Catalytic amination of lactic acid using Ru-zeolites.

In this work we investigate the synthesis of alanine from lactic acid, a biobased platform chemical, using ammonia as a nitrogen source and Ru/zeolite catalysts. We report a high alanine selectivity when using Ru/BEA of 80-93%. Reaction side products were identified as ethanol, propionic acid or propanamide and the reaction mechanism was investigated. We further optimised reaction conditions resulting in turn over numbers five times higher than previously reported and could reduce Ru leaching by 30-40%. However, leaching and catalyst stability remains a concern. Furthermore, we critically analyse the benefits of Ru/zeolites versus their stability under the basic, high temperature reaction conditions.

Quali-quantitative monitoring of chemocatalytic cellulose conversion into lactic acid by FT-NIR spectroscopy.

Chemocatalytic conversion of cellulose into lactic acid is a valuable alternative to simple sugar fermentation. Nevertheless, the procedures still need optimization to be translated to the industrial scale. Such translation would benefit by on-line monitoring of reaction parameters by fast, inexpensive, direct spectroscopic techniques. In this work, we propose the application of FT-NIR spectroscopy as a suitable analytical tool for monitoring the chemocatalytic conversion of cellulose into lactic acid. Comparison between different FT-NIR spectra at different reaction temperatures and times was exploited to qualitatively indicate the feasibility of the reaction. Besides, an FT-NIR prediction model was proposed for rapidly estimating the molar distribution of cellulose catalytic degradation components in the reaction mixtures. The calibration model was based on reference samples analysed by HPLC. The model was validated by an external validation set. Relevant statistical values of Ratio Performance to Deviations (RPD) referred to both calibration and external validation were obtained, thus demonstrating the potential of such analytical technique in process monitoring.

Natural Deep Eutectic Solvent as Extraction Media for the Main Phenolic Compounds from Olive Oil Processing Wastes.

In this new century, sustainable development challenges chemical sciences to develop new and clean technological processes. The agri-food industry produces significant quantities of waste, raising significant economic and environmental concerns. Food waste valorization using environmentally friendly procedures is of increasing importance. This study describes the use of several Natural Deep Eutectic Solvents (NADESs) for the microwave-assisted extraction (MAE) of valuable bioactive phenolic compounds from olive oil processing wastes. The extracted samples were characterized by liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (LC-ESI-QTOF/MS) analysis and the quantification of the phenolic compounds was performed by HPLC analysis. The obtained data were compared with those obtained using water as the solvent in the same extraction conditions. The extraction process is nontoxic, simple and selective and meets most of the criteria to be considered as a sustainable process, with the solvents arising directly from nature.

Combined Ultrasound/Microwave Chemocatalytic Method for Selective Conversion of Cellulose into Lactic Acid.

Cellulose is the main component of lignocellulosic biomass. Its direct chemocatalytic conversion into lactic acid (LA), a powerful biobased chemical platform, represents an important, and more easily scalable alternative to the fermentative way. In this paper, we present the selective hydrothermal conversion of cellulose and simple sugars into LA, under mild reaction conditions in presence of ErCl3 grafted on the mesoporous silica (MCM-41) surface. High yields and selectivity were obtained for the conversion of sugars under microwave (MW) irradiation at a relatively low temperature (200 °C) and short reaction times (10 min) under microwave (MW) irradiation. Ultrasounds (US) pre-treatment was investigated to reduce the cellulose crystallinity, before the MW-assisted conversion, providing LA with a yield of 64% within 90 min at 220 °C below the subcritical water conditions with increased operational safety. We finally discuss the scalability of the process and the recyclability of the catalyst.