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

This critical review provides a survey illustrated by recent references of different strategies to achieve a sustainable conversion of biomass to bioproducts. Because of the huge number of chemical products that can be potentially manufactured, a selection of starting materials and targeted chemicals has been done. Also, thermochemical conversion processes such as biomass pyrolysis or gasification as well as the synthesis of biofuels were not considered. The synthesis of chemicals by conversion of platform molecules obtained by depolymerisation and fermentation of biopolymers is presently the most widely envisioned approach. Successful catalytic conversion of these building blocks into intermediates, specialties and fine chemicals will be examined. However, the platform molecule value chain is in competition with well-optimised, cost-effective synthesis routes from fossil resources to produce chemicals that have already a market. The literature covering alternative value chains whereby biopolymers are converted in one or few steps to functional materials will be analysed. This approach which does not require the use of isolated, pure chemicals is well adapted to produce high tonnage products, such as paper additives, paints, resins, foams, surfactants, lubricants, and plasticisers. Another objective of the review was to examine critically the green character of conversion processes because using renewables as raw materials does not exempt from abiding by green chemistry principles (368 references).

Conversion of biomass to selected chemical products

https://courses.washington.edu/cfr523/documents/Alonso2010CatalyticConversion.pdf

Catalytic conversion of biomass to biofuels

Lignocellulosic biomass: a sustainable platform for the production of bio-based chemicals and polymers

The biorefinery concept: Using biomass instead of oil for producing energy and chemicals

Furfural offers a promising, rich platform for lignocellulosic biofuels. These include methylfuran and methyltetrahydrofuran, valerate esters, ethylfurfuryl and ethyltetrahydrofurfuryl ethers as well as various C(10)-C(15) coupling products. The various production routes are critically reviewed, and the needs for improvements are identified. Their relative industrial potential is analysed by defining an investment index and CO(2) emissions as well as determining the fuel properties for the resulting products. Finally, the most promising candidate, 2-methylfuran, was subjected to a road trial of 90,000 km in a gasoline blend. Importantly, the potential of the furfural platform relies heavily on the cost-competitive production of furfural from lignocellulosic feedstock. Conventional standalone and emerging coproduct processes-for example, as a coproduct of cellulosic ethanol, levulinic acid or hydroxymethyl furfural-are expensive and energetically demanding. Challenges and areas that need improvement are highlighted. In addition to providing a critical review of the literature, this paper also presents new results and analysis in this area.

Furfural—A Promising Platform for Lignocellulosic Biofuels

The first generation of biofuels is presently produced fromsugars, starches, and vegetable oil. Although instrumental indeveloping the market, these biofuels are not likely to deliverthe large volumes needed for the transport sector becausethey directly compete with food for their feedstock. A morepromising feedstock is lignocellulosic material, which is moreabundant, has a lower cost, and is potentially more sustain-able.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201000655

Valeric Biofuels: A Platform of Cellulosic Transportation Fuels

Governments across the world are stimulating the valorization of local biomass to secure the energy supply, reduce the emissions of fossil CO2 and support the rural economy. A fi rst generation of fuels and chemicals is being produced from high-value sugars and oils. Meanwhile, a second generation, based on cheaper and more abundant lignocellulosic feedstock, is being developed. This review addresses the variety of chemistries and technologies that are being explored to valorize lignocellulosic biomass. It shows the need to 'deoxygenate' the biomass and reviews the main chemical routes for it, i.e. • the pyrolysis to char, bio-crude or gas;

Lignocellulose conversion: an introduction to chemistry, process and economics

Methanol synthesis: a short review of technology improvements

Cellulosic biofuel: Ethyl levulinate is a promising biofuel that can be obtained from lignocellulosic residues. A byproducts, furfural, can be converted into ethyl levulinate in an acid-based process. Here, the use of solid acid catalysts for the conversion of furfuryl alcohol into ethyl levulinate is reported.

Furfural, a potential coproduct of levulinic acid, can be converted into levulinic acid via hydrogenation to furfuryl alcohol and subsequent ethanolysis to ethyl levulinate. The ethanolysis reaction is known to proceed in the presence of H2SO4. We show here that several strongly acidic resins are comparably effective catalysts for this reaction. Optimal performance is achieved by balancing the number of acid sites with their accessibility in the resin. Acidic zeolites such as H-ZSM-5 also catalyze this reaction, although with a lower activity and a higher coproduction of diethyl ether.

Jean-Paul Lange

Papers

Furfural—A Promising Platform for Lignocellulosic Biofuels

Valeric Biofuels: A Platform of Cellulosic Transportation Fuels

Lignocellulose conversion: an introduction to chemistry, process and economics

Methanol synthesis: a short review of technology improvements

Conversion of furfuryl alcohol into ethyl levulinate using solid acid catalysts.