Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9 min of ultrasonic irradiation (20 kHz, 750 W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.     

Use of Chènevotte,a Valuable Co-Product of Industrial Hemp Fiber,as Adsorbent for Pollutant Removal. Part I: Chemical,Microscopic, Spectroscopic and Thermogravimetric Characterization of Raw and Modified Samples

FINEAU (2021–2024) is a trans-disciplinary research project involving French, Serbian, Italian, Portuguese and Romanian colleagues, a French agricultural cooperative and two surface-treatment industries, intending to propose chènevotte, a co-product of the hemp industry, as an adsorbent for the removal of pollutants from polycontaminated wastewater. The first objective of FINEAU was to prepare and characterize chènevotte-based materials. In this study, the impact of water washing and treatments (KOH, Na₂CO₃ and H₃PO₄) on the composition and structure of chènevotte (also called hemp shives) was evaluated using chemical analysis, X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray computed nanotomography (nano-CT), attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy, solid state NMR spectroscopy and thermogravimetric analysis. The results showed that all these techniques are complementary and useful to characterize the structure and morphology of the samples. Before any chemical treatment, the presence of impurities with a compact unfibrillated structure on the surfaces of chènevotte samples was found. Data indicated an increase in the crystallinity index and significant changes in the chemical composition of each sample after treatment as well as in surface morphology and roughness. The most significant changes were observed in alkaline-treated samples, especially those treated with KOH.     

Separation of organophosphorus pesticides by using nano-liquid chromatography

In the present research, the separation of a series of organophosphorus pesticides (fensulfothion, fenamiphos, profenofos, fonofos, isofenphos, dialifos, sulprofos and prothiofos), by using nano-liquid chromatography (nano-LC) with UV detection is described. Three 100 μm ID capillary columns, packed with different silica-based stationary phases (CN, C₁₈, and phenyl), were investigated. Among these, the phenyl column offered the best results in terms of chromatographic performance, and was selected for pesticide analyses. Parameters, such as sample dilution solvent, injection volume, mobile phase composition and flow rate, were optimized in order to define the ideal experimental conditions. With the aim of improving sensitivity, on-column focusing of large injection volumes was applied: a sensitivity increase of circa 100-fold was attained, with limits of detection (LODs) and quantification (LOQs) within the 4.4–37.5 and 14.5–125.0 ng/mL ranges, respectively. The method was validated, with satisfactory results, through the measurement of the following parameters: limits of detection and quantification, precision, linearity and recovery. Finally, five different baby foods, previously fortified with a solution of the eight aforementioned pesticides, and then subjected to liquid–liquid extraction and solid-phase extraction clean-up, were analyzed.     

Square-planar mixed ligand nickel dithiolenes as second-order non-linear chromophores: synthesis and characterisation of [Ni(Me2pipdt)(dddt)]

Abstract  

The novel [Ni(Me₂pipdt)(dddt)] complex based on the Me₂pipdt (1,4-dimethylpiperazine-3,2-dithione) and dddt (5,6-dihydro-1,4-dithine-2,3-dithiolate) ligands has been synthesised and characterised. Structural data, vibrational marker, solvatochromic behaviour of the typical absorption in the near infrared region, and approximate theoretical calculations suggest that an unbalanced electron distribution at the dithiolene core occurs in the ground and excited states. In particular, the dddt ligand gives a prevailing contribution to the HOMO, and Me₂pipdt to the LUMO. The charge-transfer character of the HOMO–LUMO transition makes this complex a potential second-order non-linear optic chromophore.     

Routes to HIV-integrase inhibitors: efficient synthesis of bicyclic pyrimidones by ring expansion or amination at a benzylic position

Ring expansion of [6,6] bicyclic pyrimidones led, through an aziridinium intermediate, to potent HIV-integrase inhibitors with a [7,6] core. A more flexible and diversity-oriented synthesis of functionalized pyrimidohexahydrodiazepines was then developed; the key benzylic substituent was introduced in one pot by using sequentially DDQ and BnMeNH. Both synthetic routes are described.     

Non-linear viscoelastic behavior of polymer melts interpreted by fractional viscoelastic model

Very recently, researchers dealing with constitutive law pertinent viscoelastic materials put forward the successful idea to introduce viscoelastic laws embedded with fractional calculus, relating the stress function to a real order derivative of the strain function. The latter consideration leads to represent both, relaxation and creep functions, through a power law function. In literature there are many papers in which the best fitting of the peculiar viscoelastic functions using a fractional model is performed. However there are not present studies about best fitting of relaxation function and/or creep function of materials that exhibit a non-linear viscoelastic behavior, as polymer melts, using a fractional model. In this paper the authors propose an advanced model for capturing the non-linear trend of the shear viscosity of polymer melts as function of the shear rate. Results obtained with the fractional model are compared with those obtained using a classical model which involves classical Maxwell elements. The comparison between experimental data and the theoretical model shows a good agreement, emphasizing that fractional model is proper for studying viscoelasticity, even if the material exhibits a non-linear behavior.     

On the behavior of a three-dimensional fractional viscoelastic constitutive model

In this paper a three-dimensional isotropic fractional viscoelastic model is examined. It is shown that if different time scales for the volumetric and deviatoric components are assumed, the Poisson ratio is time varying function; in particular viscoelastic Poisson ratio may be obtained both increasing and decreasing with time. Moreover, it is shown that, from a theoretical point of view, one-dimensional fractional constitutive laws for normal stress and strain components are not correct to fit uniaxial experimental test, unless the time scale of deviatoric and volumetric are equal. Finally, the model is proved to satisfy correspondence principles also for the viscoelastic Poisson’s ratio and some issues about thermodynamic consistency of the model are addressed.     

Probabilistic prediction of credit ratings: a filtering approach

In a financial market, to analyze the credit quality of firms, this note proposes a dynamical model. The population of firms is divided into a finite number of classes, depending on their credit status. The cardinality of the population can increase during the time, since new firms can enter in the market. Due to changes in credit quality and to the defaults, each firm can move from a class to another, or can go to the class of the defaulted firms. Different rating agencies are considered, each of them defines its own partition of the population. Aim of this note is to find the probabilistic prediction of the actual partition of the population, and of the conditional distribution of the distance to defaults. In a partial observing setting, this topic is discussed using stochastic filtering techniques.