Pistachio and walnut shells accumulate in large quantities as waste during food processing and represent a promising lignocellulosic biomass for the extraction of valuable components. Subcritical water technology was used as an environmentally friendly technique to study the extraction of active ingredients and other valuable degradation products from walnut and pistachio waste. Subcritical water extraction (SWE) was carried out under different process conditions (temperature (150–300 °C) and short reaction times (15–60 min)) and compared with conventional extraction using different organic solvents (acetone, 50% acetone and ethanol). The extracts obtained from pistachio and walnut shell waste are rich in various bioactive and valuable components. The highest contents of total phenols (127.08 mg GA/g extract at 300 °C for 15 min, from walnut shells), total flavonoids (10.18 mg QU/g extract at 200 °C for 60 min, from pistachio shells), total carbohydrates (602.14 mg TCH/g extract at 200 °C for 60 min, from walnut shells) and antioxidant activity (91% at 300 °C, for 60 min, from pistachio shells) were determined when the extracts were obtained via subcritical water. High contents of total phenols (up to 86.17 mg GA/g extract) were also determined in the conventional extracts obtained with ethanol. Using the HPLC method, sugars and their valuable derivatives were determined in the extracts, with glucose, fructose, furfurals (5-hydroxymethylfurfural (5-HMF) and furfural) and levulinic acid being the most abundant in the extracts obtained by subcritical water. The results show that subcritical water technology enables better exploitation of biowaste materials than conventional extraction methods with organic solvents, as it provides a higher yields of bioactive components such as phenolic compounds and thus extracts with high antioxidant activity, while at the same time producing degradation products that are valuable secondary raw materials.

Corncobs are a widespread and renewable by-product of corn cultivation that are typically considered waste or low-value material. Corncobs contain hemicellulose, cellulose, and lignin, which can be converted into valuable products using suitable techniques. Subcritical water is increasingly used as a green medium for the extraction of valuable components from biomass, as it has many advantageous properties (high yield, pure extracts, shorter times) compared to other organic solvents. For this reason, subcritical water was used in this study to extract valuable components from corncobs at different temperatures (150–250 °C) and reaction times (10–60 min). During the decomposition of corncobs, numerous valuable products are formed in the aqueous phase depending on the temperature and reaction time. In addition to sugars and their derivatives, phenolic compounds were also formed, which are of great importance in numerous applications. It was found that at low temperatures (150–170 °C) the hemicellulose in the corncobs begins to decompose and, in particular, the sugars (glucose, xylose, arabinose, and galactose) are initially formed in the aqueous phase. Higher temperatures (200 and 250 °C) are more favorable for the decomposition of corncobs into valuable components. The yield of sugars increases with temperature due to the degradation of the cellulose content of the lignocellulosic biomass. At the same time, several new valuable products (furfural, 5-hydroxymethylfurfural (5-HMF), 1,3-dihydroxyacetone, levulinic acid, and formic acid as well as phenolic components) are formed through the degradation of lignin and the further degradation of sugars. The most important products are certainly the furfurals, which are central platform compounds. The highest furfural content was reached at 200 °C and 60 min and accounted for almost half of all components in the aqueous phase (472.01 ± 5.64 mg/g dry extract). These biomass-derived sugars and derivatives can be used in the production of fuels, pharmaceuticals, biodegradable polymers, and surfactants.