Advances in catalytic routes for the production of carboxylic acids from biomass: a step forward for sustainable polymers.

Polymers are ubiquitously present in our daily life because they can meet a wide range of needs and fields of applications. This success, based on an irresponsible linear consumption of plastics and the access to cheap oil, is creating serious environmental problems. Two lines of actions are needed to cope with them: to adopt a circular consumption of plastics and to produce renewable carbon-neutral monomers. This review analyses the recent advances in the chemocatalytic processes for producing biomass-derived carboxylic acids. These renewable carboxylic acids are involved in the synthesis of relevant general purpose and specialty polyesters and polyamides; some of them are currently derived from oil, while others can become surrogates of petrochemical polymers due to their excellent performance properties. Polyesters and polyamides are very suitable to be depolymerised to other valuable chemicals or to their constituent monomers, what facilitates the circular reutilisation of these monomers. Different types of carboxylic acids have been included in this review: monocarboxylic acids (like glycolic, lactic, hydroxypropanoic, methyl vinyl glycolic, methyl-4-methoxy-2-hydroxybutanoic, 2,5-dihydroxypent-3-enoic, 2,5,6-trihydroxyhex-3-enoic acids, diphenolic, acrylic and δ-amino levulinic acids), dicarboxylic acids (2,5-furandicarboxylic, maleic, succinic, adipic and terephthalic acids) and sugar acids (like gluconic and glucaric acids). The review evaluates the technology status and the advantages and drawbacks of each route in terms of feedstock, reaction pathways, catalysts and economic and environmental evaluation. The prospects and the new research that should be undertaken to overcome the main problems threatening their economic viability or the weaknesses that prevent their commercial implementation have also been underlined.

Cyclopentyl methyl ether: a green co-solvent for the selective dehydration of lignocellulosic pentoses to furfural.

The effects of cyclopentyl methyl ether (CPME) addition during the aqueous xylose dehydration reaction to furfural are reported here. These investigations were conducted by using pure xylose and Cynara cardunculus (cardoon) lignocellulose as sugar source and H(2)SO(4) as catalyst. The research was also applied to aqueous solutions containing NaCl, since it has been previously demonstrated that NaCl incorporation to these reaction mixtures remarkably increases the furfural formation rate. It has been found that CPME incorporation inhibits the formation of undesired products (resins, condensation products and humins). Thus, cardoon lignocellulosic pentoses were selectively transformed into furfural (near 100%) at the following reaction conditions: 1 wt.% H(2)SO(4), 4 wt.% biomass referred to aqueous solution, 30 min reaction, 443 K, CPME/aqueous phase mass ratio equals to 2.33, and NaCl/aqueous solution mass ratio of 0.4. In contrast, no effect was observed for cellulosic glucose transformation into hydroxymethylfurfural and levulinic acid at identical reaction conditions.

Chemical analysis of used three-way catalysts by total reflection X-ray fluorescence.

The methodology developed for evaluating, by total reflection X-ray fluorescence, the main elements in used three-way catalysts for cars after more than 59 000 km is described. The analytical method does not require chemical manipulation of the samples, is quick (30 min for sample preparation and 10 min for analysis), precise (between 1% and 10% of variation coefficient), and simple. The two catalytic monoliths contained in the cartridge of a car with more than 59,000 km have been analyzed. The mass relationships between the detected elements and Si, a component of the cordierite ceramic substrate, have been used to follow the axial and radial profiles of the elements. Information concerning the loss of active elements and the retention of contaminating elements as a consequence of the working conditions was attained by comparison between the results obtained for the used catalyst (59 000 km) with those of a fresh catalyst (0 km). The interface effect between the first and the second catalytic bricks was also studied.