Kinetics modeling for the mixed reforming of methane over Ni-CeO_2/MgAl_2O_4 catalyst

Kinetics model was developed for the mixed （steam and dry） reforming of methane, which is useful for the control of H2/CO ratio. The equilibrium constants of reaction rate were determined using the experimental equilibrium data at different reaction temperatures, while the forward reaction rate constants were estimated using the experimental data under non-equilibrium （high inert fraction and high space velocity） conditions. The comparison between calculated and experimental data clearly showed that the developed model described satisfactorily, and further analysis using the parametric sensitivity determined the wall temperature and CO2 fraction in the feed gas as effective parameters for the manipulation of CH4 conversion and H2/CO ratio of synthesis gas under the equilibrium condition. Meanwhile, the inert fraction, rather than the residence time, was selected as additional parameter under non-equilibrium condition.

Kinetics model of aerobic phase in hybrid anoxic-oxic process

Kinetics models of COD degradation,biomass growth of the anoxic-oxic ( A/O) system as well as NH3-N degradation in aerobic phase were presented according to the mass balance theory,reaction-diffusion theory and Fick law. Then these models were testified by comparson with experimental results. It is demonstrated that the variation trends of theoretical and experimental values for COD degradation and biomass growth are similar. The deviation rate between theoretical and experimental values is always under 20% even it increases along with the fluctuation of influent organic loading. In terms of NH3-N degradation,nitrification can also be well simulated by the model as the substrates of influent are sufficient. It indicates that the model can accurately reflect the reaction in hybrid A/O process. Models presented herein provide a theoretical basis for the design, operation and control of hybrid A/O process.

Modeling the Drying Kinetics of Pigeon Pea [Cajanus cajan (L.) Millspaugh]

We set out to model the oven-drying kinetics of a legume known as pigeon pea, harvested in the Bouenza department in the south-west of the Republic of Congo. The drying kinetics of pigeon peas was carried out in an oven under experimental conditions using temperatures of: 50°C, 60°C and 70°C. Seven mathematical models were used to describe pigeon pea drying. During drying, water loss was faster and shorter at 70°C [10.446 g/25 g wet weight (wwb) for 320 min (5.3 h)] compared to 50°C [10.996 g/25 g wet weight (wwb) for 520 min (8.6 h)] and 60°C [10.616 g/25 g wet weight (wwb) for 420 min (7.0 h)] where it was slower and longer. With regard to modeling, and based on the principle of choosing the right model focusing on the high value of R2 and low values of χ2 and RMSE, two models were selected, the Midili model for temperatures of 50°C and 60°C and the Henderson and Pabis model modified for temperature of 70°C showed better results. The R2, χ2 and RMSE values calculated for pigeon pea are 0.99985, 3.93404E-5 and 0.00627;0.9997, 9.245E-5 and 0.00962;0.99996, 1.56332E-5 and 0.00395 respectively at 50°C, 60°C and 70°C.

Modeling analysis of cobalt-based Fischer-Tropsch catalyst particles

The influences of particle size,shape,and catalyst distribution on the reactivity and hydrocarbon product selectivity of a cobalt-based catalyst for Fischer-Tropsch synthesis were investigated in the present work.A self-consistent kinetic model for Fischer-Tropsch reaction proposed here was found to correlate experimental data well and hence was used to describe the consumption rates of reactants and formation rates of hydrocarbon products.The perturbed-chain statistical associating fluid theory equation of state was used to describe vapor-liquid equilibrium behavior associated with Fischer-Tropsch reaction.Local interaction between intraparticle diffusion and Fischer-Tropsch reaction was investigated in detail.Results showed that in order to avoid the adverse influence of intraparticle diffusional limitations on catalyst reactivity and product selectivity,the use of small particles is necessary.Large eggshell spherical particles are shown to keep the original catalyst reactivity and enhance the selectivity of heavy hydrocarbon products.The suitable layer thickness for a spherical particle with a diameter of 2 mm is nearly 0.15 mm.With the same outer diameter of 2 mm,the catalyst reactivity and heavy product selectivity of hollow cylindrical particles with a layer thickness of 0.25 mm are found to be larger than eggshell spherical particles.From the viewpoint of catalytic performance,hollow cylindrical particles are a better choice for industrial applications.

Static Recrystallization Kinetics Model After Hot Deformation of Low-Alloy Steel Q345B

The static recrystallization behavior of low-alloy steel Q345B during double-pass hot compression deformation tests was investigated in the temperature range of 900-1000 ℃,the true strain range of 0.15-0.25 and the interpass time range of 0.5-50 s on Gleeble-3500 thermo-simulation machine.The results show that static recrystallization during the interpass time is observed.As the deformation temperature and strain increase,softening caused by static recrystallization is obvious.According to the analysis and calculation of thermo-simulation data,the static recrystallization activation energy was obtained and static recrystallization kinetics model was built.Finally,the error analysis of static recrystallization kinetics model proved that the model had good accuracy.Therefore,this model provides a theoretical basis for static recrystallization（SRX）and will contribute to the development of multipass hot rolling process,in order to control the rolling process more accurately.

Fixed-Bed Column Adsorption Modeling of MnO4- Ions from Acidic Aqueous Solutions on Activated Carbons Prepared with the Biomass

Activated carbons calcined at 400˚C and 600˚C (AC-400 and AC-600), prepared using palm nuts, collected in the town of Franceville in Gabon, were used to study the dynamic adsorption of MnO4- ions in acidic media on fixed bed column and on the kinetic modeling of experimental data of breakthrough curves of MnO4- ions obtained. Results on the adsorption of MnO4- ions in fixed-bed dynamics obtained on AC-400 and AC-600 adsorbents beds indicated that the AC-400 bed appears to be the most efficient in removing MnO4- ions in acidic media. Indeed, the adsorbed amounts, the adsorbed capacities at saturation and the elimination percentage of MnO4- ions obtained with AC-400 (31.24 mg;52.06 mg·g-1 and 41.65% respectively) were higher compared to those obtained with AC-600 (9.87 mg;16.45 mg·g-1 and 17.79% respectively). The breakthrough curves kinetic modeling revealed that the Thomas model and the pseudo-first-order kinetic model were the most suitable models to describe the adsorption of MnO4- ions on adsorbents studied in our experimental conditions. The results of the intraparticle diffusion model showed that intraparticle diffusion was involved in the adsorption mechanism of MnO4- ions on investigated adsorbents and was not the limiting step and the only process controlling MnO4- ions adsorption. In contrast to AC-400, the intraparticle diffusion on AC-600 bed plays an important role in the adsorption mechanism of MnO4- ions.

Modeling and Estimation of the Kinetics of Seeded Solvent-mediated Phase Transformation in a Batch Crystallizer

Modeling the kinetics of the preparing process is necessary to produce a product with the appropriate particle properties and minimum production cost.Owing to the lackness of crystal size distributor （CSD） information,however,solvent-mediated phase transformation encounters difficulty in modeling the kinetics as compared to solution crystallization.Consequently,a model was established by making the product CSD to move along by horizontal translation to obtain the CSDs of the stable phase in the process of transformation.Then the moment method was used to solve the popular balance equation,and the least square nonlinear regression method was applied to estimate the kinetics parameters.The model has been successfully used to simulate the transformation of CaSO4？2H2O to α-CaSO4？1/2H2O in an isothermal seeded batch crystallizer with different stirring speeds,and it is beneficial to producing high performance α-CaSO4？1/2H2O crystals which have the right particle characteristics.

A comparative single-pulse shock tube experiment and kinetic modeling study on pyrolysis of cyclohexane,methylcyclohexane and ethylcyclohexane

The pyrolysis of cyclohexane,methylcyclohexane,and ethylcyclohexane have been studied behind reflected shock waves at pressures of 5 and10 bar and at temperatures of 930-1550 K for 0.05%fuel diluted by Argon.A single-pulse shock tube(SPST)is used to perform the pyrolysis experiments at reaction times varying from 1.65 to 1.74 ms.Major products are obtained and quantified using gas chromatography analysis.A flame ionization detector and a thermal conductivity detector are used for species identification and quantification.Kinetic modeling has been performed using several detailed and lumped chemical kinetic mechanisms.Differences in modeling results among the kinetic models are described.Reaction path analysis and sensitivity analysis are performed to determine the important reactions controlling fuel pyrolysis and their influence on the predicted concentrations of reactant and product species profiles.The present work provides new fundamental knowledge in understating pyrolysis characteristics of cyclohexane compounds and additional data set for detailed kinetic mechanism development.

Extend ethylene aromatization single-event kinetic modeling with physical and chemical descriptor based on ZSM-5 catalyst

The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distribution concept were established and extend for the ethylene aromatization process,which can reduce the kinetic parameters and simplify the reaction network by comparison with the SEMK model including subtype elementary steps based on the type of carbenium ions.Further introducing deactivation parametersφinto the model and applying the linear free energy model to the deactivation experimental data,the obtained deactivation parametersφindicate that the carbon deposition precursors have the greatest impact on reducing the reaction rate of single-molecular reactions and the smallest impact on the hydrogen transfer reaction.Meanwhile,according to the change of reaction enthalpy,effect of carbenium ion structure on methylation,ethylation,cyclization and endo-βscission was investigated by introducing linear free energy concept into the SEMK model.The effect of different acid strengths on elementary steps was investigated based on the acid strength distribution model,it was found that the methylation and oligomerization reactions,the ali-βscission reaction,endo-βscission reaction and the cyclization reaction were more sensitive to strong acidity sites.The physisorption and chemisorption heat are separated from the protonation heat in the linear free energy kinetic model and the acid strength distribution kinetic model,and the absolute values of the obtained physisorption and chemisorption heat increase with the carbon number of carbenium ions.Furthermore,the parameters of the acid strength distribution kinetic model were applied to propane dehydroaromatization on H-ZSM-5 and the ethane dehydroaromatization on Zn/ZSM-5 to confirm the independence of parameters in the SEMK model with the similar reaction network.

Hot-deformation kinetics analysis and extrusion parameter optimization of a dilute rare-earth free magnesium alloy

The fundamental research on thermo-mechanical conditions provides an experimental basis for high-performance Mg-Al-Ca-Mn alloys.However, there is a lack of systematical investigation for this series alloys on the hot-deformation kinetics and extrusion parameter optimization. Here, the flow behavior, constitutive model, dynamic recrystallization(DRX) kinetic model and processing map of a dilute rare-earth free Mg-1.3Al-0.4Ca-0.4Mn(AXM100, wt.%) alloy were studied under different hot-compressive conditions. In addition, the extrusion parameter optimization of this alloy was performed based on the hot-processing map. The results showed that the conventional Arrhenius-type strain-related constitutive model only worked well for the flow curves at high temperatures and low strain rates. In comparison, using the machine learning assisted model(support vector regression, SVR) could effectively improve the accuracy between the predicted and experimental values. The DRX kinetic model was established, and a typical necklace-shaped structure preferentially occurred at the original grain boundaries and the second phases. The DRX nucleation weakened the texture intensity, and the further growth caused the more scattered basal texture. The hot-processing maps at different strains were also measured and the optimal hot-processing range could be confirmed at the deformation temperatures of 600~723 K and the strain rates of 0.018~0.563 s^(-1). Based on the optimum hot-processing range, a suitable extrusion parameter was considered as 603 K and 0.1 mm/s and the as-extruded alloy in this parameter exhibited a good strength-ductility synergy(yield strength of ~ 232.1 MPa, ultimate strength of ~ 278.2 MPa and elongation-to-failure of ~ 20.1%). Finally, the strengthening-plasticizing mechanisms and the relationships between the DRXed grain size, yield strength and extrusion parameters were analyzed.

Kinetic Modeling of an Opinion Model on Social Networks

It is commonly accepted that, on social networks, the opinion of the agents with a higher connectivity, i.e., a larger number of followers, results in more convincing than that of the agents with a lower number of followers. By kinetic modeling approach, a kinetic model of opinion formation on social networks is derived, in which the distribution function depends on both the opinion and the connectivity of the agents. The opinion exchange process is governed by a Sznajd type model with three opinions, ±1, 0, and the social network is represented statistically with connectivity denoting the number of contacts of a given individual. The asymptotic mean opinion of a social network is determined in terms of the initial opinion and the connectivity of the agents.

Environmental dynamics of nitrogen and phosphorus release from river sediments of arid areas

Human activities lead to the accumulation of a large amount of nitrogen and phosphorus in sediments in rivers.Simultaneously,nitrogen and phosphorus can be affected by environment and re-enter the upper water body,causing secondary pollution of the river water.In this study,laboratory simulation experiments were conducted initially to investigate the release of nitrogen and phosphorus from river sediments in Urumqi City and the surrounding areas in Xinjiang Uygur Autonomous Region of China and determine the factors that influence their release.The results of this study showed significant short-term differences in nitrogen and phosphorus release characteristics from sediments at different sampling points.The proposed secondary kinetics model(i.e.,pseudo-second-order kinetics model)better fitted the release process of sediment nitrogen and phosphorus.The release of nitrogen and phosphorus from sediments is a complex process driven by multiple factors,therefore,we tested the influence of three factors(pH,temperature,and disturbance intensity)on the release of nitrogen and phosphorus from sediments in this study.The most amount of nitrate nitrogen(NO_(3)^(–)-N)was released under neutral conditions,while the most significant release of ammonia nitrogen(NH_(4)^(+)-N)occurred under acidic and alkaline conditions.The release of nitrite nitrogen(NO_(2)^(-)-N)was less affected by pH.The dissolved total phosphorus(DTP)released significantly in the alkaline water environment,while the release of dissolved organic phosphorus(DOP)was more significant in acidic water.The release amount of soluble reactive phosphorus(SRP)increased with an increase in pH.The sediments released nitrogen and phosphorus at higher temperatures,particularly NH_(4)^(+)-N,NO_(3)^(–)-N,and SRP.The highest amount of DOP was released at 15.0℃.An increase in disturbance intensity exacerbated the release of nitrogen and phosphorus from sediments.NH_(4)^(+)-N,DTP,and SRP levels increased linearly with the intensity of disturbance,while NO_(3)^(–)-N and NO_(2)^(–)-N were more stable.This study provides valuable information for protecting and restoring the water environment in arid areas and has significant practical reference value.

Control system design for a pressure-tube-type supercritical water-cooled nuclear reactor via a higher order sliding mode method

Nuclear power plants exhibit non-linear and time-variable dynamics.Therefore,designing a control system that sets the reactor power and forces it to follow the desired load is complicated.A supercritical water reactor(SCWR)is a fourth-generation conceptual reactor.In an SCWR,the non-linear dynamics of the reactor require a controller capable of control-ling the nonlinearities.In this study,a pressure-tube-type SCWR was controlled during reactor power maneuvering with a higher order sliding mode,and the reactor outgoing steam temperature and pressure were controlled simultaneously.In an SCWR,the temperature,pressure,and power must be maintained at a setpoint(desired value)during power maneuvering.Reactor point kinetics equations with three groups of delayed neutrons were used in the simulation.Higher-order and classic sliding mode controllers were separately manufactured to control the plant and were compared with the PI controllers speci-fied in previous studies.The controlled parameters were reactor power,steam temperature,and pressure.Notably,for these parameters,the PI controller had certain instabilities in the presence of disturbances.The classic sliding mode controller had a higher accuracy and stability;however its main drawback was the chattering phenomenon.HOSMC was highly accurate and stable and had a small computational cost.In reality,it followed the desired values without oscillations and chattering.

Reduction kinetics of iron oxide pellets with H_2 and CO mixtures

Reduction of hematite pellets using H2-CO mixtures with a wide range of H2/CO by molar （1：0, 3：1, 1：1, 1：3, and 0：1） at different reducing temperatures （1073, 1173, and 1273 K） was conducted in a program reducing furnace. Based on an unreacted core model, the effective diffusion coefficient and reaction rate constant in several cases were determined, and then the rate-control step and transition were analyzed. In the results, the effective diffusion coefficient and reaction rate constant increase with the rise in temperature or hydrogen content. Reduction of iron oxide pellets using an H2-CO mixture is a compound control system; the reaction rate is dominated by chemical reaction at the very beginning, competition during the reduction process subsequently, and internal gas diffusion at the end. At low hydrogen content, increasing temperature takes the transition point of the rate-control step to a high reduction degree, but at high hydrogen content, the effect of temperature on the transition point weakens.

Kinetics of phenol and m-cresol biodegradation by an indigenous mixed microbial culture isolated from a sewage treatment plant

An acclimatized mixed microbial culture,predominantly Pseudomonas sp.,was enriched from a sewage treatment plant,and its potential to simultaneously degrade mixtures of phenol and m-cresol was investigated during its growth in batch shake flasks.A 22 full factorial design with the two substrates at two different levels and different initial concentration ranges(low and high),was employed to carry out the biodegradation experiments.The substrates phenol and m-cresol were completely utilized within 21 h when ...

Electroreduction Kinetics for Molten Oxide Slags

The oxygen-ion conductor, the reducing agent, and the molten oxide slag containing electroactive matter were used as constituent of a galvanic cell. Metal was directly electroreduced from molten slag using a short-circuit galvanic cell. The following galvanic cell was assembled in the present experiment： graphite rod, [-O]Fe-C saturated ｜ZrO2 （MgO） ｜ Cu（1） ＋ （FeO）（slag） , and molybdenum wire. The FeO electroreduction reaction was studied through measuring short circuit current by controlling factors such as temperature, the FeO content in molten slags, and the external circuit resistance. An overall kinetics model was developed to describe the process of FeO electroreductiono It was found that the modeled curves were in good agreement with the experimental values. The new oxide reduction method in the metallurgy with controlled oxygen flow was proposed and the metallurgical theory with controlled oxygen flow was developed.

Flotation kinetics performance of different coal size fractions with nanobubbles

The flotation kinetics of different size fractions of conventional and nanobubble(NB) flotation were compared to investigate the effect of NBs on the flotation performance of various coal particle sizes. Six flotation kinetics models were selected to fit the flotation data, and NBs were observed on a hydrophobic surface under hydrodynamic cavitation by atomic force microscope scanning. Flotation results indicated that the best flotation performance of size fraction at-0.125+0.074 mm can be obtained either in conventional or NB flotation. NBs increase the combustible recovery of almost all the size fractions, but they increase the product ash content of-0.25+0.074 mm and reduce the product ash content of-0.045 mm at the same time. The first-order models can be used to fit the flotation data in conventional and NB flotation, and the classical first-order model is the most suitable one. NBs considerably enhance flotation rate on coarse size fraction(-0.5+0.25 mm) but decrease the flotation rate of the medium size(-0.25+0.074 mm). The improvement of flotation speed on fine coal particles(-0.074 mm) is probably the reason for the improved performance of raw sample flotation.

Thermodynamics and kinetics insights into naphthalene hydrogenation over a Ni-Mo catalyst

Hydrocracking represents an important process in modern petroleum refining industry,whose performance mainly relies on the identity of catalyst.In this work,we perform a combined thermodynamics and kinetics study on the hydrogenation of naphthalene over a commercialized NiMo/HY catalyst.The reaction network is constructed for the respective production of decalin and methylindane via the intermediate product of tetralin,which could further undergo hydrogenation to butylbenzene,ethylbenzene,xylene,toluene,benzene,methylcyclohexane and cyclohexane.The thermodynamics analysis suggests the optimum operating conditions for the production of monoaromatics are 400℃,8.0 MPa,and 4.0 hydrogen/naphthalene ratio.Based on these,the influences of reaction temperature,pressure,hydrogen/-naphthalene ratio,and liquid hourly space velocity(LHSV)are investigated to fit the Langmuir-Hinshelwood model.It is found that the higher temperature and pressure while lower LHSV favors monoaromatics production,which is insensitive to the hydrogen/naphthalene ratio.Furthermore,the high consistence between the experimental and simulated data further validates the as-obtained kinetics model on the prediction of catalytic performance over this kind of catalyst.

Effect of solvent on the initiation mechanism of living anionic polymerization of styrene:A computational study

For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.

Two-dimensional modeling of the self-limiting oxidation in silicon and tungsten nanowires

Self-limiting oxidation of nanowires has been previously described as a reaction- or diffusion-controlled process. In this letter, the concept of finite reactive region is introduced into a diffusion-controlled model, based upon which a two-dimensional cylindrical kinetics model is developed for the oxidation of silicon nanowires and is extended for tungsten. In the model, diffusivity is affected by the expansive oxidation reaction induced stress. The dependency of the oxidation upon curvature and temperature is modeled. Good agreement between the model predictions and available experimental data is obtained. The de- veloped model serves to quantify the oxidation in two-dimensional nanostructures and is expected to facilitate their fabrication via thermal oxidation techniques.