk/~szolcsanyi/education/files/Chemia%20heterocyklickych%20zlucenin/Prednaska%207/Doplnkove%20studijne%20materialy/Hydroxymethylfurfural/Conversion%20of%20biomass%20platform%20molecules%20into%20fuel%20additives%20and%20liquid%20hydrocarbon%20fuels.pdf

Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels

The production of future transportation fuels and chemicals requires the deployment of new catalytic processes that transform biomass into valuable products under competitive conditions. Furfural has been identified as one of the most promising chemical platforms directly derived from biomass. With an annual production close to 300 kTon, furfural is currently a commodity chemical, and the technology for its production is largely established. The aim of this review is to discuss the most relevant chemical routes for converting furfural to chemicals, biofuels, and additives. This review focuses not only on industrially produced chemicals derived from furfural, but also on other not yet commercialised products that have a high potential for commercialisation as commodities. Other chemicals that are currently produced from oil but can also be derived from furfural are also reviewed. The chemical and engineering aspects such as the reaction conditions and mechanisms, as well as the main achievements and the challenges still to come in the pursuit of advancing the furfural-based industry, are highlighted.

/pdf/furfural-a-renewable-and-versatile-platform-molecule-for-the-4iuy4h5ydr.pdf

Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels

http://www.chtf.stuba.sk/~szolcsanyi/education/files/Chemia%20heterocyklickych%20zlucenin/Prednaska%207/Doplnkove%20studijne%20materialy/Hydroxymethylfurfural/Catalytic%20dehydration%20of%20C6%20carbohydrates%20for%20the%20production%20of%20HMF.pdf

Catalytic dehydration of C6 carbohydrates for the production of hydroxymethylfurfural (HMF) as a versatile platform chemical

The aldol condensation reactions of furfural/hydroxymethylfurfural (furfurals) with acetone/propanal in water–methanol solvents were studied over the solid base catalysts MgO–ZrO 2 , NaY and nitrogen-substituted NaY (Nit-NaY). The reactions were conducted at 120 °C and 750 psig of He in batch reactors. Nit-NaY exhibited catalytic activity for aldol condensation comparable to MgO–ZrO 2 and much higher than that of NaY, indicative of the increased base strength after replacing the bridging oxygen with the lower electronegativity nitrogen over Nit-NaY. The aldol condensation of furfurals with acetone produces two different products, the monomer and the dimer. The monomer is formed from reaction of furfurals with acetone. The dimer is formed from reaction of the monomer with furfurals. MgO–ZrO 2 had a higher selectivity towards dimer formation. In contrast, Nit-NaY was more selective towards the monomer product due to the cage size in the FAU structure, indicating that Nit-NaY is a shape selective base catalyst. Increasing the water concentration in the feed solution or increasing the feed concentration led to both increased catalytic activity and dimer selectivity. The Nit-NaY catalyst was not stable and lost catalytic activity when recycled due to leaching of the framework nitrogen. Different characterization techniques, including XRD, high resolution Ar adsorption isotherm, basic sites titration, CO 2 TPD-MS, TGA and 29 Si SP MAS NMR, were used here to characterize the fresh and spent catalysts. The results show that Nit-NaY maintains only part of the FAU-type crystal structure. Furthermore, the base strength over Nit-NaY was found to be between that of Mg 2+ –O 2− pair and Mg(OH) 2 . The reaction mechanism over Nit-NaY was discussed.

/pdf/liquid-phase-aldol-condensation-reactions-with-mgo-zro2-and-3gh1vc46f0.pdf

Wenqin Shen

Papers

Liquid phase aldol condensation reactions with MgO-ZrO2 and shape-selective nitrogen-substituted NaY

Vapor phase butanal self-condensation over unsupported and supported alkaline earth metal oxides