Giorgio Grillo

Biodiesel production process intensification using a rotor-stator type generator of hydrodynamic cavitation

Triglyceride transesterification for biodiesel production is a model reaction which is used to compare the conversion efficiency, yield, reaction time, energy consumption, scalability and cost estimation of different reactor technology and energy source. This work describes an efficient, fast and cost-effective procedure for biodiesel preparation using a rotating generator of hydrodynamic cavitation (HC). The base-catalyzed transesterification (methanol/sodium hydroxide) has been carried out using refined and bleached palm oil and waste vegetable cooking oil. The novel HC unit is a continuous rotor-stator type reactor in which reagents are directly fed into the controlled cavitation chamber. The high-speed rotation of the reactor creates micron-sized droplets of the immiscible reacting mixture leading to outstanding mass and heat transfer and enhancing the kinetics of the transesterification reaction which completes much more quickly than traditional methods. All the biodiesel samples obtained respect the ASTM standard and present fatty acid methyl ester contents of >99% m/m in both feedstocks. The electrical energy consumption of the HC reactor is 0.030kWh per L of produced crude biodiesel, making this innovative technology really quite competitive. The reactor can be easily scaled-up, from producing a few hundred to thousands of liters of biodiesel per hour while avoiding the risk of orifices clogging with oil impurities, which may occur in conventional HC reactors. Furthermore it requires minimal installation space due to its compact design, which enhances overall security.

Microwave-Assisted γ-Valerolactone Production for Biomass Lignin Extraction: A Cascade Protocol

The general need to slow the depletion of fossil resources and reduce carbon footprints has led to tremendous effort being invested in creating “greener” industrial processes and developing alternative means to produce fuels and synthesize platform chemicals. This work aims to design a microwave-assisted cascade process for a full biomass valorisation cycle. GVL (γ-valerolactone), a renewable green solvent, has been used in aqueous acidic solution to achieve complete biomass lignin extraction. After lignin precipitation, the levulinic acid (LA)-rich organic fraction was hydrogenated, which regenerated the starting solvent for further biomass delignification. This process does not requires a purification step because GVL plays the dual role of solvent and product, while the reagent (LA) is a product of biomass delignification. In summary, this bio-refinery approach to lignin extraction is a cascade protocol in which the solvent loss is integrated into the conversion cycle, leading to simplified methods for biomass valorisation.

Sonochemical preparation of alumina-spheres loaded with Pd nanoparticles for 2-butyne-1,4-diol semi-hydrogenation in a continuous flow microwave reactor

A novel protocol for microwave-assisted alkyne semi-hydrogenation under heterogeneous catalysis in a continuous flow reactor is reported herein. This challenging task has been accomplished using a multifaceted strategy which includes the ultrasound-assisted preparation of Pd nanoparticles (average O 3.0 ± 0.5 nm) that were synthesized on the μ-metric pores of sintered alumina spheres (O 0.8 mm) and a continuous flow reaction under H2 (flow rate 7.5 mL min−1) in a microwave reactor (counter-pressure 4.5 bar). The semi-hydrogenation of 2-butyne-1,4-diol in ethanol was chosen as a model reaction for the purposes of optimization. The high catalyst efficiency of the process, in spite of the low Pd loading (Pd content 111.15 mg kg−1 from ICP-MS), is due to the pivotal role of ultrasound in generating a regular distribution of Pd nanoparticles across the entire support surface. Ultrasound promotes the nucleation, rather than the growth, of crystalline Pd nanoparticles and does so within a particularly narrow Gaussian size distribution. High conversion (>90.5%) and selectivity to (Z)-2-butene-1,4-diol (95.20%) have been achieved at an alkyne solution flow rate of 10 mL min−1. The lead-free, alumina-stabilized Pd catalyst was fully characterized by TEM, HR-TEM, EDX, IR, XRPD and AAS. Highly dispersed Pd nanoparticles have proven themselves to be stable under the reaction conditions employed. The application of the method is subject to the dielectric properties of substrates and solvents, and is therefore hardly applicable to apolar alkynes. Considering the small volume of the reaction chamber, microwave-assisted flow hydrogenation has proven itself to be a safe procedure and one that is suitable for further scaling up to industrial application.

Non-conventional Ultrasound-Assisted Extraction of Alginates from Sargassum Seaweed: From Coastal Waste to a Novel Polysaccharide Source

Sargassum algae are brown free-floating seaweed found worldwide in temperate and tropical regions and provide shelter and food for many animal species. In recent years, their wide-spread presence has gone out of control, leaving dense clumps of rotting weeds and toxic waste along urban beaches. Nevertheless, this harmful brown seaweed is a valid source of sodium alginate (SA), a well-known biodegradable and biocompatible polysaccharide, widely used in food, pharmaceutical and biomedical applications due to its stabilizing and gelling properties. The aim of this paper was the extraction and chemico-physical characterization of sodium alginate from Sargassum seaweeds wastes by using unconventional ultrasound method.

Cocoa bean shell waste valorisation; extraction from lab to pilot-scale cavitational reactors

The use of zero-waste processes to integrate food-waste valorisation into the circular economy equation is currently one of the hottest topics in sustainability research. This goal is still far from being fully achieved despite the release of a number of patents and papers that deal with the topic. The present work aims to valorise cocoa shells, one of the main by-product of the roasting process, in order to enhance the effective extraction of high added value compounds by means of green protocols. The high potential added value of the residual waste has been demonstrated via a direct analytical comparison of extracts and bean composition. A range of raw matrix extraction procedures have been investigated in order to define the best solvent and technology; ultrasound (US) and hydrodynamic cavitation (HC) were compared with conventional methods. The high-energy microenvironments generated by cavitation substantially promote fast biomass deconstruction with low energy consumption. The optimized protocol couples a HC reactor with a ternary water/ethanol/hexane mixture, simultaneously providing a hydrophilic product, which is rich in methylxanthines and polyphenols, and a lipid layer. Sequential milling and sieving pretreatment provided an enriched shell fraction via the partial removal of husk fibres (54.45 vs. 81.36 w/w % total fibres). The disposal of the latter reduces mass balance, but is rerouted into animal feedstock components and crop mulching. The protocols herein reported produce valuable extracts, which are rich in antioxidant flavanols (catechins and epicatechins), theobromine (32.7 ± 0.12 mg/g shells), caffeine (1.76 ± 0.08 mg/g shells) and cocoa butter, in a simple and easy manner. This new valorisation process afforded 20.5 w/w % and 15.8 w/w % hydrophilic and lipophilic fractions, respectively, when scaled up to function in a pilot flow reactor. The fatty acids, obtained in remarkable yield (forming the 96.4 w/w % of the total light part) well match the commercial cocoa butter profile. The antioxidant extract shows an impressive total phenolic content of 197.4 mg/g extract (gallic acid eq.), with a radical scavenging activity of 62.0 ± 3.1 μg/mL (expressed in DPPH EC50). This work should facilitate industrial design for the convenient recovery of cocoa by-products as part of a zero-waste strategy.