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

Conversion of Biomass into Chemicals over Metal Catalysts

Green and sustainable manufacture of chemicals from biomass: state of the art

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

Based on the principles and metrics of green chemistry and sustainable development, biocatalysis is both a green and sustainable technology. This is largely a result of the spectacular advances in molecular biology and biotechnology achieved in the past two decades. Protein engineering has enabled the optimization of existing enzymes and the invention of entirely new biocatalytic reactions that were previously unknown in Nature. It is now eminently feasible to develop enzymatic transformations to fit predefined parameters, resulting in processes that are truly sustainable by design. This approach has successfully been applied, for example, in the industrial synthesis of active pharmaceutical ingredients. In addition to the use of protein engineering, other aspects of biocatalysis engineering, such as substrate, medium, and reactor engineering, can be utilized to improve the efficiency and cost-effectiveness and, hence, the sustainability of biocatalytic reactions. Furthermore, immobilization of an enzyme ...

/pdf/role-of-biocatalysis-in-sustainable-chemistry-5b3e0qe0ep.pdf

Role of Biocatalysis in Sustainable Chemistry

The electrocatalytic conversion of furanic compounds, i.e. mainly furfural and 5-hydroxymethylfurfural, has recently emerged as a potentially scalable technology for both oxidation and hydrogenation processes because of its highly valuable products. However, its practical application in industry is currently limited by low catalytic activity and product selectivity. Thus, a better understanding of the catalytic reactions as well as a strategy for the catalyst design can bring solutions for a complete and selective conversion into desired products. In this perspective, we review the status and challenges of electrocatalytic oxidation and hydrogenation of furanic compounds, including thermodynamics, voltammetric studies, and bulk electrolysis with important reaction parameters (i.e., catalyst, electrolyte, temperature, etc.) and reaction mechanisms. In addition, we introduce methods of energy-efficient electrocatalytic furanic synthesis by combining yields of anodic and cathodic reactions in a paired reacto...

Electrocatalytic Conversion of Furanic Compounds

5-Hydroxymethylfurfural (HMF) is considered an important building block for future bio-based chemicals. Here, we present an experimental study using different ketoses (fructose, sorbose, tagatose) and aldoses (glucose, mannose, galactose) under aqueous acidic conditions (65gL(-1) substrate, 100-160 degrees C, 33-300mM H2SO4) to gain insights into reaction pathways for hexose dehydration to HMF. Both reaction rates and HMF selectivities were significantly higher for ketoses than for aldoses, which is in line with literature. Screening and kinetic experiments showed that the reactivity of the different ketoses is a function of the hydroxyl group orientation at the C3 and C4 positions. These results, in combination with DFT calculations, point to a dehydration mechanism involving cyclic intermediates. For aldoses, no influence of the hydroxyl group orientation was observed, indicating a different rate-determining step. The combination of the knowledge from the literature and the findings in this work indicates that aldoses require an isomerization to ketose prior to dehydration to obtain high HMF yields.

Dehydration of Different Ketoses and Aldoses to 5-Hydroxymethylfurfural

A challenge of today’s industry is to transform low-value side products into more value-added materials. Humins, a byproduct derived from sugar conversion processes, can be transformed into high value-added products. Thermosetting furanic composites were elaborated with cellulose filters. Large quantities of humins were included into a polyfuranic thermosetting network. Comparisons were made with composites generated with polyfurfuryl alcohol (PFA) and with PFA/lignin. It was concluded that new chemical interactions were created between the side-chain oxygen groups of the humins and the PFA network. Analysis of the fracture surface of the composites containing humins lead to the conclusion that higher interfacial bonding and more efficient stress transfer between the matrix and the fibers is present. The higher ductility of the humins-based matrix allows for a two-fold higher tensile strength in comparison with other composites tested. Incorporation of humins decreases the brittleness of the furanic compo...

Valorization of Biorefinery Side-Stream Products: Combination of Humins with Polyfurfuryl Alcohol for Composite Elaboration

Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels-Alder (DA) aromatization route, to effectively block retro-DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal-based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80% selectivity in a solid-phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H-Y was found to perform the best and can be easily reused after calcination.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/ange.201509346

Jan C. van der Waal

Papers

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources

Electrocatalytic Conversion of Furanic Compounds

Dehydration of Different Ketoses and Aldoses to 5-Hydroxymethylfurfural

Valorization of Biorefinery Side-Stream Products: Combination of Humins with Polyfurfuryl Alcohol for Composite Elaboration

A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics.