Study on kinetics of propylene polymerizationat different temperatures via Monte Carlo simulation

The elementary reactions of propylene polymerization catalyzed by conventional Ziegler-Natta catalysts was proposed according to the comprehensive view and without considering the effect of any impurity in the material on propylene polymerization. The Monte Carlo simulation technique was employed to investigate the kinetics of propylene polymerization in order to determine the validity of the stationary state assumption and the effects of the polymerization temperature on the polymerization. The simulated total amount of active species, which only increases quickly at the beginning of the polymerization, indicates that the stationary state assumption in the studied system is valid. Moreover, significant effects of polymerization temperature on the polymerization conversion, and the molecular weight and its distribution were also analyzed. The simulated results show that the consumption rate of propylene increases with the increase of polymerization temperature; the maximum values of the number-average degree of polymerization are constant at different polymerization temperatures, however, the peak appears earlier with the higher temperature; as the polymerization temperature increases, the average molecular weight decreases and the molecular weight distribution changes greatly.

Molecular simulation study of the microstructures and properties of pyridinium ionic liquid[HPy][BF_(4)]mixed with acetonitrile

The microstructures and thermodynamic properties of mixed systems comprising pyridinium ionic liquid[HPy][BF_(4)]and acetonitrile at different mole fractions were studied using molecular dynamics simulation in this work.The following properties were determined:density,self-diffusion coefficient,excess molar volume,and radial distribution function.The results show that with an increase in the mole fraction of[HPy][BF_(4)],the self-diffusion coefficient decreases.Additionally,the excess molar volume initially decreases,reaches a minimum,and then increases.The rules of radial distribution functions(RDFs)of characteristic atoms are different.With increasing the mole fraction of[HPy][BF_(4)],the first peak of the RDFs of HA1-F decreases,while that of CT6-CT6 rises at first and then decreases.This indicates that the solvent molecules affect the polar and non-polar regions of[HPy][BF_(4)]differently.

Simulation of porous medium engine using a detailed chemical kinetics model

The Senkin code of package is used to simulate the the Chemkin chemical kinetics combustion process of a porous medium（PM） engine fueled by n-heptane. The code is modified to incorporate the Woschni heat transfer correlation and heat transfer model within a porous medium. A detailed chemistry mechanism of NOx formation is coupled with the detailed chemical kinetics mechanism of n-heptane. The code is applied to a zero- dimensional single-zone model of engine combustion. Influences of operating parameters on the performance of the PM engine are discussed. With the increase in the intake temperature and compression ratio, or with the decrease of the excess air ratio, the ignition timing of the PM engine obviously advances. It is found that the porous medium acting as a heat recuperator can considerably preheat the fuel-air mixture, which promotes the ignition and combustion in the cylinder. And the initial PM temperature is a critical factor controlling the compression ignition of the mixture.

Magnetopause properties at the dusk magnetospheric flank from global magnetohydrodynamic simulations,the kinetic Vlasov equilibrium,and in situ observations--Potential implications for SMILE

We derived the properties of the terrestrial magnetopause(MP)from two modeling approaches,one global–fluid,the other local–kinetic,and compared the results with data collected in situ by the Magnetospheric Multiscale 2(MMS2)spacecraft.We used global magnetohydrodynamic(MHD)simulations of the Earth’s magnetosphere(publicly available from the NASA-CCMC[National Aeronautics and Space Administration–Community Coordinated Modeling Center])and local Vlasov equilibrium models(based on kinetic models for tangential discontinuities)to extract spatial profiles of the plasma and field variables at the Earth’s MP.The global MHD simulations used initial solar wind conditions extracted from the OMNI database at the time epoch when the MMS2 observes the MP.The kinetic Vlasov model used asymptotic boundary conditions derived from the same in situ MMS measurements upstream or downstream of the MP.The global MHD simulations provide a three-dimensional image of the magnetosphere at the time when the MMS2 crosses the MP.The Vlasov model provides a one-dimensional local view of the MP derived from first principles of kinetic theory.The MMS2 experimental data also serve as a reference for comparing and validating the numerical simulations and modeling.We found that the MP transition layer formed in global MHD simulations was generally localized closer to the Earth(roughly by one Earth radius)from the position of the real MP observed by the MMS.We also found that the global MHD simulations overestimated the thickness of the MP transition by one order of magnitude for three analyzed variables:magnetic field,density,and tangential speed.The MP thickness derived from the local Vlasov equilibrium was consistent with observations for all three of these variables.The overestimation of density in the Vlasov equilibrium was reduced compared with the global MHD solutions.We discuss our results in the context of future SMILE(Solar wind Magnetosphere Ionosphere Link Explorer)campaigns for observing the Earth’s MP.

Multi-lump Kinetic Parameter Estimation and Simulation of Trickle-bed Reactor for Ultra-deep Hydrodesulfurization of Diesel

A three-lumping Langmuir-Hinshelwood kinetic model was established based on the structures and reactivities of sulfur compounds.This model described the ultra-deep hydrodesulfurization(UDHDS)performance of diesel,reducing sulfur content from 10000μg/g to less than 10μg/g,with experimental and predicted data showing a discrepancy of less than 10%.The diesel UDHDS reaction was simulated by combining the mass transfer,reaction kinetics model,and physical properties of diesel.The results showed how the concentrations of H2S,hydrogen,and sulfur in the gas,liquid,and solid phases varied along the reactor length.Moreover,the study discussed the effects of each process parameter and impurity concentrations(H2S,basic nitrogen and,non-basic nitrogen)on diesel UDHDS.

Gyrokinetic simulations of the kinetic electron effects on the electrostatic instabilities on the ITER baseline scenario

The linear and nonlinear simulations are carried out using the gyrokinetic code NLT for the electrostatic instabilities in the core region of a deuterium plasma based on the International Thermonuclear Experimental Reactor(ITER)baseline scenario.The kinetic electron effects on the linear frequency and nonlinear transport are studied by adopting the adiabatic electron model and the fully drift-kinetic electron model in the NLT code,respectively.The linear simulations focus on the dependence of linear frequency on the plasma parameters,such as the ion and electron temperature gradientsκ_(Ti,e)≡R=L_(Ti,e),the density gradientκ_(n)≡R/L_(n)and the ion-electron temperature ratioτ=T_(e)=T_(i).Here,is the major radius,and T_(e)and T_(i)denote the electron and ion temperatures,respectively.L_(A)=-(δ_(r)lnA)^(-1)is the gradient scale length,with denoting the density,the ion and electron temperatures,respectively.In the kinetic electron model,the ion temperature gradient(ITG)instability and the trapped electron mode(TEM)dominate in the small and large k_(θ)region,respectively,wherek_(θ)is the poloidal wavenumber.The TEMdominant region becomes wider by increasing(decreasing)κ_(T_(e))(κ_(T_(i)))or by decreasingκ_(n).For the nominal parameters of the ITER baseline scenario,the maximum growth rate of dominant ITG instability in the kinetic electron model is about three times larger than that in the adiabatic electron model.The normalized linear frequency depends on the value ofτ,rather than the value of T_(e)or T_(i),in both the adiabatic and kinetic electron models.The nonlinear simulation results show that the ion heat diffusivity in the kinetic electron model is quite a lot larger than that in the adiabatic electron model,the radial structure is finer and the time oscillation is more rapid.In addition,the magnitude of the fluctuated potential at the saturated stage peaks in the ITGdominated region,and contributions from the TEM(dominating in the higher k_(θ)region)to the nonlinear transport can be neglected.In the adiabatic electron model,the zonal radial electric field is found to be mainly driven by the turbulent energy flux,and the contribution of turbulent poloidal Reynolds stress is quite small due to the toroidal shielding effect.However,in the kinetic electron model,the turbulent energy flux is not strong enough to drive the zonal radial electric field in the nonlinear saturated stage.The kinetic electron effects on the mechanism of the turbulence-driven zonal radial electric field should be further investigated.

Monte Carlo Simulation of Kinetics of Ammonia Oxidative Decomposition over the Commercial Propylene Ammoxidation Catalyst (Mo-Bi)

Monte Carlo method is applied to investigate the kinetics of ammonia oxidative decomposition over the commercial propylene ammoxidation catalyst(Mo-Bi). The simulation is quite in agreement with experimental results. Monte Carlo simulation proves that the process of ammonia oxidation decomposition is a two-step reaction.

The decay kinetics of residual chlorine in cooling seawater simulation experiments

To find out the decay character of residual chlorine （RC） in the sea water, the concentration of RC was analyzed by N, N-diethyl-p-phenylenediamine （DPD） method under different simulation experimental conditions, in which salinity, temperature, and Chemical Oxygen Demand （COD） were selected. The water used in the experiment was the mixture of aging ocean water, coastal water and extracting solution of coastal sediment at appropriate level. Results are shown as follows： （1） Piecewise function can well reflect the decay dynamics of RC in the cooling seawater. Concretely, the decay dynamics of first 1 min is too rapid to ascertain using a specific kinetic function, and that of the time from 1 to 30 min is fit for the first-order kinetic model. （2） The results could be the foundation of the chemical behavior of RC in seawater, and be used as not only the guidance of the coastal power plants production and sea water desalting companies, but also the establishment of the correlative trade standard.

Effect of Lauroyl Glutamine on Biodegradation of Lubricating Oil and Simulation of Biodegradation Kinetics

Small amount of lauroyl glutamine was incorporated into HVI 350 mineral lubricating oil and the biodegradabilities of neat oil and the formulated oil in soils were evaluated. Thereafter, the biodegradation rate equations for the two lubricating oils were simulated based on the exponential model. The results indicated that lauroyl glutamine effectively promoted biodegradation of HVI 350 mineral lubricating oil. Under given test conditions, the exponential model well fitted the biodegradation of lubricating oils in soils. The biodegradation rate equation for HVI 350 mineral lubricating oil can be described as ln(St/S0) = –0.0155t, while that for the oil formulated with lauroyl glutamine as ln(St/S0) = –0.0235t. The biodegradation half-lives of neat oil and the formulated oils were 44.72 days and 29.50 days, respectively.

A SIMULATIONAL STUDY OF PRECIPITATION KINETICS AND MORPHOLOGY IN NITRIDATION OF ALLOY STEELS

An atomic model of compound precipitation in alloys, which couples cellular automaton growth/dissociation of precipitates and randomwalk diffusion, has been developed and programmed for 2 dimensional computer simulation. With boundary condition parameters and diffusion parameters variable, a series of simulation experiments were carried out for a qualitative study of nitride precipitation behavior in nitridation of alloy steels. Effects of nitrogen potential and alloy composition on kinetics and microstructure of the precipitation were addressed, and the so called "iso-activity aging" phenomenon was examined.

Simulation Experiments and Kinetics for the Formation of Organic Sulfide in Marine Carbonate Reservoirs

Thermal simulation experiments on the system of gasoline and magnesium sulfate were carried out using an autoclave operating at high temperature and high pressure in the presence of water. Properties of the gas-oil-solid 3-phase products were analyzed by some advanced analytical methods including gas chromatography, microcoulometry, capillary gas chromatography in combination with a pulsed flame photometric detector, FT-IR and X-ray diffraction. The results showed that the reaction could proceed at 450℃ - 550℃ to produce MgO, S, C, H2S, CO2 and a series of organic sulfides such as mercaptans, sulfoethers and thiophenes as the main products. According to the reaction kinetics, the calculated activation energy of the reaction is 68.9 kJ·mol-1.

RANS Simulation of Methane Diffusion Flame： Comparison of Two Chemical Kinetics Mechanisms

Turbulent non-premixed combustion of gaseous fuels is of importance for many technical applications, especially for the steel and refractory industry. Accurate turbulent flow and temperature fields are of major importance in order to predict details on the concentration fields. The performances of the GRI-Mech 3.0 and the Jones and Lindstedt mechanisms are compared. Detailed chemistry is included with the GRI-Mech 3.0 and J-L kinetic mechanisms in combination with the laminar flamelet combustion model. The combustion system selected for this comparison is a confined non-premixed methane flame surrounded by co-flowing air The simulation results are compared with experimental data of Lewis and Smoot （2001）.

Characteristics and pharmacokinetics of tripterygium glycosides nano-carries transdermal delivery systems:skin-blood synchronous microdialysis and numerical simulation

The traditional Chinese medicine tripterygium glycosides(TPG)is used clinically to treat some Rheumatism,Eczema,immunosuppression and tumor,with the activities of hypnosis,antipyretic,analgesic,antiinflammatory,allergy and antitumor.However TPG has low water solubility and low skin permeability,so its clinical use is limited.Transdermal delivery systems can provide a controlled drug release rate that can keep constant concentrations of drug in the plasma for up to multiple days,improved patient compliance,and the possibility ofreducing the rate and severity of side effects.In this study,a fast and sensitive technique skin-blood two sites synchronous microdialysis coupled with LC-MS was used to study the pharmacokinetic parameter of three different formulations(TPG nanoemulsion,TPG nanoemulsion based gels and TPG gel).Creating a multilayer model,use the model to simulate the three formulations dynamics in transdermal-drug delivery system.The experiment results showed that the TPG nanoemulsion,TPG nanoemulsion based gels can significantly raise the drug concentrations in skin more than that of TPG gels.The numerical simulation results indicating that TPG gel and TPG nanoemulsion are close to practical measurements,only in the concentration increase phase the numerical simulation result has some difference with the experimental results.TPG nanoemulsion based gels have significant difference with the experimental results,both in concentration increase stage and concentration decreasing stage,but its trend was same.The study shows that the skin-blood synchronous microdialysis technique provided a new method for the pharmacokinetics study of nanocarriers transdermal delivery systems.In addition,the microdialysis technique combined with mathematical modeling provides a very good platform for the further study of transdermal delivery system.

Hydrodearomatization Kinetics of Diesel Fraction and Catalyst Stacking Simulation

The kinetics of hydrodearomatization (HDA) is studied in an isothermal high-throughput reactor over three catalysts (CoMo, NiMo, and NiMoW) to produce clean diesel fuel according to China’s latest emission standards. The influences of reaction temperature, pressure, the ratio of H2 to oil, and space time were systematically investigated. By analyzing the reaction mechanism, a four-lump kinetic model considering the influence of competitive adsorption was proposed for the hydrodearomatization reaction, and the model parameters were optimized with good fitting. It was found that nitrogen compounds inhibited the hydrodearomatization reaction. The simulation of various catalyst stacking schemes based on the HDA kinetic model is close to the experimental data, proving the reliability of the model. The concentration of aromatic compounds of different loading sequences was predicted with the catalyst gradation model.

Modeling and Simulation of the Autocatalytic Kinetics of Haemoglobin SS Polymerization: Onset of Polymerization

We report a fresh and simpler approach to the modelling of the kinetics of the polymerization of Hb SS in sickle cell patients that couples the kinetics and the hydrodynamics of blood flow in mechanistic understanding of the process. The well-known two-step autocatalytic reaction scheme was used for the polymerization reaction with the assumption of simpler first-order reaction scheme for each stage. In addition, the forces acting on a particle in motion were also introduced to account for compelling settling of the red cells that lead to vessel occlusion (vaso-occlusion). A first attempt on the prediction of vessel blockage was made using this novel model. The time for the onset of the polymerization reaction was derived from hydrodynamic considerations and kinetics while the kinetic rate constants were obtained from the autocatalytic nature of the reaction. Experimental data for model validation were obtained from recruited SS patients and in vitro data of Hofrichter. Over 100 volunteers were recruited for participation in this work but less than 40% met the inclusion criteria. Participants were of age range 13 - 43 (with a mean of 26 ± 8 years) for SCD patients and 18 - 43 (with a mean of 28 ± 7 years) for control participants. Blood indices and Transcranial Doppler (TCD) test parameters of all participants were the principal parameters used for model validation. Constant k2/k1 ratios was obtained for individual in vivo/in vitro system. This ratio is unique for any individual, independent on protein sequence and also suggests the degree of expression of the symptoms of Sickle Cell Disease (SCD) with higher values reflecting greater propensity to pain crisis. Delay time, tD, was found to have an inverse relationship with the kinetic constant for the residual reaction, k1. Therefore, long delay times calculated, offer insight on why SCD patients are not in perpetual crises because enough time is provided the cells to escape microcirculation while keeping the residual reaction at the minimum. Sensitivity analysis was carried out to obviate the limitations encountered in the course of the work. Results showed the onset of occlusion to be most sensitive to the diameter of the blood vessel.

Experimental observation and computer simulation on non-equilibrium grain-boundary segregation kinetics of phosphorus

An experimental study and computer simulation on non-equilibriumgrain-boundary segregation kinetics and the critical time for phosphorus in 12CrlMoV steel (which isused in steam pipeline of ships) are put forward in this paper. The segregation level ofphosphorus with solution temperature 1 050 ℃ at the isothermal holding temperature of 5401 , havebeen measured at grain-boundaries. A non-equilibrium grain-boundary segregation kinetics curve ofphosphorus is given. The critical time for phosphorus non-equilibrium grain-boundary segregation isabout 500h at 540 ℃ for the experimental steel. When the holding time is longer than 1 500 h ,non-equilibrium segregation disappears and the level of segregation reaches full equilibrium. Thesimulation using the kinetic equations of non-equilibrium grain-boundary segregation is in goodaccordance with the experimental observation for phosphorus in steel 12Crl MoV. The non-equilibriumgrain-boundary segregation kinetic model is therefore proved.

Atomistic simulations of graphene origami:Dynamics and kinetics

Origami offers two-dimensional(2D)materials with great potential for applications in flexible electronics,sensors,and smart devices.However,the dynamic process,which is crucial to construct origami,is too fast to be characterized by using state-of-the-art experimental techniques.Here,to understand the dynamics and kinetics at the atomic level,we explore the edge effects,structural and energy evolution during the origami process of an elliptical graphene nano-island(GNI)on a highly ordered pyrolytic graphite(HOPG)substrate by employing steered molecular dynamics simulations.The results reveal that a sharper armchair edge is much easier to be lifted up and realize origami than a blunt zigzag edge.The potential energy of the GNI increases at the lifting-up stage,reaches the maximum at the beginning of the bending stage,decreases with the formation of van der Waals overlap,and finally reaches an energy minimum at a half-folded configuration.The unfolding barriers of elliptical GNIs with different lengths of major axis show that the major axis should be larger than 242 A to achieve a stable single-folded structure at room temperature.These findings pave the way for pursuing other 2D material origami and preparing origami-based nanodevices.

Numerical Simulations of One-Directional Fractional Pharmacokinetics Model

In this paper,we present a three-compartment of pharmacokinetics model with irreversible rate constants.The compartment consists of arterial blood,tissues and venous blood.Fick’s principle and the law of mass action were used to develop the model based on the diffusion process.The model is modified into a fractional pharmacokinetics model with the sense of Caputo derivative.The existence and uniqueness of the model are investigated and the positivity of the model is established.The behaviour of the model is investigated by implementing numerical algorithms for the numerical solution of the system of fractional differential equations.MATLAB software is used to plot the graphs for illustrating the variation of drug concentration concerning time.Therefore,the numerical simulations of the model are presented for different values ofαwhich verified the theoretical analysis.Besides,we also observed the pattern of the simulations at the three-compartment of the model by using different values of initial conditions.

Simulation Analysis of Neutron Time-space Kinetics for Venus-Ⅱ Lead Cold Zero Power Reactor Based on IQS/MC program

Accelerator driven sub-critical system is driven by an external neutron source which are generated by spallation reaction and maintains the stable operation of sub-critical core,while the external neutron source increases the complexity of reactor neutron kinetics processes.Numerical simulation of neutron space-time kinetics for the spallation neutron source coupled with sub-critical core is of significance on the research of dynamics process and transient simulation studies.IQS/MC is a program for simulation analysis of neutron time-space kinetics utilizing improved quasi-static approximation combined with Monte Carlo neutron transport code.A GUI-based control platform on MATLAB solving amplitude function and shape functions can achieves the dynamics simulation process.This work achieves the simulation of source change and safety rod dropping transient process of lead cooled zeropower experimental reactor by IQS/MC program.

Simulation of chemical kinetics in sodium-concrete interactions

Sodium-concrete interaction is a key safety-related issue in safety analysis of liquid metal cooled fast breeder reactors (LMFBRs). The chemical kinetics model is a key component of the sodium-concrete interaction model. Conservation equations integrated in sodium-concrete interaction model cannot be solved without a set of re-lationships that couple the equations together, and this may be done by the chemical kinetics model. Simultaneously, simulation of chemical kinetics is difficult due to complexity of the mechanism of chemical reactions between sodium and concrete. This paper describes the chemical kinetics simulation under some hypotheses. The chemical kinetics model was integrated with the conservation equations to form a computer code. Penetration depth, penetration rate, hydrogen flux, reaction heat, etc. can be provided by this code. Theoretical models and computational procedure were recounted in detail. Good agreements of an overall transient behavior were obtained in a series of sodium-concrete interaction experiment analysis. Comparison between analytical and experimental results showed that the chemical kinetics model presented in this paper was creditable and reasonable for simulating the sodium-concrete interactions.