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In recent years, the development of renewable energy and the improvement of technologies for its production has aroused particular interest. In this perspective, pressurised anaerobic digestion (PAD), i.e. the anaerobic digestion process occurring at a pressure higher than the atmospheric one, has attracted significant attention. PAD enables the production of pressurised biogas, reducing energy costs required for biogas upgrading and injection into the distribution grid. In addition, PAD presents the advantage that by increasing pressure, the solubilisation of CO2, as compared to CH4, increases, resulting in the production of biogas with a high content of CH4 (v/v% CH4 = 90%). Furthermore, results in the literature reported the potential of the autogenerative PAD, in which biogas accumulates in the headspace of the reactor and leads to a gradual increase in autogenerated pressure. In this research, the effect of autogenerated final pressure on the specific methanogenic yield (SMY) was investigated by simulating an autogenerative PAD process of sodium acetate and using a modified ADM1 (Anaerobic Digestion Model No 1) model in batch mode; moreover, the kinetic parameters of the process were assessed. Simulation results showed a good agreement with experimental results and highlighted that SMY increases by increasing the autogenerated final pressure.

Thanks to their properties, fossil fuel-based plastics are widely used daily (for industrial, domestic and environmental applications). However, they are not biodegradable, and their end of life is the cause of one of the most dangerous pollution in the world. Plastic, if recovered, can be recycled or used to recover energy, but it is not possible to recover all the tons of waste produced, so some end up in landfills. Therefore all non-recycled and non-collected plastic can take up to a thousand years to degrade. So the scientific idea is to produce biodegradable plastic capable of replacing conventional plastics. One possible solution is the poly(3-Hydroxybutyrate) (PHB) of the polyhydroxyalkanoates (PHA) family. PHB is a biopolymer accumulated in intracellular granules, under unfavourable growth conditions, by many prokaryotes and can be extracted with eco-friendly solvents. In particular, the extraction phase consists of the disruption of the cells and the subsequent separation of the biopolymer from the non-biopolymeric material (non-PHB). Currently, solvent extraction is the most used method for PHB recovery because it guarantees a high recovery yield and keeps the characteristics of the extracted biopolymer almost unaltered. In this study, the extraction of PHB with eco-friendly solvents was investigated. Simulations were carried out using 1,2-propylene carbonate as the solvent and acetone as the anti-solvent. Two process schemes were analyzed, without and with the recirculation of solvents (by distillation) and with two different types of biomass (wet and dry). The present work aims to study the final recovery yield in different operating conditions and the influence of PHB solubility on the process. The simulation results confirm the importance of solubility for optimizing the extraction process and underline the problem related to the lack of data in the literature.

Polyhydroxyalkanoates (PHAs) are biobased and biodegradable polymers that may be considered to replace fossil-based materials. However, their widespread deployment is slowed down because of the high production cost and their low quality. Using methane during the generation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-co-HV) could reduce the production costs, which are usually owed to the carbon source used, and enhance the performance of the material. In fact, the properties of PHB-co-HV make it more suitable than the most common homopolymer, named poly(3-hydroxybutyrate) (PHB), for many applications since it is more flexible, has a wider thermal processing range, a lower crystallinity and permeability to water. In this work, the production of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) was simulated using an innovative process scheme consisting of two bioreactors working in series equipped with a gas recycling unit, which was designed to increase the methane mass transfer from the gas to the liquid. During the first step, a Methylocystis dominated culture was grown on ammonia and methane to reach a high cell concentration; then, the cells were moved to the second bioreactor and subjected to nutrients starvation to favour the metabolic pathway addressed to the accumulation of PHB-co-HV. The effect of the variation of valeric acid concentration (100-400 ppm), which was used as co-substrate, on the fraction of PHB-co-HV stored in the cells and the percentage of 3-hydroxyvalerate (3-HV) was investigated: results showed that the highest the valeric acid concentration, the lower the total polymer content and the higher the HV fraction accumulated.

Replacing fossil plastic with green and biobased alternatives is one of the most significant challenges of this century. Polyhydroxyalkanoates, more specifically, poly(3-hydroxybutyrate) (PHB), have been found as a very promising alternative to traditional plastics, but currently, they are about 2% of the bioplastics produced. In this work, the growth of a methanotrophic strain belonging to the Methylocystis species, a natural producer of poly(3-hydroxybutyrate), was modelled in a bubble column bioreactor fed with methane, considering a discontinuous feeding strategy. Three-dimensional simulations were performed by using a CFD approach. The biomass growth strategy based on the variation of the methane bubble diameter, in a range of 0.003–0.005 m, and the aspect ratio, in the range 5–16, was simulated. Their effects were assessed on the process efficiency and performance in terms of methane fed, biomass and PHB yields. When the bubble diameter was varied, the best performance was achieved at a diameter of 0.005 m with methane fed of 34.2 g, biomass yield of 0.534 gbiomass/gCH4 and PHB yield of 0.327 gPHB/gCH4. When the aspect ratio was varied, the best performance was achieved at an aspect ratio of 10 with methane fed of 34.9 g, biomass yield of 0.523 gbiomass/gCH4 and PHB yield of 0.321 gPHB/gCH4. Finally, the estimation of the PHB yield was performed. CFD analysis allowed to verify the absence of death or stagnant zones inside the reactor.

Poly(3-hydroxybutyrate) (PHB) is a thermoplastic polyester that can be synthesised by many bacteria under unfavourable growth conditions. Among all its properties, biodegradability is the most attractive since it makes PHB a potential alternative to non-biodegradable plastics. However, the current market penetration of this polymer is limited by the high production costs, which accounts for approximately 40% of the total price, and the complexity in scaling-up the biological process. In this work, an innovative approach is presented, simulating the production of PHB through a double stage aerobic fermentation in which a Methylocystis strain grows and accumulates PHB granules. The effects of the reactor geometry on PHB yields were investigated in terms of aspect ratio (A), which was varied in the range 5-16 both at constant volume and variable volume: in the first case, the working volume was kept constant at 100 L and the diameter of the reactor was varied in the range 0.2-0.3 m; in the second case, the working volume was varied between 100 and 340L, keeping constant the diameter at 0.3 m. The effect of the geometry on transition parameters was evaluated as well. Results show that a maximum transition superficial gas velocity (Ut) of 0.05 ms-1 was obtained at A=16; while the productivity of PHB ranged between 0.12 and 0.25 kgm-3d-1.

Polyhydroxyalkanoates (PHAs) are a very promising alternative to traditional plastic materials since they are biobased and can degrade in soil, water, and sediments. Among all the existing PHAs, Poly-3-hydroxybutyrate (PHB) is the most well-known homopolymer. However, to the current state, PHAs represent only about 2% of the total bioplastics produced because their diffusion on a large scale is still limited due to their high market price. Techno-economic assessments showed that raw materials, such as sugars and oils account for up to 40% of the total costs. In this work, an innovative PHB production process scheme is presented. The expensive carbon sources are replaced by methane, which is cheap, abundant, and can be found as natural gas and in the biogas derived from the anaerobic digestion, thus allowing an integrated biorefinery. Process simulations were carried out to estimate the Poly-3-hydroxybutyrate production yields. Two aerobic fermentations were simulated into 400L semi-continuous reactors: the first for biomass growth in the presence of micro and macro-nutrients; the second for the PHB accumulation in a nutrient-deprived medium. Since both the biomass growth and PHB accumulation reactions take place in the liquid phase, the mass transfer from a gas to a liquid need to be maximised to increase biopolymer production. In this context, the effects of the superficial gas velocity (Ug) on the mass transfer rates and PHB yields were assessed. Several values of Ug, in the range 0.004 to 0.027 m s-1, that does not limit the viability of the cells, were tested. The PHB production increased with the superficial gas velocity.

Polyhydroxybutyrate (PHB) is a possible sustainable alternative to fossil-based plastic, today the cause of one of the primary forms of pollution in the world, since it is biodegradable, recyclable and compostable. Furthermore, PHB can be accumulated in several bacterial strains as a product of their metabolic activity. Solvent extraction (SE) is the most used technique, thanks to the high recovery yields and purity, to extract PHB from bacteria. In particular, a two-step SE is required: the accumulated PHB in the bacterial biomass is firstly dissolved in a solvent to obtain a mixture rich in PHB; then, an anti-solvent is added to reduce the total solubility allowing the biopolymer to precipitate and to be recovered from the residual biomass. However, despite its wide application, the SE technique is characterised by several limitations, such as the high cost and the use of halogenated solvents (i.e. chloroform). In this work, a non-halogenated based extraction process for PHB recovery from wet bacterial biomass is proposed. Simulations were carried out using butyl acetate (BA) as solvent and hexane (HEX) as anti-solvent. The process scheme also includes a distillation column and a cooling system (when necessary) to recover both the solvent and the anti-solvent. The effects of the PHB solubility during the precipitation step and the solvent recovery on process performance were investigated. The recovery yield was higher than 90% and increased as the solubility decreased. The simulation results highlighted that the proposed strategy is an effective and sustainable alternative to conventional processes for PHB recovery.

Bubble column reactors basically consist of a vertical cylinder filled by a liquid phase in which a gas phase is distributed in the liquid at the column bottom by an appropriate distributor system and moves along the column in the form of bubbles. The aim of a bubble column is to control the rate of mass transfer and reaction between the phases. The liquid phase is modelled as a continuous phase and can be operated in batch mode, or it may move co-currently or counter-currently to the flow of the gas phase. Two-phase and slurry bubble columns are widely used in the chemical- and biochemical industry for carrying out gas-liquid and gas-liquid-solid (catalytic) reaction; in particular, they are used for microalgae growth, aerobic fermentations processes, aerobic treatment of small quantities of highly polluted effluents, as well as oxidation, hydrogenation, chlorination, chemical gas cleaning and, also various biotechnological applications. In this paper, the mass transfer of CH4 to liquid in a bubble column was investigated by means of Computational Fluid Dynamic simulations in a turbulent regime. The effects of the variation of the most significant fluid dynamic parameters, such as inlet gas velocity, on CH4 concentration in the liquid phase and mass transfer from gas to liquid were studied by using COMSOL Multiphysics® Modeling Software. Results point out that the higher inlet velocities, the higher the mass transfer rate, which trend shows a pick after which it reduces to zero when CH4 concentration in the liquid becomes equal to saturation one.

Anaerobic digestion is a technology used to biologically convert organic substrates into biogas in the absence of oxygen. The resulting biogas is a renewable energy source mainly consisting of a mixture of methane (60÷70% v/v) and carbon dioxide (30÷40% v/v), with traces of some minor compounds, such as H2S and NH3. Anaerobic digestion takes place through a sequence of four biological phases - hydrolysis, acidogenesis, acetogenesis, and methanogenesis - performed by the action of particular species of bacteria. Operating parameters such as temperature, pH, pressure and organic substrates govern the process and affect the starting biomass transformation and the content of methane into the biogas. The biogas from anaerobic digestion can be upgraded to biomethane by removing CO2 and the minor compounds. The techniques commonly used for this purpose, like pressure swing adsorption and membrane separation, are energy-intensive as they require the compression of biogas. In this paper, an innovative energy-saving approach for biogas production and its upgrading to biomethane is proposed. The concept is based on anaerobic digestion carried out at a pressure higher than the atmospheric one, called pressured anaerobic digestion (PAD), in order to directly produce high pressure biogas that can be upgraded to high pure biomethane (CH4 = 95% v/v) avoiding the compression phase during the upgrading. The variation of the main operating parameters has been simulated in order to investigate their effect on biomethane production and composition and to define the best operating conditions. The simulation of the process has been carried out by using Aspen Plus®.

This work aims at contributing to the development of a revolutionary technology based on shape memory alloy (SMA) coatings deposited on-site to large-scale metallic structural elements, which operate in extreme environmental conditions, such as steel bridges and buildings. The proposed technology will contribute to improve the integrity of metallic civil structures, to alter and control their mechanical properties by external stimuli, to contribute to the stiffness and rigidity of an elastic metallic structure, to safely withstand the expected loading conditions, and to provide corrosion protection. To prove the feasibility of the concept, investigations were carried out by depositing commercial NiTinol Ni50.8Ti (at.%) powder, onto stainless steel substrates by using high-velocity oxygen-fuel thermal spray technology. While the NiTinol has been known since decades, this intermetallic alloy, as well as no other alloy, was ever used as the SMA-coating material. Due to the influence of dynamics of spraying and the impact energy of the powder particles on the properties of thermally sprayed coatings, the effects of the main spray parameters, namely, spray distance, fuel-to-oxygen feed rate ratio, and coating thickness, on the quality and properties of the coating, in terms of hardness, adhesion, roughness, and microstructure, were investigated.