The agri-food sector generates substantial quantities of waste material on farm and during the processing of these commodities, creating serious social and environmental problems. However, these wastes can be resources of raw material for the production of valuable chemicals with applications in various industrial sectors (e.g., food ingredients, nutraceuticals, bioderived fine chemicals, biofuels etc.). The recovery, purification and biotransformation of agri-food waste phytochemicals from this microbial spoilage-prone, complex agri-food waste material, requires appropriate fast pre-treatment and integration of various processes. This review provides a brief summary and discussion of the unique advantages and the importance of membrane technology in sustainable recycling of phytochemicals from some of the main agri-food sectors. Membrane-based pressure -driven processes present several advantages for the recovery of labile compounds from dilute streams. For example, they are clean technologies that can operate at low temperature (20–60 °C), have low energy requirements, there is no need for additional chemicals, can be quite automated and electrifiable, and have low space requirements. Based on their permselective properties based on size-, shape-, and charge-exclusion mechanisms, membrane-based separation processes have unpaired efficiency in fractionating biological components while presenting their properties. Pressure-driven membrane processes, such as microfiltration (MF), ultrafiltration (UF) and nanofiltration (NF), as well as other advanced membrane-based processes such as membrane bioreactors (MBR), membrane emulsification (ME) and membrane distillation (MD), are presented. The integration of various membrane technologies from the initial recovery of these phytochemicals (MF, UF, NF) to the final formulation (by ME) of commercial products is described. A good example of an extensively studied agri-food stream is the olive processing industry, where many different alternatives have been suggested for the recovery of biophenols and final product fabrication. Membrane process integration will deliver in the near future mature technologies for the efficient treatment of these streams in larger scales, with direct impact on the environmental protection and society (production of compounds with positive health effects, new job creation, etc.). It is expected that integration of these technologies will have substantial impact on future bio-based societies over forthcoming decades and change the way that these chemicals are currently produced, moving from petrochemical-based linear product fabrication to a sustainable circular product design based in agri-food waste biomass.

Tomato leaves have been shown to contain significant amounts of important metabolites involved in protection against abiotic and biotic stress and/or possessing important therapeutic properties. In this work, a systematic study was carried out to evaluate the potential of a sustainable process for the fractionation of major biomolecules from tomato leaves, by combining aqueous extraction and membrane processes. The extraction parameters (temperature, pH, and liquid/solid ratio (L/S)) were optimized to obtain high amounts of biomolecules (proteins, carbohydrates, biophenols). Subsequently, the aqueous extract was processed by membrane processes, using 30–50 kDa and 1–5 kDa membranes for the first and second stage, respectively. The permeate from the first stage, which was used to remove proteins from the aqueous extract, was further fractionated in the second stage, where the appropriate membrane material was also selected. Of all the membranes tested in the first stage, regenerated cellulose membranes (RC) showed the best performance in terms of higher rejection of proteins (85%) and lower fouling index (less than 15% compared to 80% of the other membranes tested), indicating that they are suitable for fractionation of proteins from biophenols and carbohydrates. In the second stage, the best results were obtained by using polyethersulfone (PES) membranes with an NMWCO of 5 kDa, since the greatest difference between the rejection coefficients of carbohydrates and phenolic compounds was obtained. In vivo bioactivity tests confirmed that fractions obtained with PES 5 kDa membranes were able to induce plant defense against P. syringae.

Promising initial results from the use of membrane-fractionated extracts of tomato leaf as crop protection agents have recently been reported. This paper provides additional evidence from larger scale experiments that identify an efficient pipeline for the separation of tomato leaf extracts to generate a fraction with significant defence elicitor activity. A UF tubular membrane 150 kDa, with an internal diameter of 5 mm, proved appropriate for initial extract clarification, whereas afterwards a UF 10 kDa and three NF membranes (200–800 Da) in sequence were evaluated for the subsequent fractionation of this tomato extract. The compositions of sugars, proteins and total biophenols were changed in these fractions with respect to the initial extract. The initial extract ratio of sugars: proteins: biophenols was 1:0.047:0.052, whereas for the retentate of the 800 Da NF membrane, which has the higher crop protection activity, this ratio was 1:0.06:0.1. In this regard, it appears that the main crop protection effect in this fraction was due to the sugars isolated. It was found that with the appropriate membrane cascade selection (UF 150 kDa, UF 10 kDa and NF 800 Da) it was possible to produce (easily and without the need of additional chemicals) a fraction that has significant activity as an elicitor of disease resistance in tomato, whereas the remaining fractions could be used for other purposes in a biorefinery. This is very promising for the wider application of the proposed approach for the relatively easy formulation of bio-based aqueous streams with bio-pesticide activities.