Modeling and Experimental Investigation of Sulfurous Compounds Removal from Gas Condensate through Ultrasound-Assisted Oxidative Desulfurization Method.

This study employed an ultrasound-assisted oxidative desulfurization process (UAOD) to investigate the degradation of three sulfurous compounds in the synthetic gas condensate. Various parameters, including oxidizers (hydrogen peroxide, sodium peroxide, potassium superoxide), promoters (formic acid, acetic acid), catalysts (phosphotungstic acid, ferrous(II) sulfate, zirconium dioxide, vanadium pentoxide, aluminum oxide γ, copper(II) oxide), and phase transfer agents (isobutanol, tetraoctylammonium bromide, and tetra-n-butylammonium fluoride), were examined to identify the optimal combination for reducing sulfurous compounds in the UAOD process. The influence of the extraction stage and reactor vessel material on the desulfurization efficiency was also investigated. Results revealed that hydrogen peroxide, formic acid, phosphotungstic acid, and isobutyl alcohol were the most effective oxidizers, promoters, catalysts, and phase transfer agents, respectively. Response surface methodology was used to determine the optimal conditions by evaluating different concentrations of these reagents within specific ranges. The study considered ranges such as 10-70 vol % of hydrogen peroxide, 5-70 vol % of formic acid, 1-30 wt % of phosphotungstic acid, 1-30 vol % of isobutanol, and 5-40 min of ultrasonic ripple time. Empirical models were developed for each sulfurous compound type, providing optimal conditions for sulfur removal with an error margin of less than 0.1%. The validity of the suggested models was confirmed through an industrial data analysis. Additionally, it was observed that increasing the number of extraction stages improved desulfurization efficiency, and using a stainless-steel reactor vessel was more suitable than using a glass vessel.

Preparation of new hydrogels by visible light cross-linking of dextran methacrylate and poly(ethylene glycol)-maleic acid copolymer.

In this work, a series of new biodegradable and biocompatible hydrogels were synthesized by photopolymerization of dextran-methacrylate (DXM) with poly(ethylene glycol)-maleic acid copolymer (poly(PEG-co-MA, PEGMA)) using (-)-riboflavin as a visible light photoinitiator and L-arginine as a co-photoinitiator. DXM was prepared by acylation of dextran (DX) with methacryloyl chloride (MAC), and PEGMA was synthesized by polycondensation of poly(ethylene glycol) (PEG) and maleic acid (MA). The DXM and PEGMA were characterized by FT-IR and 1HNMR spectroscopy. Different types of hydrogels from various ratios of DXM and PEGMA were prepared and characterized by SEM. The results showed that the prepared hydrogel by photo-cross-linking of DXM (DPHG0) was transparent and flexible, and its physical shape was excellent, but it was sticky. The stickiness was reduced by increasing the PEGMA contents, and different types of DXM/PEGMA hydrogels (DPHG1-4) with various properties were prepared. For example, DPHG2 (PEGMA content was 0.25 g) was transparent and flexible, its physical shape was excellent, and it was not sticky. The prepared hydrogels showed excellent cytocompatibility, and their tensile and compressive strength were also evaluated. Additionally, the in vitro degradation and swelling ratios of the prepared hydrogels were studied in buffer solution at different pHs.

Efficient hydrolysis of starch by α-amylase immobilized on cloisite 30B and modified forms of cloisite 30B by adsorption and covalent methods.

In this paper, α-amylase from Bacillus subtilis was successfully immobilized on three supports. First, α-amylase was immobilized on cloisite 30B via the adsorption method. Then cloisite 30B was activated with tosyl chloride and epichlorohydrin. These activated supports were used for covalent immobilization of α-amylase, and their enzymatic activities were effectively tested in the starch hydrolysis. The results demonstrated that the specific activity of α-amylase immobilized on cloisite 30B was 2.39 ± 0.03, for α-amylase immobilized on activated cloisite 30B with epichlorohydrin was 1.96 ± 0.05 and for α-amylase immobilized on activated cloisite 30B with tosyl chloride was 2.17 ± 0.05 U mg-1. The optimum pH for the activity of free α-amylase was 7, but for α-amylase immobilized on cloisite 30B was 8, and for α-amylase immobilized on activated supports was 7.5. The immobilized enzymes had better thermal resistance and storage stability than free α-amylase, and they also showed excellent reusability.

Covalent immobilization of lipase from Candida rugosa on epoxy-activated cloisite 30B as a new heterofunctional carrier and its application in the synthesis of banana flavor and production of biodiesel.

In this paper, an epoxy-activated cloisite (ECL) was prepared as a new heterofunctional carrier via a reaction between cloisite 30B (CL) and epichlorohydrin and utilized for covalent immobilization of lipase from Candida rugosa. The lipase immobilized on the ECL (LECL) was successfully used in the olive oil hydrolysis, synthesis of isoamyl acetate (banana flavor), and biodiesel production. The TGA, FT-IR, SEM, and XRD were used to characterize CL, ECL, and LECL. The influences of temperature, pH, thermal stability, and storage capacity were examined in the olive oil hydrolysis. The effects of solvent, temperature, time, water content, and substrates molar ratio on the yields of ester and biodiesel were also investigated. In the optimized conditions, the hydrolytic activity of LECL was 1.85 ± 0.05 U/ mg, and the maximum yield of ester and biodiesel was 91.6% and 95.4%, respectively. The LECL showed good thermal stability and storage capacity compared to the free lipase. Additionally, LECL was reusable for both esterification and transesterification after being used for nine cycles.

Population inversion of binary Lennard-Jones mixtures in nanoslit pores (a density functional theory study).

The aim of this work is to investigate the population inversion of binary asymmetric Lennard-Jones mixtures inside nanoslit pores due to confinement effects for both vapor and liquid phases. For this purpose we have used mean field fundamental measure theory, and the effect of different parameters such as interaction strength and size ratios of the components, confinement size, and thermodynamic state on the population distribution of molecules have been studied. It has been shown that in the case of bulk liquid mixtures, increasing the role of confinement effects can lead to preferential adsorption of the component with larger size and weaker intermolecular interactions into the nanopore in spite of its minority in the bulk which is referred as population inversion. This population inversion phenomenon is terminated by a sudden condensation which, interestingly, involves a simultaneous adsorption and desorption for more and less bulk concentrated species, respectively. We have demonstrated that this condensation phenomenon shifts to higher bulk densities with increasing the role of confinement effects such that in some cases population inversion is observable for the whole range of densities. In consideration of the conditions in which vapor Lennard-Jones mixtures undergo capillary condensation, the population distribution of components in the vapor- and liquidlike phases was studied. It has been shown that variation of parameters such as interaction strength and size ratios, temperature, and confinement size can lead to conditions in which capillary condensation is accompanying with a population inversion phenomenon. In these cases, whereas the composition of vaporlike phases is the same as bulk fluid, liquidlike phases are richer in the component with less bulk concentration.

How wall curvature affects the structure of fluid around a cylindrical nanoparticle: a DFT approach.

In this work, the perturbative fundamental measure theory has been employed to obtain the two-dimensional density distributions of the two hard-sphere and hard-core Two-Yukawa fluids around a hard cylindrical nanoparticle. We have performed our calculations for different densities and temperatures. It has been observed that the oscillatory behavior of structure of molecules around a cylindrical nanoparticle increases with density and with decreasing wall curvature. In fact, energy and entropy effects determine fluid structure around the cylindrical nanoparticle. Our results show that, in the absence of any long-range wall-molecule and molecule-molecule interactions, hard-sphere-hard-wall, the effect of wall curvature on structure is determined by entropy effects. In this case, molecules show a reduced tendency to accumulate at the wall with increasing curvature and a minimal tendency to position themselves at the nanoparticle edges. Energy effects in fluids with molecule-molecule attractions, Yukawa fluids, may lead to an increase in the tendency of their molecules to accumulate at more curved walls. In these systems, the competition between energy and entropy effects may reverse their molecular behavior such that they have the greatest tendency to accumulate at the edges rather than at other regions. Cases have been observed in which the domination of energy effects causes the depletion phenomenon near the walls. In this study, these observations have been confirmed by studying the local excess adsorptions around different regions of a cylindrical nanoparticle.