A Network of Processes for Biorefining Burdock Seeds and Roots.

In this work, a novel sustainable approach was proposed for the integral valorisation of Arctium lappa (burdock) seeds and roots. Firstly, a preliminary recovery of bioactive compounds, including unsaturated fatty acids, was performed. Then, simple sugars (i.e., fructose and sucrose) and phenolic compounds were extracted by using compressed fluids (supercritical CO2 and propane). Consequently, a complete characterisation of raw biomass and extraction residues was carried out to determine the starting chemical composition in terms of residual lipids, proteins, hemicellulose, cellulose, lignin, and ash content. Subsequently, three alternative ways to utilise extraction residues were proposed and successfully tested: (i) enzymatic hydrolysis operated by Cellulases (Thricoderma resei) of raw and residual biomass to glucose, (ii) direct ethanolysis to produce ethyl levulinate; and (iii) pyrolysis to obtain biochar to be used as supports for the synthesis of sulfonated magnetic iron-carbon catalysts (Fe-SMCC) to be applied in the dehydration of fructose for the synthesis of 5-hydroxymethylfurfural (5-HMF). The development of these advanced approaches enabled the full utilisation of this resource through the production of fine chemicals and value-added compounds in line with the principles of the circular economy.

Variability of food waste chemical composition: Impact of thermal pre-treatment on lignocellulosic matrix and anaerobic biodegradability.

A comprehensive sustainable Food Waste (FW) management is globally needed in order to reduce the environmental pollution and the financial costs due to FW disposal; anaerobic digestion is considered as one of the best environmental-friendly alternatives to this aim. A deep investigation of the chemical composition of different Food waste types (cooked kitchen waste (CKW), fruit and vegetable scraps (FVS) and organic fraction of municipal solid waste (OFMSW)) is here reported, in order to evaluate their relevant substance-specific properties and their impact on anaerobic biodegradability by means of a sophisticated automatic batch test system. Suitability for a mild thermal pre-treatment (T = 134 °C and p = 3.2 bar) to enhance the biological degradation of hardly accessible compounds was investigated. The pre-treatment affected significantly the carbohydrates solubilisation, and was able in reducing part of the lignocellulosic matrix. Moreover, in mesophilic conditions, the high solubilized sugars content favoured the initial recovery of hydrogen (not consumed by hydrogenotrophic methanogenesis), allowing to newly assess the extent of prompt fermentability. Pre-treatment enhanced hydrogen yields of FVS and OFMSW, with gains up to +50%, while the successive methane production, occurring in the same reactor, resulted affected by the lack of the soluble part of carbohydrates, "subtracted" for H2 production. Only in thermophilic conditions, when no hydrogen in the biogas was detected, pre-treatment of OFMSW significantly increased methane yield (from 0.343 to 0.389 L CH4 g-1 VSfed). A thermal pre-treatment seems the recommended solution in order to reduce part of the recalcitrant lignocellulosic matrix of food waste, to improve energy recovery and to eliminate the extra cost needed for pasteurization.

Lewis-Brønsted acid catalysed ethanolysis of the organic fraction of municipal solid waste for efficient production of biofuels.

A combined Lewis-Brønsted acid ethanolysis of sugars was thoroughly investigated with the aim of producing ethyl levulinate (EL) in a single step. Ethanolysis carried out at 453 K for 4 h using H2SO4 (1 wt%) and AlCl3·6H2O (30 mol % with respect to sugars) produced a yield of 60 mol % of EL respect to glucose and starch. Such optimised conditions were positively applied directly on different food waste, preliminarily characterised and found to be mainly composed by simple (10-15%) and relatively complex sugars (20-60%), besides proteins (6-10%) and lipids (4-10%), even in their wet form. The catalytic system resulted robust enough to the point that the copresence of proteins, lignin, lipids and mineral salts not only did not negatively affect the overall reactivity, but resulted efficiently converted into soluble species, and specifically, into other liquid biofuels of different nature.

Amorphous boron-doped sodium titanates hydrates: Efficient and reusable adsorbents for the removal of Pb2+ from water.

Amorphous titanium hydroxide and boron-doped (B-doped) sodium titanates hydrates were synthetized and used as adsorbents for the removal of Pb2+ from water. The use of sodium borohydride (NaBH4) and titanium(IV) isopropoxide (TTIP) as precursors permits a very easy synthesis of B-doped adsorbents at 298K. The new adsorbent materials were first chemically characterized (XRD, XPS, SEM, DRIFT and elemental analysis) and then tested in Pb2+ adsorption batch experiments, in order to define kinetics and equilibrium studies. The nature of interaction between such sorbent materials and Pb2+ was also well defined: besides a pure adsorption due to hydroxyl interaction functionalities, there is also an ionic exchange between Pb2+ and sodium ions even working at pH 4.4. Langmuir model presented the best fitting with a maximum adsorption capacity up to 385mg/g. The effect of solution pH and common ions (i.e. Na+, Ca2+ and Mg2+) onto Pb2+ sorption were also investigated. Finally, recovery was positively conducted using EDTA. Very efficient adsorption (>99.9%) was verified even using tap water spiked with traces of Pb2+ (50ppb).

Organic Carbonates: Efficient Extraction Solvents for the Synthesis of HMF in Aqueous Media with Cerium Phosphates as Catalysts.

We describe a process for the selective conversion of C6 -polyols into 5-hydroxymethylfurfural (5-HMF) in biphasic systems of organic carbonate/water (OC/W), with cerium(IV) phosphates as catalysts. Different reaction parameters such as the OC/W ratio, catalyst loading, reaction time, and temperature, were investigated for the dehydration of fructose. Under the best reaction conditions, a yield of 67.7 % with a selectivity of 93.2 % was achieved at 423 K after 6 h of reaction using [(Ce(PO4)1.5 (H2 O)(H3 O)0.5 (H2 O)0.5)] as the catalyst. A maximum yield of 70 % with the same selectivity was achieved after 12 h. At the end of the reaction, the catalyst was removed by centrifugation, the organic phase was separated from water and evaporated in vacuo (with solvent recovery), and solid 5-HMF was isolated (purity >99 %). The recovery and reuse of the catalyst and the relationship between the structure of the OC and the efficiency of the extraction are discussed. The OC/W system influences the lifetime of the catalysts positively compared to only water.

Cerium-based binary and ternary oxides in the transesterification of dimethylcarbonate with phenol.

Diphenyl carbonate (DPC) plays a key role in phosgene-free carbonylation processes. It can be produced by transesterification of dimethyl carbonate (DMC) with phenol in the presence of catalysts. Methyl phenyl carbonate (MPC) is first produced that is then converted into DPC by either disproportionation or further transesterification with phenol. Cerium-based bimetallic oxides (with the heterometal being niobium, iron, palladium, or aluminum) are used as catalysts in the transesterification of DMC to synthesize MPC. The catalytic activity is affected by the type and concentration of the heterometal. XPS, IR and elementary analyses are employed to characterize the new catalysts. Differently from pure oxides, the mixed oxides produce a significant increase of the conversion and selectivity towards MPC.