Highly efficient supported AlCl3-based cationic catalysts to produce polyα-olefin oil base stocks

The main aim of this research is to decrease the amount of AlCl₃ content that is very corrosive and hazardous in the catalytic system, required for the α-olefin oligomerization without substantial change of final oil features. This was successfully achieved by supporting AlCl₃ on different carriers. More precisely, a series of supported bimetallic catalysts was synthesized by immobilization of AlCl₃ and TiCl₄ onto Al₂O₃, SiO₂, and mixed supports, that is, Al₂O₃/FeCl₃ and SiO₂/FeCl₃. It was found that silica and alumina-based catalysts had higher catalytic activities compared to support free AlCl₃; however, this enhancement for silica-based supports was more significant. According to gel permeation chromatography (GPC) results, the use of single supports, that is, Al₂O₃ and SiO₂, increased oligomer's molecular weight, while the application of mixed supports resulted in the decrease of molecular weight of the oligomers. Viscosity characteristics of the synthesized oligomers have also been studied at two different temperatures of 40 and 100°C (KV⁴⁰ and KV¹⁰⁰). The viscosity index (VI) values, derived from KV⁴⁰ and KV¹⁰⁰, of the prepared oligomers were in the range of 126–145. The molecular weight and termination mechanisms of the oligomers were studied by ¹H-NMR spectroscopy. The obtained results disclosed that the employed reaction conditions led to the production of oligomer chains with various structures including vinylidene (Vd), and di and three-substituted vinylene (2Vn, 3Vn) structures.     

Bi-supported Ziegler–Natta TiCl4/MCM-41/MgCl2 (ethoxide type) catalyst preparation and comprehensive investigations of produced polyethylene characteristics

Bi-supported Ziegler–Natta catalysts (TiCl₄/MCM-41/MgCl₂ (ethoxide type)) were synthesized to improve the morphology and the properties of polyethylene. The morphology control is a crucial issue in polymerization process, while tailoring the properties of polymers is needed for specific applications. The catalysts were synthesized in different ratios of two supports with impregnation method. The polymerization process was carried out in atmospheric slurry reactor. The catalysts were characterized with scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM–EDX), inductively coupled plasma, Fourier transform infrared spectrometry (FTIR), and Brunauer-Emmett-Teller (BET) methods. The polymers were analyzed with scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry, FTIR, and tensile-strength analyses. Ubbelohde viscometer and frequency sweep measurements showed that the synthesized polymers are ultra-high-molecular-weight polyethylene. Mechanical properties of polymers showed higher Young's modulus in samples containing MCM-41, having higher thermal stability supported by TGA analysis. SEM images of bi-supported catalyst showed a controlled spherical morphology with uniform size distribution. SEM analysis support that the polymers replicate their morphology from catalyst, improving their morphology comparing to MgCl₂-supported catalyst. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48553.     

Optimization of a continuous ultrasound assisted oxidative desulfurization (UAOD) process of diesel using response surface methodology (RSM) considering operating cost

A continuous-flow ultrasound-assisted oxidative desulfurization(UAOD) of partially hydro-treated diesel has been investigated using hydrogen peroxide-formic acid as simple and easy to apply oxidation system. The effects of different operating parameters of oxidation stage including residence time(2–24 min), formic acid to sulfur molar ratio(10–150), and oxidant to sulfur molar ratio(5–35) on the sulfur removal have been studied using response surface methodology(RSM) based on Box–Behnken design. Considering the operating costs of the continuous-flow oxidation stage including chemical and electrical energy consumption, the appropriate values of operating parameters were selected as follows: residence time of 16 min, the formic acid to sulfur molar ratio of 54.47, and the oxidant to sulfur molar ratio of 8.24. In these conditions, the sulfur removal and the volume ratio of the hydrocarbon phase to the aqueous phase were 86.90% and 4.34, respectively. By drastic reduction in the chemical consumption in the oxidation stage, the volume ratio of the hydrocarbon phase to the aqueous phase was increased up to 10. Therefore, the formic acid to sulfur molar ratio and the oxidant to sulfur molar ratio were obtained 23.64 and 3.58, respectively, which lead to sulfur removal of 84.38% with considerable improvements on the operating cost of oxidation stage in comparison with the previous works.     

Potency of Different Carbon Sources in Reduction of Microsilica to Synthesize SiC from Mechanically Activated Powder Mixtures

In the present study, the influences of three different types of carbon (carbon black, graphite, and petroleum coke) on SiC synthesis via mechanical activation and sintering were evaluated. In this regard, the phase components, morphology, and the formation mechanism were investigated. SiC nanoparticles were detected to be formed after 4 h of milling and sintering at 1450°C, regardless of the sources of carbon. The carbon types exert their effects on the morphology of the as‐synthesized particles, where carbon black leads to form rod‐like SiC particles and the other two carbon types result in semi‐spherical SiC particles. This is due to the dominant mechanism in the mentioned process. The rod‐like particles obtained from the carbon black‐containing powder were synthesized via the VSL mechanism, whereas the solid‐state reactions occurred to form the SiC particles in the graphite‐ or petroleum coke‐containing samples. In the VSL mechanism, any increase in the milling time leads to facilitate the SiC formation due to entrance of Fe debris, whereas in the other samples (graphite or petroleum coke) the procedure is reversed.     

Poly1‐hexene: New impact modifier in HIPS technology

Poly1‐hexene was prepared using a conventional heterogeneous Ziegler–Natta catalyst and its stereoregularity was characterized using ¹³C‐NMR analysis. New kind of high impact polystyrene (HIPS) was prepared by radical polymerization of styrene in the presence of different amounts of synthesized poly1‐hexene (PH) as impact modifier (HIPS/PH) and compared with conventional high impact polystyrene with polybutadiene (HIPS/PB) as rubber phase. Scanning electron microscopy (SEM) revealed that the dispersion of poly1‐hexene in polystyrene matrix was more uniform compared with it in HIPS/PB. The impact strength of HIPS/PH was 29–79% and 80–289% higher than that in HIPS/PB and neat polystyrene, respectively. FTIR was used to confirm more durability of HIPS/PH samples toward ozonation. To study the effect of rubber type and amount on the T_gs of polystyrene, differential scanning calorimetry was employed. Results obtained from TGA demonstrated higher thermal stability of HIPS/PH sample in comparison with conventional HIPS/PB one. Our obtained results suggest new high impact polystyrene that in all studied aspects has better performance than the conventional HIPS. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43882.     

Effects of Rheological Behavior of Viscoelastic Surfactants on Formation Damage in Carbonate Rocks

Viscoelastic surfactants (VES) are used in various oilfield applications such as matrix stimulation and enhanced oil recovery. The loss of surfactants during the propagation of VES could result in a significant reduction in the permeability of the rock (formation damage). The objective of the current work was to identify the effect of rheological behavior of the VES on the formation damage using core‐flooding experiments, nuclear magnetic resonance (NMR), and scanning electron microscopy (SEM) analysis. A combination of core‐flooding, NMR, and SEM techniques was used to quantify and identify the location of formation damage in carbonate core samples. The viscosity and storage modulus strongly depend on the nature and concentration of salts. The viscosity increased by increasing the salt concentration up to a specific point (15 wt% CaCl₂) and then starts decreasing. The VES formulations that displayed the maximum and minimum viscosities were used to identify the impact of rheological behavior on formation damage. Core‐flooding experiments were performed to assess the formation damage due to high‐viscosity and low‐viscosity VES formulations. The reduction in the permeability of carbonate rocks reaches more than 90% of the initial permeability. It was found that low‐viscosity VES caused more damage compared with high‐viscosity VES when they were used at constant concentrations. NMR and core‐flooding results revealed that the damage took place both in pore body and pore throat. However, most of the surfactant was retained at the pore throat.     

Removal of zinc ions from aqueous solution using a cation exchange resin

The present study is concerned with the mass transfer and kinetics study of zinc ions removal from aqueous solution using a cation exchange resin packed in a rotating cylindrical basket reactor. The effect of various experimental parameters on the rate of zinc ion removal, such as initial zinc ion concentration, packed bed rotation speed and temperature has been investigated. In addition to find a suitable equilibrium isotherm and kinetic model for the zinc ion removal in a batch reactor. The experimental isotherm data were analyzed using the Langmuir, Freundlich and D–R equations. The equilibrium data fit well in the Langmuir isotherm. The experimental data were analyzed using four sorption kinetic models, pseudo-first and second-order equations, the Elovich and the intraparticle diffusion model equation, to determine the best fit equation for the biosorption of zinc ions onto purolite C-100 MH resin. Results show that the Elovich equation provides the best correlation for the biosorption process.     

Identification of the flow structures and regime transition in gas–solid fluidized beds through moment analysis

Using statistic parameters of solids holdup signals, a moment consistency data processing method (MCDPM) was proposed. Experiments were carried out using FCC particles of 76 μm under different operating conditions, and MCDPM was used to successfully obtain solids holdups of the dense and dilute phases and the phase fractions over five fluidization regimes, bubbling (BFB), turbulent (TFB), circulating turbulent (CTFB), high‐density circulating (HDCFB), and circulating (CFB) fluidized bed systems. In BFB, TFB, and CTFB regimes, only dense phase fraction decreased with increasing air velocity, while the transition from HDCFB to CFB experienced appreciable change in the solids holdup of the dense phase. From the low‐velocity to the high‐velocity regimes, both the solids holdup and the fraction of the dense phase experienced a drastic decrease, suggesting that this transition corresponded to a profound change in flow structure and further suggesting that CTFB is in reality still a TFB. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1479–1490, 2013     

Minimum-gain minimum-time deadbeat controllers

This paper considers the design of minimum-gain minimum-time deadbeat controllers (MGMTDC) for linear discrete-time systems. A new direct method for constructing the MGMTDC of minimum Frobenius norm is developed. Compared with many existing techniques, the proposed method gives analytic expressions for the constructed MGMTDC, requires less computational effort, and does not require that the transition matrix be nonsingular.