Brewer’s spent grain (BSG) was chemically characterized obtaining 52.1% of carbohydrates, 17.8% protein, 5.9% lipids, 13.5% insoluble lignin and 24.3% of water-soluble extractives. This work has been focused on the study of polyphenol extraction of the extractive fraction by water ultrasound-assisted extraction. Selected extraction conditions were 47 °C and 21.7 mL water/g_dry-BSG. The effect of solvent polarity on polyphenol extraction was studied by using ethanol aqueous mixtures, from 20% to 100% ethanol. The kinetics of polyphenol extraction have been fitted to the power law and the Weibull models yielding mean values of the root mean square deviation lower than 7.5%. Extracts have been characterized in terms of quantification of individual phenolic compounds by HPLC-DAD and protein and sugar soluble fractions (glucose, xylose, and arabinose). Polyphenol profile has been compared with other hydrolytic techniques, such as acid, basic and enzymatic hydrolysis, showing that ultrasound was not as effective as basic hydrolysis to release the phenolic acids esterified to the cell wall. A further centrifuge ultrafiltration concentration step was able to yield a retentate enriched in the protein fraction while individual phenolic compounds where mainly transferred to the permeate.

The valorization of the brewer's spent grain (BSG) generated in a craft beer industry was studied by subcritical water hydrolysis in a semi-continuous fixed-bed reactor. Temperature was varied from 125 to 185 °C at a constant flow rate of 4 mL/min. Biomass hydrolysis yielded a maximum of 78% of solubilized protein at 185 °C. Free amino acids presented a maximum level at 160 °C with a value of 55 mg free amino acids/gprotein-BSG. Polar amino acid presented a maximum at lower temperatures than non-polar amino acids. The maximum in total phenolic compounds was reached at 185 °C. This maximum is the same for aldehyde phenolic compounds such as vanillin, syringic and protocatechuic aldehyde; however, for hydroxycinnamic acids, such as ferulic acid and p-coumaric, the maximum was obtained at 160 °C. This allows a fractionation of the bioactive compounds. Subcritical water addresses opportunities for small breweries to be incorporated within the biorefinery concept.

Food industry generates substantial waste, raising economic and environmental concerns. Green Chemistry (GC) highlights the extraction of nutritional and bioactive compounds as a key strategy for waste valorization, driving interest in sustainable methods to recover valuable compounds efficiently. This review evaluates the sustainability of widely used emerging extraction technologies—Microwave-, Ultrasound- and Enzyme-Assisted, as well as Supercritical Fluid Extraction—and their alignment with GC principles for agri-food waste valorization. It first outlines the principles, key parameters, and main advantages and limitations of each technique. Subsequently, sustainability is then assessed in selected studies using the Analytical GREEnness Metric Approach (AGREEprep). By calculating the greenness score (GS), this metric quantifies the adherence of extraction processes to sustainability standards. The analysis reveals variations within the same extraction method, influenced by solvent choice and operating conditions, as well as differences across the techniques, highlighting the importance of process design in achieving green and efficient valorization.