Sharif Digital Repository

Hydrocracking is one of the most versatile petroleum refining processes for production of valuable products including gasoline, gas oil, and jet fuel. In this paper, a five-parameter continuous lumping model was used for kinetic modeling of hydrocracking of vacuum gas oil (VGO). The model parameters were estimated from industrial data obtained from a fixed bed reactor operating at an average temperature of 400°C and residence time of 0.3 h. Product distributions were obtained in terms of the weight fraction of various boiling point cuts. The model parameters were estimated using the Nelder-Mead optimization procedure and were correlated with temperature. Comparison of experimental and... 

In this work, a new model based on multilayer kinetic adsorption mechanism has been proposed to account asphaltene adsorption in porous media under dynamic condition and the model was verified using experimental data obtained in this work and also with those reported in the literature. In the proposed model two steps are considered for asphaltene adsorption. The first step is taken as adsorption of asphaltenes on the surface of the porous media and the second step is taken as adsorption of asphaltenes on the asphaltenes already adsorbed on the porous media. The Crank-Nicholson method, central difference in space and trapezoidal rule in time, giving second order convergence in time was... 

A reduction in catalyst's activity with time-on-stream and the formation of side products are two of the problems associated with catalytic propane dehydrogenation (PDH). Previous studies have indicated that the presence of small amounts of oxygenated additives such as water can reduce coke formation and enhance catalyst activity. The aim of the present work was to develop an appropriate kinetic model for PDH over a commercial Pt-Sn/γ-Al 2O3 catalyst in the presence of small amounts of water. Experimental data were obtained from a previous study where catalytic PDH was carried out in a bench scale reactor system at atmospheric pressure in the temperature range of 575-620°C in the presence of... 

In the present work, the synergetic effect of Ti-based catalysts (TiH2 and TiO2 particles) on hydrogen desorption kinetics of nanostructured magnesium hydride was investigated. Nanostructured 84mol% MgH2-10%mol TiH2-6%mol TiO2 nanocomposite powder was prepared by high-energy ball milling and subjected to thermal analyses. Evaluation of the absorption/desorption properties revealed that the addition of the Ti-based catalysts significantly improved the hydrogen storage performance of MgH2. A decrease in the decomposition temperature (as high as 100°C) was attained after co-milling of MgH2 with the Ti-based catalysts. Meanwhile, solid-state chemical reactions between MgH2 and TiO2 nanoparticles... 

Propane dehydrogenation was carried over a commercial Pt-Sn/γ-Al 2O3 catalyst at atmospheric pressure and reaction temperatures of 580, 600, and 620°C and WHSV of 11 h-1 in an experimental tubular quartz reactor. Propane conversions were measured for catalyst time on stream of up to nine days. The amounts of coke deposited on the catalyst were measured after one, three, six, and nine days on stream using a thermogravimetric differential thermal analyzer (TG-DTA) for each reaction temperature. The coke formation kinetics was successfully described by a coke formation model based on a monolayer-multilayer mechanism. In addition, catalyst deactivation was presented by a time-dependant... 

This research aimed at finding the factors with more impact on the bioleaching of a spent hydrocracking catalyst by thermophilic acidophilic archaea called Acidianus brierleyi and determining the optimal condition in order to reach the maximum metals recovery. Initially, four more significant factors affecting the bioleaching efficiency including pH, pulp density, inoculation and elemental sulfur concentration, were screened and identified among ten key factors using Plackett-Burman factorial design. Next, a central composite design was applied to obtain the optimum conditions for achieving the maximum efficiency of the bioleaching process. pH 1.6, pulp density 0.6% (w/v), inoculation 4%... 

Thermal oxidation of commercial ilmenite concentrate from Kahnouj titanium mines, Iran, at 500-950 C was investigated for the first time. Fractional conversion was calculated from mass change of the samples during oxidation. Maximum FeO to Fe2O3 conversion of 98.63 % occurred at 900 C after 120 min. Curve fit trials together with SEM line scan results indicated constant-size shrinking core model as the closest kinetic mechanism of the oxidation process. Below 750 C, chemical reaction with activation energy of 80.65 kJ mol-1 and between 775 and 950 C, ash diffusion with activation energy of 53.50 kJ mol-1 were the prevailing mechanisms. X-ray diffraction patterns approved presence of... 

In this research nano γ-Al 2O 3 catalyst was synthesized through precipitation process then characterized and utilized for methanol dehydration reaction in a slurry batch reactor in route to the indirect synthesis of the dimethyl ether (DME). In this venue, effects of the key parameters on methanol conversion and catalyst stability were investigated. Moreover, the internal and external mass transfer resistances were eliminated; hence the intrinsic kinetics controlled the reaction. Therefore, the optimum conditions for temperature, methanol concentration, catalyst mass and stirrer speed were determined to be 300°C, 1.18mol/l, 1.5g and 1100rpm, respectively. Next, different reaction rate... 

In this research, an algorithm based on the Q-state Potts model is presented for modeling the austenite to ferrite transformation. In the algorithm, it is possible to exactly track boundary migration of the phase formed during transformation. In the algorithm, effects of changes in chemical free energy, strain free energy and interfacial energies of austenite-austenite, ferrite-ferrite and austenite-ferrite during transformation are considered. From the algorithm, the kinetics of transformation and mean ferrite grain size for different cooling rates are calculated. It is found that there is a good agreement between the calculated and experimental results  

A novel method is proposed in order to find the kinetics of dynamic recovery in the form of Avrami relation using hot flow curves. The relation is derived on the basis of variation of dislocation density with strain. The model is applied on an Al-Mg alloy  

In this experimental study, a kinetic model has been developed for Fischer-Tropsch synthesis reactions by using sol-gel technique and Fe/Ni/Al 2O 3 as the catalyst (40% Fe/60% Ni/40 wt.%Al 2O 3) in a differential fixed-bed micro reactor assuming no internal or external diffusion. Operating conditions of the reactor were as follows: total pressure 1-12 atm; Temperature 220-260 °C; H 2/CO feed ratio 1.5-2; gas hourly space velocity 2100-7000 cm 3(STP)/h/ g cat and conversions of 6-37% of hydrogen and 7-21% of carbon monoxide. Mass transfer limitations were investigated by changing synthesis gas velocity in reactors which differ in size. Based on the hypothesis that water inhibits the intrinsic... 

Dinuclear cis-dioxomolybdenum(VI) complex [{MoO 2(Bz 2Benzenediyldtc)} 2] coordinated by a quadradentate dithiocarbamate (Bz 2Benzenediyldtc 2- = 1,4-benzenediylbis(benzyldithiocarbamate)(2-)) has been prepared and characterized by elemental analysis, 13C NMR, IR and UV-vis spectroscopy. The kinetics of the oxygen atom transfer between [{MoO 2(Bz 2Benzenediyldtc)} 2] and PPh 3 was studied spectrophotometrically in CH 2Cl 2 medium at 520 nm and four different temperatures, 288, 293, 298 and 303 K, respectively. The reaction follows second order kinetics with the rate constant k = 0.163(2) M -1 S -1 and its increasingly strong absorption at 520 nm clearly indicate the formation of a μ-oxo... 

A simple bio-conjugation procedure to surround a single horseradish peroxidase (HRP) enzyme molecule with dendritic polyester macromolecules (polyester-32-hydroxyl-1-carboxyl bis-MPA dendron, generation 5) was proposed. The characterization of resultant nanoparticles entitled HRP dendrozyme, was performed by transmission electron microscopy, dynamic light scattering, gel permeation chromatography and Fourier transform infrared spectroscopy. The results showed that HRP nanoparticles were spherical in shape and have an average size of 14 ± 2. nm in diameter. Furthermore, bio-conformational characterization of HRP dendrozyme was performed by means of circular dichroism and fluorescence... 

The current study was carried out to investigate the kinetics of reactions for the pressure oxidative leaching of a molybdenite concentrate in less than one hour. The effects of oxygen pressure, stirring speed, pulp density, acid concentration and temperature on the leaching rate of the molybdenum were studied. It was found that about 85% of molybdenite was oxidized to molybdic oxide precipitate with remaining molybdenum dissolved in the leaching liquor. Analysis of experimental data showed that the reaction is chemically controlled with activation energy of 68.8 kJ/mol. Furthermore SEM images showed no significant boundary diffusion layer and it was noted that the molybdic oxide... 

In this work, the effect of carbon dioxide partial pressure on the calcination kinetics of high purity zinc carbonate hydroxide has been studied. Non-isothermal analysis has been performed on samples at different CO 2 partial pressures by TGA and DTA. It has been found that the calcination behaviour of this material corresponds to the shrinking core model and the reaction mechanism is phase boundary controlled. The calcination reaction of zinc carbonate hydroxide starts at 240 °C. Increasing the carbon dioxide partial pressure can result in an increase in the reaction start temperature of up to 30°C. The activation energy for the reaction is calculated as 180 ± 5 kJ/mol at... 

Progressive conversion/shrinking core (PC-SC) models of constant-size cylinders were exploited to interpret the decarburization reactions of MgO-C-Si bricks heated up under blown air. Chemical adsorption/solid (or pore) diffusion mechanisms governed the reaction rate. With 5% silicon, chemical adsorption vanished at 1000 and 1100°C. The oxidation rate lowered then with temperature. This was due apparently to the blocking of the pore-end gorges by the voluminous compounds (like Forstrite). Arrhenius plots of the specific rates yielded the activation energies of the prevailing steps. Without Si antioxidant, three steps were appreciated having activation energies of 51.65 (for chemical... 

In micron-scale, powder consolidation process is driven by diffusion phenomenon, while in nano-scale the higher surface energy of particles leads to some anomalous behaviors within the process. In order to investigate the nano-sintering occurrence, an atomistic approach is employed via molecular dynamics simulations. Within this approach, the effect of particle size and temperature is examined. The study of particle structure emphasizes on a transition on the governing mechanism of process depending on the material energy levels. The results show that in a specific particle size at low temperatures, the main sintering mechanism is the plastic deformation, while at elevated temperatures it... 

A new nonlinear optimization method for parameter estimation in Michaelis-Menten equation has been developed. This method is based on a special mathematical form of the Michaelis-Menten equation to finding the best fit of the linear plot of R versus S/(S + Km) where R, S, and Km are the reaction rate, concentration of substrate, and the Michaelis-Menten constant, respectively. By setting the intercept of this line to zero, the proper Km will be obtained and the slope would give the saturation rate, Vmax. As a result, a nonlinear, two-parameter optimization is simplified into finding the roots of a nonlinear equation. Generated data sets were used... 

The thorough knowledge of the asphaltene aggregation phenomena and pressure/temperature related kinetics is helpful for accurate prediction/control of the asphaltene issues in all facets of petroleum production/processing. However, characterizing the asphaltene aggregation phenomena in live oils at high pressure-high temperature conditions is not well discussed in the available literature. In this work, the asphaltene aggregation phenomena as well as the kinetics of aggregation at different levels of pressure and temperature are investigated in light and heavy live oils using high pressure microscope. The results are presented and discussed in terms of asphaltene onset pressure, aggregates... 

The oxidation behavior of three types of stainless steels, namely AISI 321, AISI 316, and AISI 409, was compared. In all stainless steels, oxide layers were formed and their masses and thicknesses increased with oxidation time. Among them, AISI 409 ferritic stainless steel demonstrated higher oxidation rate. According to the kinetical oxidation behavior of them at elevated temperatures, the oxidation mechanism was determined. Among them, the AISI 409 ferritic stainless steel showed the lowest and AISI 321 austenitic stainless steel demonstrated the highest oxidation resistance. Based on the experimental results, it was suggested that the kinetic of oxide growth in stainless steels was...