Carlo Pirola

University of Milan | UNIMI · Department of Chemistry

The hydrogenation of muconic acid (MA) to bio-adipic acid (AdA) is one of the green chemical processes that has attracted the most interest in recent years. Indeed, MA can be readily obtained from biomass through fermentative processes. Here, we aimed to investigate the synergic effect of electronic promotion that the addition of a second metal, ev...

The paper presents the design of the experimental apparatus developed in order to analyse the performance of a prototype of a pyrolysis system for the exploitation of the plastic residues of industrial processes and the end-of-life tires. The small-scale pilot prototype is specifically designed for carrying out an experimental campaign aimed at det...

Metallosilicates are tunable molecular sieves that have been applied in Fischer-Tropsch synthesis as supports and promoters of cobalt-based catalysts. Here, for the first time, we synthesize iron based catalysts over Ce, Zr, V, and Ti metallosilicates with an nonhydrolytic surfactant assisted sol–gel method adapted from literature. The catalysts we...

The CO2 photoreduction is a promising way to convert one of the most abundant greenhouse gases to valuable chemicals. The photoreduction in the liquid phase is limited by the low solubility of CO2 in water, but this point is overcome here by using an innovative photoreactor, which allows one to work up to pressures of 20 bar, improving the overall...

Kinetic modelling covers a key role in process simulation and design. Recently the methanol sector is assisting a remarkable enhancement due to its applications as fuel, solvent, and precursor as shown in Bozzano and Manenti (2016). The increasing number of patents, the market prospects, and recent research witness this renewed interest. However, d...

Sustainable development has become the cornerstone of environmental policy worldwide and a leading principle for innovative industrial processes. The philosophy lies in the progress in balance with nature that ensures the existing productive systems' survival through a new design paradigm shift. Even in the industrial framework, the sustainability...

The hydrogenation reaction of muconic acid, produced from biomass using fermentative processes, to bio-adipic acid is one of the most appealing green emerging chemical process. This reaction can be promoted by catalysts based on a metal belonging to the platinum group, and the use of a second metal can preserve and increase their activity. Pd–Au bi...

Recently, we have witnessed a booming development of composites and multi-dopant metal oxides to be employed as novel photocatalysts. Yet the practical application of photocatalysis for environmental purposes is still elusive. Concerns about the unknown fate and toxicity of nanoparticles, unsatisfactory performance in real conditions, mass transfer...

Recently, we have witnessed a booming development of composites and multi-dopant metal oxides to be employed as novel photocatalysts. Yet the practical application of photocatalysis for environmental purposes is still elusive. Concerns about the unknown fate and toxicity of nanoparticles, unsatisfactory performance in real conditions, mass transfer...

The paper presents the design of the experimental apparatus developed in order to analyse the performance of a prototype of a pyrolysis system for the exploitation of the plastic residues of industrial processes and the end of life tires. The small scale pilot prototype is specifically designed for carrying out an experimental campaign aimed at det...

Nowadays environmental sustainability is a fundamental requirement for the development of any process. In this regard, European Union applied directives on emission reduction commitments. In such circumstances, it is mandatory for industries or facilities to adopt proper pollution control measures to meet the requirements. The absorption process ca...

Process simulation software designs equipment, simulates operations, optimizes a plant's configuration (heat exchangers network, for example), estimates operating and capital expenses, and serves as an educational tool. However, mastering the theoretical background minimizes common mistakes such as applying an incorrect thermodynamic method, select...

The hydrogenation of trans,trans-muconic acid was investigated on a Pt/C 5% (wt) catalyst in a batch slurry reactor at constant hydrogen pressure (4 bar) and temperature (323, 333 and 343 K), with the purpose of developing a kinetic model able to predict conversions and product distributions. A dual-site Langmuir-Hinshelwood-Hougen-Watson (LHHW) mo...

Carbon dioxide concentration level is reaching a non-returning point. Carbon capture technologies are immature and short-term actions are necessary. The conversion of CO2 into methanol is a technical challenge. Commercial copper-zinc-alumina catalysts convert maximum 7% carbon dioxide in syngas at high pressures (5 MPa to 10 MPa) and moderate tempe...

The new educational EYE4EDU project, based on proposing to bachelor degree students different exercises on a Virtual immersive Crude Distillation Unit (VCDU), is described. The VCDU combines the action of EYESIM and DYNSIM software from AVEVA Company, for the physical representation and the dynamic chemical behavior of the plant. The educational im...

The techno-economic feasibility of three biogas utilization processes was assessed through computer simulations on commercial process simulator Aspen HYSYS: HPC (biogas to methanol), BioCH4 (biogas to biomethane) and CHP (biogas to heat & electricity). The last two processes are already used commercially with the aid of subsidy policies. The econom...

The potential of Humidified Enriched Air (HEA) on Diesel engine combustion is investigated, by means of 3D CFD combustion simulations, on a current production 4-cylinder turbocharged Diesel engine. HEA is supposed to be obtained by water degassing operation, exploiting the different vapor-liquid equilibria of it main constituents, nitrogen and oxyg...

The nonsteroidal anti-inflammatory drug sodium diclofenac (DC) is an emerging water pollutant which resists conventional wastewater treatments. Here the sonophotocatalytic degradation of DC was carried out using micrometric TiO2 (both pristine and Ag-decorated), UV-A irradiation and 20 kHz pulsed ultrasound. Sonophotocatalytic tests were compared w...

The effect of support, stabilizing agent, and Pd nanoparticles (NPs) size was studied for sodium muconate and t,t-muconic acid hydrogenation to bio-adipic acid. Three different activated carbons (AC) were used (Norit, KB, and G60) and carbon morphology did not affect the substrate conversion, but it greatly influenced the adipic acid yield. 1% Pd/K...

Thermal programmed desorption (TPD) is a powerful technique for materials and catalysts characterization. By analyzing TPD curves it is possible to calculate important parameters as the desorption activation energy, Ed, that depends on the surface coverage (θ) by a nonlinear polynomial function, ie, . The Polanyi‐Wigner equation, , can be used as t...

TiO2 is employed as both photocatalytic and structural materials, leading to its applications in external coatings or in interior furnishing devices, including cement mortar, tiles, floorings, and glass supports. The authors have already demonstrated the efficiency of photoactive micro-sized TiO2 and here its industrial use is reported using the di...

Polymeric dielectrics are employed extensively in the power transmission industry, thanks to their excellent properties; however, under normal operating conditions these materials tend to degrade and fail. In this study, samples of low-density polyethylene, polypropylene, polymethyl methacrylate, and polytetrafluorethylene were subjected to corona...

sodium muconate and trans,trans‐muconic acid were heterogeneously hydrogenated to adipic acid, a strategic intermediate for the industry of polyamides and high performance polymers. Hydrogen pressure, metal to substrate ratio, substrate concentration and reaction temperature were varied to study the effect of these parameters on the reaction produc...

The aim of this work is to evaluate the potential application of a new sustainable technology, called Acid Gas to Syngas, on steam reforming process in order to reduce the carbon dioxide emissions. Indeed, steam reforming has high emissions of carbon dioxide, at almost 7 kg of carbon dioxide per 1 kg of hydrogen produced. The key idea of the new te...

Distillation is one of the most important separation process in industrial chemistry. This operation is based on a deep knowledge of the fluid phase equilibria involved in the mixture to be separated. In particular, the most important aspects are the determination of the vapor pressures of the single compounds and the correct representation of the...

A series of Au/TiO2 based catalysts with low gold loading (0.1–0.5 wt%) were prepared by a modified deposition–precipitation method and their activity was tested for CO2 photoreduction in liquid phase at high pressure (7 bar). Methanol, formic acid and formaldehyde were detected as major products in liquid phase, whilst gas phase products, CO, CH4...

The present work presents the results of 3D CFD combustion simulations of a current production 4-cylinder turbocharged Diesel engine using oxygen-enriched and humidified combustion air. Enriched Air (EA) is supposed to be produced by desorption from water, exploiting the different Henry constants of N 2 and O 2 . Simulation results show that EA per...

A new process for oxygen enriched air (EA) production has been applied to Claus Process. This process is simple and requires few process units. Matlab and Aspen Hysys have been used for simulations and system sizing. The results demonstrate that it could be an alternative to traditional EA processes from an economical point of view.

The photoreduction of CO2 is an intriguing process which allows the synthesis of fuels and chemicals. One of the limitations for CO2 photoreduction in the liquid phase is its low solubility in water. This point has been here addressed by designing a fully innovative pressurized photoreactor, allowing operation up to 20 bar and applied to improve th...

The ingredients of Pharmaceuticals and Personal Care Products (PPCPs) persist in water and conventional treatment plants are not able to remove them efficiently. Sonochemical treatment is insufficient to mineralize organics such as ibuprofen into CO2 and H2O. TiO2 degrades ibuprofen (IBP) under UV light; however, it does not reach a high grade of c...

The photoreduction of CO2 is an intriguing process, which allows the synthesis of fuels and chemicals. One of the limitations for CO2 photoreduction in the liquid phase is its low solubility in water. This point has been here addressed by designing a fully innovative concept of pressurized photoreactor, allowing operation up to 20 bar and applied t...

Temperature programmed reduction (TPR) characterizes the oxido‐reduction properties of bulk and supported catalysts. H2 or CO pass over a pre‐conditioned solid sample as a furnace ramps the temperature at a constant rate. A thermal conductivity detector (TCD) or mass spectrometer records the effluent concentration. In the pre‐conditioning step, Ar...

Pharmaceutical compounds and their metabolites raise worrying questions because of their continuous release and lack of efficient removal by conventional wastewater treatments; therefore, they are being detected in groundwater, surface water and drinking water in increasing concentrations. Paracetamol and aspirin are two of the most commonly used d...

Today biogas produced from anaerobic digestion is used mainly for thermic and electric energy production. Its use as raw material for syngas production and further upgrading to chemical products like methanol (MeOH), dimethyl ether (DME) or acetic acid could be an interesting option as process intensification. In this work the sustainability of a B...

A fraction of the petroleum extracted from oil reservoirs contains associated natural gas. Rather than building infrastructure to recover low volumes of this natural gas, the industry flares or vents it to the atmosphere, which contributes to atmospheric greenhouse gas emissions but also reduces the air quality locally because it contains gaseous s...

Oxygen enriched air intensifies oxidation processes since smaller reactors reach the same conversion of typical unit operations that employ simple air as reactant. However, the cost to produce pure oxygen or oxygen enriched air with traditional methods, i.e. cryogenic separation or membrane technologies, may be unaffordable. Here, we propose a new...

A number of reaction processes undergo yield drops since an intermediate target species can further react with one of the reactants generating lower volatility by-products. Such reactions are typically fast and non-selective, so that a gradual conversion of the reactants is recommended because of safety and quality constraints; when dealing with re...

The functionalization of multi-walled carbon nanotubes (MW-CNTs) was obtained by generating reactive perfluoropolyether (PFPE) radicals that can covalently bond to MW-CNTs' surface. Branched and linear PFPE peroxides with equivalent molecular weights of 1275 and 1200 amu, respectively, have been thermally decomposed for the production of PFPE radic...

Methanol can be produced from different sources. The most prominent industrial processes for its synthesis are based on the use of traditional fossil fuels, natural gas and coal. Although the methanol process is considered to be a well-established technology, from an environmental and societal point of view, its main drawback is the use of fossil f...

Cobalt catalysts are known to have a high activity and selectivity in the Fischer–Tropsch reaction converting synthesis gas to higher hydrocarbons (C5+). These catalysts have been supported by different porous materials. Porous carbon materials like activated carbon (AC) have physical and chemical surface properties that affect the preparation of s...

Volatile and semi volatile organic compounds' concentration have dramatically increased in indoor environments in recent years. UV light promotes titanium dioxide, which oxidises various molecules; however, most of the studies report the degradation of a single VOC. Here, we investigate the photo-oxidation of 17 molecules in mixture to have a reali...

Methanol is an important intermediate in the synthesis of different chemicals. It is mainly produced by reforming of natural gas in centralized facilities with productive capacities on the order of 109 tons per day. Production of methanol from biomass suffers from the cost and logistics of the transportation of biomass and it has not yet maturated...

Downstream processing of biofuels and bio-based chemicals often represents the bottleneck for the economic sustainable development of new processes. It is also a challenging problem for process synthesis and optimization, due to the intrinsic nonideal thermodynamics of the liquid mixtures derived from the (bio)chemical conversion of biomass. In thi...

Here we developed an early-stage attributional LCA of an innovative production process of oxygen-enriched air by water desorption. We compared LCA's results with a rigorous economic model, in an eco-design optimization perspective. We developed the life cycle analysis using primary data from the lab-scale plant. We used SimaPro 8.1.1.16 for the LCA...

In this work trans,trans-muconic acid was hydrogenated to adipic acid, a strategic intermediate for the industry of polyamides and high performance polymers. This study: (1) develops a new and robust analytical method for the evaluation of muconic acid conversion and adipic acid selectivity, (2) defines a standard procedure for the confirmation of...

Micro-sized TiO2 catalyst was employed to degrade pharmaceutical compounds, i.e. aspirin and paracetamol, two of the most widely used drugs, purchasable without prescription. Their active agents, acetylsalicylic acid and acetaminophen, are characterized by different substituent groups, linked to the aromatic ring, which affect both the photodegrada...

Fatty acid methyl esters (biodiesel) synthesized by transesterifying vegetable oil and fats with methanol are unsuitable for northern climates and alpine regions. Isopropyl esters derived from oil and isopropanol have superior cold flow properties and lower cloud point but reaction rates are slow in batch liquid phase processes. To accelerate the r...

In economy nowadays, methanol is already a key compound widely employed as building block for producing intermediates or synthetic hydrocarbons, solvent, energy storage medium, and fuel. In recent times, methanol has been employed in a number of innovative applications. It is a clean and sustainable energy resource that can be produced starting fro...

In this work an industrial Biomass-To-Liquid (BTL) plant simulation and optimization are presented. Biomass is first gasified with oxygen and steam, and the produced syngas is fed to a multi-tubular fixed bed reactor for Fischer-Tropsch (FT) synthesis, obtaining a distribution of hydrocarbons with different molecular weight. A simplified model for...

The hydrogenation of muconic acid to adipic acid is studied in a three phases slurry reactor. This is the last step of a novel biotechnological process which, starting from lignocellulosic biomass, allows the production of renewable PA 6,6. A new Pt/C 5% catalyst was selected, which outperformed all the catalysts mentioned in previous literature, a...

In recent times, the methanol was employed in numerous innovative applications and is a key compound widely used as a building block or intermediate for producing synthetic hydrocarbons, solvents, energy storage medium and fuel. It is a source of clean, sustainable energy that can be produced from traditional and renewable sources: natural gas, coa...

In this work (part of a series in which different biomass conversion routes are studied) a novel coupling between gasification and pyrolysis is described: by means of a design parameter (α) biomass is distributed between these two operations. In order to characterize the quality of the syngas produced, simulations are performed with a gasification...

Biogas is one of the energy sources that are gaining more and more importance in Europe and, in particular, in Italy and Germany. Nowadays, it is used for the combined production of heat and power. Here we propose to use all of its major components (CO2 and CH4) to produce methanol. A feasibility study of this process is reported, where we optimize...

Due to their massive production, H2S and CO2 are two critical pollutants. H2S is toxic and CO2 is responsible for impacts on ecological and environmental system. The aim of this work is to propose and demonstrate the revamping industrial feasibility of an innovative and sustainable process that improves the production of syngas compared to the trad...

A laboratory experience concerning a continuous distillation column for Industrial Chemistry and Chemical Engineering students is presented. The experience is based on practical exercise of the column running at infinite and finite reflux and on the elaboration of the collected data by both classical equations and computer simulation. The compariso...

Biomass-to-liquid Fischer-Tropsch (FT) is an industrial process that converts bio-syngas in hydrocarbons ranging from C1 to C100. Bio-syngas, a syngas mixture produced from biomass, is characterized by a H2/CO molar ratio in the range 1.0–1.5. An iron-based catalyst supported on silica for CO hydrogenation with 30 wt% of metal was prepared, charact...

The separation of water and acetic acid mixtures is a challenging task in the terephthalic acid production process. This study addresses the techno-economical optimization of an heteroextractive distillation column that uses p-xylene as entrainer. The optimization of this column is performed by means of robust optimizers belonging to the BzzMath li...

This chapter presents the use of a commercial micro-sized TiO2 powder as an alternative to the traditional nano-powders as semiconductors in photocatalytic processes. Results of the photocatalytic efficiency towards the photodegradation of the traditional pollutant molecules both in gas phase (nitrogen oxides (NOx) and volatile organic compounds (V...

Oxygen enriched air with a composition of oxygen till 35% can be produced by water desorption by simple water degassing. This work reports the simulation of a small bench-scale plant for the continuous production of oxygen-enriched air by simple water degassing. The basic thermodynamic principle involved is the higher water solubility of oxygen com...

The sonochemical synthesis of nanostructured materials owes its origins to the extreme conditions created during acoustic cavitation, i.e., the formation of localized hot spots in the core of collapsing bubbles in a liquid irradiated with high intensity ultrasound (US). In particular, in the present work a sonochemical synthesis has been investigat...

Cobalt catalysts are known to have a high activity in the Fischer-Tropsch (FT) reaction converting synthesis gas into hydrocarbons and waxes. Co catalysts have also proven to have a high selectivity to higher hydrocarbons (C5+). These catalysts have been supported by a number of supports, such as Al2O3, SiO2 and TiO2. Many recent reviews deals with...

The technology of the organic/inorganic hybrid coating was employed in the preparation of a hydrophobic coating (contact angle higher than 140°) for fouling mitigation on stainless steel heat transfer surfaces. A commercial triethoxysilane perfluoropolyethers was combined with a sol-gel silica network with the aim to increase the mechanical and the...

Organic inorganic hybrid coatings were prepared using a commercial triethoxysilane α,ω substituted perfluoropolyether as organic phase in combination with tetraethyl orthosilicate (TEOS) as inorganic phase. The coatings were prepared by sol-gel synthesis of a silica coating in co-presence with the commercial polymer, and deposited on stainless stee...

The paper deals with the application of the novel Acid Gas To Syngas (AG2S™) technology to the gasification of solid fuels. The AG2S technology is a completely new effective route of processing acid gases: H2S and CO2 are converted into syngas (CO and H2) by means of a regenerative thermal reactor. To show the application of the AG2S technology, mo...

Natural gas emissions contribute to climate change, and equally importantly, affect the health of populations near gas fields. [1] At night, the flares from the Bakken fields in North Dakota burn as bright as the lights in cities as large as Minneapolis. Rather than flaring (or worse, venting), this associated natural gas represents a multi‐billion...

Flame spray pyrolysis (FSP) is an innovative and scalable technique, used to synthesize monometallic and bimetallic Co-Ru catalysts with 5% wt. Co, 10% wt. Co and 0.4% wt. Ru supported on SiO2 active in the Gas-to-Liquids (GTL)-Fischer-Tropsch (FT) process, which converts syngas to hydrocarbons. The catalysts were characterized by TEM, FE-SEM-EDX,...

The most important drawback of the use of TiO2 as photocatalyst is its lack of activity under visible light. To overcome this problem, the surface modification of commercial micro-sized TiO2 by means of high-energy ultrasound (US), employing CuCl2 as precursor molecule to obtain both metallic copper as well as copper oxides species at the TiO2 surf...