Nonisothermal suspension polymerization of vinyl chloride for enhanced productivity

In the present study, a mathematical model is developed to numerically predict nonisothermal batch suspension polymerization of vinyl chloride. Free volume theory was used to consider diffusion‐controlled reactions. Model predictions were validated against field data obtained in a pilot scale stirred tank reactor. Variable temperature trajectory was considered during the course of the reaction to improve productivity by reducing the polymerization time for a certain conversion. Variable temperature during the course of the polymerization was successfully implemented by considering the predefined K value. By using variable temperatures during the course of the reaction, the density of the short branches per 1,000 monomer units as a criterion for structure defect remained relatively unchanged. Maximum reduction in reaction time relative to the isothermal case with the same K value and final conversion was 44% for the best temperature trajectory. J. VINYL ADDIT. TECHNOL., 22:470–478, 2016. © 2015 Society of Plastics Engineers     

A new mechanistic model to predict gas–liquid interface shape of gas–liquid flow through pipes with low liquid loading

Devising a new mechanistic method to predict gas–liquid interface shape in horizontal pipes is concerned in this article. An experiment was conducted to find the pressure gradients of air–water flow through a 1‐in. pipe diameter. Comparing results of model with some experimental data available in the literature demonstrates that the model provides quite better predictions than existed models do. This model also predicts flow regime transition from stratified to annular flow better than Apparent Rough Surface and Modified Apparent Rough Surface models for both 1‐ and 2‐in. pipe diameters. The model also leads to reliable predictions of wetted wall fraction experimental data. Although one parameter of new model was evaluated based on air–water flow pressure loss experimental data for 1 in. pipe, it was considerably successful to predict pressure drop, liquid holdup, stratified‐annular transition and wetted wall fraction for other gas–liquid systems and pipe diameters. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1043–1053, 2015     

An improved mechanism for capacity payment based on system dynamics modeling for investment planning in competitive electricity environment

Many countries have experienced restructuring in their electric utilities. This restructuring has presented the power industries with new challenges, the most important of which is long-term investment planning under uncertain conditions. This paper presents an improved mechanism for capacity payment. The mechanism has been investigated based on system dynamic modeling. In our proposed mechanism, generators will recover a part of their investment through capacity payment. While the payment for any plant remains constant during the operation period, it depends on the investment needed to build it. The main factors affecting long-term planning have been considered in our model. The approach can be used to investigate the effects of fixed as well as variable capacity payment in market investment. We used the probability density function of load as a new concept to calculate average market price. Delays in unit constructions, estimation of demand, and market capacity growth during construction periods have been included in the proposed algorithm as parameters, which affect the regulator's decision for changing capacity payment. The model can be used by regulators to investigate strategies that may affect the fluctuations in the market.     

Seismic soil–structure interaction analysis of wind turbines in frequency domain

In this paper, the seismic behavior of wind turbines sitting on a finite flexible soil layer is investigated in three‐dimensional space. A numerical algorithm formulated in frequency domain is proposed in order to simulate the dynamic soil–structure interaction (SSI). The wind turbine is discretized using finite element method (FEM) while, the underlying soil is represented by complex dynamic stiffness functions based on cone models. A parametric study consisting of 24 ground motions and three soil profiles is carried out, and different response quantities of the wind tower model are calculated and presented in the paper. The free‐field ground motions are estimated based on an equivalent linear approach using SHAKE2000 computer software. Transfer functions for total acceleration of the wind tower are obtained under the considered soil profiles and the modal frequencies of the coupled wind turbine–soil foundation are estimated. It is shown that the response quantities such as displacement, rotation, acceleration, base shear and moment are significantly affected by SSI, although the effect of SSI on the fundamental frequencies of the wind tower is insignificant. The moment and shear force distribution along the height of the tower is highly influenced as the soil stiffness decreases. The change in seismic demand distribution along the tower height because of SSI is not addressed by simplified design approached and should be carefully considered in seismic design of wind towers. Copyright © 2016 John Wiley & Sons, Ltd.     

A comparative study of ethylene polymerization by bis(aminotropone) Ti catalysts

A series of titanium aminotropone complexes bearing a pair of chelating [O–N] ligands have been synthesized and used for polymerization of ethylene successfully. Ethylene polymerization reactions were carried out at different conditions using the prepared catalysts. The activities for ethylene polymerization were significantly dependent on the catalyst structure. The polymerization activity increased with increasing of the both monomer pressure and [MAO]:[Ti] ratio. The highest activity of the catalysts was obtained at about 30–40 °C. It was demonstrated that unlike the high performance Ti–FI catalysts, bis(aminotropone) Ti catalysts do not require the presence of steric bulk in close proximity to the oxygen moiety. Introduction of the bulky alkyl substitution next to the oxygen moiety decreased the activity of the catalysts. Density Functional Theory (DFT) studies reveal that the active species derived from these catalysts normally possess higher electrophilicity nature compared with those produced using bis(phenoxy-imine) Ti catalysts (Ti–FI catalysts). Hydrogen was used as the chain transfer agent. The activities of the catalysts were increased with hydrogen concentration to some extent, but the M _v values of the obtained polymers were decreased. Crystallinity and melting point of the obtained polymer were between 42–62% and 102–124 °C, respectively. Higher pressure increased both the crystallinity and the M _v values of the resulting polymers. The catalyst 8a also produced PE with almost narrow polydispersities (1.10–2.55) as is typical for single-site catalysts. However, PDI was broadened by time.     

Modeling the oxidative coupling of methane using artificial neural network and optimizing of its operational conditions using genetic algorithm

The effect of some operating conditions such as temperature, gas hourly space velocity (GHSV), CH₄/O₂ ratio and diluents gas (mol% N₂) on ethylene production by oxidative coupling of methane (OCM) in a fixed bed reactor at atmospheric pressure was studied over Mn/Na₂WO₄/SiO₂ catalyst. Based on the properties of neural networks, an artificial neural network was used for model developing from experimental data. To prevent network complexity and effective data input to the network, principal component analysis method was used and the number of output parameters was reduced from 4 to 2. A feed-forward back-propagation network was used for simulating the relations between process operating conditions and those aspects of catalytic performance including conversion of methane, C₂ products selectivity, C2 yielding and C₂H₄/C₂H₆ ratio. Levenberg-Marquardt method is presented to train the network. For the first output, an optimum network with 4-9-1 topology and for the second output, an optimum network with 4-6-1 topology was prepared. After simulating the process as well as using ANNs, the operating conditions were optimized and a genetic algorithm based on maximum yield of C₂ was used. The average error in comparing the experimental and simulated values for methane conversion, C₂ products selectivity, yield of C₂ and C₂H₄/C₂H₆ ratio, was estimated as 2.73%, 10.66%, 5.48% and 10.28%, respectively.     

Active nano-CuPt3 electrocatalyst supported on graphene for enhancing reactions at the cathode in all-vanadium redox flow batteries

Graphene-supported monometallic (Pt) and bimetallic (CuPt₃) cubic nanocatalysts have been investigated as new positive electrode materials for improving the VO₂⁺/VO²⁺ redox process occurring in the vanadium redox flow batteries (VRB). High-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) have been employed to characterize the electrodes. The presence of the CuPt₃ nanocubes on graphene conferred higher electrocatalytic activity due to the much higher electroactive area compared to that obtained with the Pt nanoparticles. The electrochemical surface area of the nano-(CuPt₃)-decorated graphene electrode was 105% higher compared to non-decorated graphene, being then a promising alternative for improving the VRB.     

Prediction of induction time for natural gas components during gas hydrate formation in the presence of kinetic hydrate inhibitors in a flow mini‐loop apparatus

The objective of this work is the prediction of induction time (t_i) for simple gas hydrate formation in the presence or absence of kinetic hydrate inhibitors at various conditions based on the Kashchiev and Firoozabadi model in a flow mini‐loop apparatus. For this purpose, the t_i model is developed for simple gas hydrate formation in batch system for natural gas components during hydrate formation in a flow mini‐loop apparatus. A laboratory flow mini‐loop apparatus is designed and built up to measure the t_i for simple gas hydrate formation when a hydrate former (such as C₁, C₃, CO₂ and i‐C₄) is contacted with water in the absence or presence of dissolved inhibitor, such as poly vinylpyrrolidone, PVCap and L ‐tyrosine. In each experiment, a water blend saturated with pure gas is circulated up to a required pressure. Pressure is maintained at a constant value during experimental runs by means of the required gas make‐up. The average absolute deviation (AAD) of the predicted t_i values from the corresponding experimental data are found to be about 11% and 9.4% for gas hydrate formation t_i in the presence or absence of kinetic hydrate inhibitors, respectively. © 2012 Canadian Society for Chemical Engineering     

Synthesis of kappa-carrageenan-g-poly(acrylamide)/sepiolite nanocomposite hydrogels and adsorption of cationic dye

In this study, nanocomposite hydrogels from grafting of acrylamide onto kappa-carrageenan biopolymer were prepared in the presence of sepiolite clay. Methylenebisacrylamide and ammonium persulfate were used as cross-linker and initiator, respectively. The sepiolite nanoclay was introduced into hydrogel matrix without any chemical treatment. The structure of nanocomposites was investigated by FTIR, SEM, TEM, and TGA techniques. The TEM image showed that sepiolite exists as individual needle’s shape. The swelling of hydrogels were studied in distilled water, salt solutions, and various pHs. The obtained nanocomposites were evaluated to remove of cationic crystal violet (CV) dye from water. The kinetic and isotherm of adsorption of dye onto nanocomposites were studied and analyzed according to kinetic and isotherm models. The results showed that the pseudo-second-order adsorption kinetic was predominated for the adsorption of CV onto nanocomposites. The experimental equilibrated adsorption capacity of nanocomposites was analyzed using Freundlich and Langmuir isotherm models. The results corroborated that the experimental data fit the Langmuir isotherm the best. By varying the pH of initial dye solution, while the clay-free hydrogel showed relatively pH-independent adsorption behavior, the nanocomposites depicted pH-dependent adsorption.     

Synthesis of novel polyimides containing side‐chain azo‐2‐naphthol moieties

An amine‐ester derivative of isoeugenol was prepared in three steps. This amine‐ester was converted to diazonium salt and subsequently was reacted with 2‐naphthol and a novel isoeugenol ester‐azo derivative as a new monomer was obtained in quantitative yield. This monomer was characterized by high‐field ¹H‐NMR, IR, and elemental analysis and then was used for the preparation of model compound and polymerization reactions. 4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione was allowed to react with this new monomer. The reaction was very fast and gave only one double adduct by Diels–Alder and ene pathways in excellent yield. The polymerization reactions of novel monomer with bistriazolinediones [bis(p‐3,5‐dioxo‐1,2,4‐triazolin‐4‐ylphenyl)methane and 1,6‐bis(3,5‐dioxo‐1,2,4‐triazolin‐4‐yl)hexane] were carried out in N,N‐dimethylacetamide at room temperature. The reactions were exothermic, fast, and gave novel heterocyclic polyimides by repetitive Diels–Alder‐ene polyaddition reactions. Some structural characterization and physical properties of these novel heterocyclic polyimides are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1942–1951, 2003