New characterized material from biomasses [GRIP - D2.4.2]

NODES – Nord Ovest Digitale e Sostenibile FLAGSHIP PROJECT GRIP SPOKE 2 –GREEN TECHNOLOGIES AND SUSTAINABLE INDUSTRIES DELIVERABLE D2.4.2 “New characterized material from biomasses” REPORTING PERIOD Period covered: from M8 to M 28 Periodic report date and version: 30/09/2025 Deliverable # Responsible Boccaleri-Laurenti-Binda RM2 Responsible Arlorio This report is part of the project NODES which has received funding from the MUR – M4C2 1.5 of PNRR funded by the European Union - NextGenerationEU (Grant agreement no. ECS00000036) 1 List of Deliverables D. No Name Type Disseminati on Level Due Date Delivery Date (actual) [number] [name] [R — Document, report] [DEM — Demonstrator, pilot, prototype] [DEC — Websites, patent filings, videos, etc] [DATA — data sets, microdata, etc] [DMP — Data Management Plan] [ETHICS] [SECURITY] [OTHER] [PU — Public] [SEN — Sensitive] [R] [C] [S] [month number] [dd/mm/yyyy] D2.1 Data about chemical and nutritional profiling of raw wastes and by products R PU M14 18/04/2024 D2.2.1 On line lab-scale technical multi-device for waste processing* Other (material) PU M18 25/10/2024 D2.2.2 Delivery of protocols (lab-scale) ready to scale-up the production of new high-value material (in collaboration with Companies) R PU M22 16/02/2025 D2.3.1 New data about valorized matrices characterization and high value products R PU M28 30/09/2025 D2.3.2 New characterized ingredients/materials for food, nutraceuticals, pharma and cosmetic applications Other (material) PU M30 30/09/2025 D2.4.1 New data about sustainable production of new materials from biomasses R PU M24 D2.4.2 New characterized materials from biomasses Other (material) PU M30 30/09/2025 D2.5.2 Porous sorbents from biomasses valorization Other (material) PU M30 29/09/2025 D2.6.1 New material produced at pilot scale ready to the formulation or co-formulation (in collaboration with Companies) Other (material) PU M32 D2.6.2 New well characterized process and formulated pilot-products (in collaboration with Companies) R/Other (Material) PU M32 2 D2.7 Report on the adsorption and/or catalytic performances of porous solids derived from biomasses valorization and non-recyclable plastic wastes R PU M32 29/09/2025 3 A) INTRODUCTION The work and the outcomes reported in this Deliverable are related to the activity scheduled in Task 2.2 (focusing on Sub-Task 2.2.3 and Sub-Task 2.2.4). The main goal was the preparation and the characterization of the plant/recalcitrant biomasses useful to produce new material ready to be used in cement/biopolymers/polymer composite production/fine chemicals, as well as new high-value chemicals (biosurfactants). B) ROLE OF PARTNERS The role of the Partners involved in this activity (Disit-UPO, UNIPV, UNITO) was to apply the best performing methods to up-cycle the raw biomasses (from different origin, animal and plant-derived materials), in order to obtain their complete characterization, as well as some data about the high-value molecules/materials recovered. C) EXPLANATION OF THE WORK CARRIED OUT AND OVERVIEW OF THE PROGRESS Following we report the characterization of the main materials from biomasses (rice husk; soy; cow milk whey and Elodea nuttalii, used cooked oil). The characterization of further matrices (e.g. cocoa bean husks) were provided in other Deliverables. Disit-UPO Rice husk has been characterized to understand the intrinsic features and design the treatment optimization. Particular care was devoted to the evaluation of the inorganic content, as the high silica amount of the dried rice husk basically limits its conversion. Such amount, despite related to the type of rice and its geographical origin, determined after calcination, is about 20% wt. of which about 85% is composed by amorphous silica. Rice husk was provider an industrial sample provided by a rice production plant sited in Morano Po (VC). Its characterization required XRPD, TGA, XRF and SS-NMR; this characterization protocol allowed to understand its composition and validate the most efficient strategy for chemicals and materials recovery. Rice husk was calcined to obtain the inorganic 4 fraction, on which the elemental composition was evaluated by XRF using the glass disk obtained after borate flux fusion method. The elements, reported as oxides, and the relative percentages in weight are reported in the table. The composition is typical of a natural-based matrix, i.e. the presence of the soil elements (K, P, Mn, Mg..). Oxide Weight Percentage SiO2 85,64 K2O 4,14 CaO 4,05 SO3 1,40 P2O5 1,02 Fe2O3 0,96 Cl 0,84 Al2O3 0,74 MnO 0,59 MgO 0,37 Na2O 0,08 TiO2 0,06 Table 1: Elemental composition by XFR on calcined Rice husk The XRPD of the residue of the inorganic fraction (Figure 1 – right) highlights the presence of cristobalite phase (a polymorph of quartz) resulting from the densification of the silica fraction during the thermal treatment. 5 Fig. 1 On the contrary, the XRPD pattern of rice husk (Figure 1 XRPD - left) does not show signals related to Si oxides or in general to its inorganic content, while several broad peaks and some sharp signals are due to the presence of cellulose, characterized by a crystalline structure. The amorphous halos of hemicellulose, lignin and silica can be seen at the lower angles. The inserts in the XRPD figure are the images of rice husk, raw and after calcination. Figure 2: 29Si and 13C-MAS-NMR spectra Based on the high silica content, the 29Si SS-NMR was collected to define the silicon coordination (see figure NMR top). Silicon is in high polymerization state because, 6 according to the chemical shift, Q3 (3 bonds Si-O-Si and 1 OH) and Q4 (all Si-O-Si bonds) coordination’s are observed. The organic fraction was analysed by 13C SS-NMR and the spectrum is in figure - bottom. Peaks from the main components of rice husk can be observed at 63, 73, 83, 88 and 105 ppm for cellulose, at 21 and 171 ppm associated with acetate groups of hemicellulose (besides peaks in coincidence with cellulose), and at 56 and between 116 and 152 ppm (aromatic carbons) for lignin. Figure 3: TGA profile of rice husk and relative dTG recorded under airflow (RT900 °C – 10 °C/min) The thermogravimetric profile recorded under air flow shows the presence of three main weight losses: first the dehydration and the other two are the combustion of lignin and cellulose. With the help of the dTG profile, a rough organic composition can be determined, because if the first weight loss is characterized by a low combustion rate, revealing that rice husk does not contain many volatile molecules. On the other hand, the high combustion rate of the second loss is ascribable to rice husk with low lignin content. All these findings permitted the complete evaluation of the characteristics of the rice husk sample, ready for the preparation of derived material useful to be inserted in cement as additive. 7 CHEM-UniTO Soybean hulls, another biomass considered in RM2 activity, have been characterized through different techniques to study their composition and chemical-physical properties. They showed a negatively charged surface with a measured point of zero charge a pH value close to 2. The elemental composition was also studied through the elemental analysis .The wt % average content of C, H, N, S was 41.37±0.08; H 6.09±0.05; N 1.50±0.06; S 0.00 respectively while the calculated C/H ratio was 6.79. The outcomes of soybean hulls’ compositional analysis performed through the NREL protocol are reported in Figure 5-left. The main components are hemicellulose (49%) and cellulose (42%) while lignin (4%) and the lipidic fraction (5%) are a minority. These components are organized in fibrils as shown in FESEM image (Figure 5-right). Figure 4: -Composition (left) and FESEM image (right) of soybean hulls Rice husks’ ashes have been obtained from a waste-to-energy process of an important company located in Piedmont. Morphological analysis and microanalysis (Figure 6A 8 and 6B) showed an heterogeneous composition characterized by the predominance of C and Si atoms. The high Si content (22 g/100 g of ashes) was confirmed through the XRF analysis (Figure 6C) which also allowed to exclude the presence of dangerous heavy metals. Si is contained in the form of silica as evidenced by the ATR-FTIR spectra which showed the characteristic pattern of SiO2 (Figure 6D). Figure 5: Rice husk ashes characterization: A) FESEM-EDS microanalysis; B) FESEM images; C) XRF results; D) ATR-FTIR spectrum UNITO (DBIOS) Material collection, extraction and quantification of high value molecules from Elodea nuttalii UNITO (DBIOS) carried out surveys to detect the presence of the alien aquatic plantElodea nuttalliiin the stretch of the River Po between Villafranca Piemonte and Casale Monferrato. Elodea was found from spring 2023 onwards at various locations along the stretch; its biomass increased significantly during the summer months and then decreased again towards autumn. This trend was confirmed over the following 9 Figure 15. Fatty acid composition of UCO. PA= palmitic acid, SA= stearic acid, OA= oleic acid, LA= linoleic acid. 16