重质油在催化剂孔道内受限扩散及其关联模型研究进展

重质油分子结构复杂、尺寸较大且容易聚集形成缔合体,致使在加氢及催化裂化催化剂孔道内存在明显的扩散阻力,显著阻碍了反应物分子与催化剂孔道内部活性位的接触,导致反应速率与转化率明显低于轻质原料。因此,研究重油分子在催化剂孔道内扩散受阻情况可以为催化剂的设计优化提供信息与指导。尽管借助仪器或膜材料能获得溶质分子的扩散性能,但与反应条件下扩散规律差别较大,因此在实际反应体系下获得重油分子在催化剂孔道中的扩散传质具有重要的现实意义。综述采用反应动力学手段获得扩散传质数据并建立受限因子关联模型及其影响因素的研究进展,从反应物选择、反应条件及催化剂等因素的优化角度对重油分子受阻扩散研究进行展望。

Estimation of kinetics parameters in Beckmann rearrangement of cyclohexanone oxime using genetic algorithm

Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrangement of OXH+ while the SO3 acts as dehydrating agent and OXSO3 can turn to CPLSO3 ultimately. Considering self-catalyzed reaction between OXSO3 and CPLH+, kinetic model for Beckmann rearrangement was established. Corresponding parameters were estimated by using float genetic algorithm （GA） and simulation results agree well with the experimental data below -19.3℃. Industrial equipment was simulated and analyzed. Effects of key process parameters such as molar ratio of sulfuric acid to oxime and circulation ratio on the residual oxime are also discussed. The results show that the caprolactam exists as CPLH+ finally in oleum and the minimum molecular ratio of sulfuric acid to oxime can be 0.5 theoretically.

Estimation of Kinetic Parameters for Autocatalytic Oxidation of Cyclohexane Based on a Modified Adaptive Genetic Algorithm

A modified genetic algorithm of multiple selection strategies, crossover strategies and adaptive operator is constructed, and it is used to estimate the kinetic parameters in autocatalytic oxidation of cyclohexane. The influences of selection strategy, crossover strategy and mutation strategy on algorithm performance are discussed. This algorithm with a specially designed adaptive operator avoids the problem of local optimum usually associated with using standard genetic algorithm and simplex method. The kinetic parameters obtained from the modified genetic algorithm are credible and the calculation results using these parameters agree well with experimental data. Furthermore, a new kinetic model of cyclohexane autocatalytic oxidation is established and the kinetic parameters are estimated by using the modified genetic algorithm.

A simple physical mixing method for MnO2/MnO nanocomposites with superior Zn^2+storage performance

MnO2/MnO cathode material with superior Zn^2+storage performance is prepared through a simple physical mixing method.The MnO2/MnO nanocomposite with a mixed mass ratio of 12:1 exhibits the highest specific capacity(364.2 mA·h/g at 0.2C),good cycle performance(170.4 mA·h/g after 100 cycles)and excellent rate performance(205.7 mA·h/g at 2C).Analysis of cyclic voltammetry(CV)data at various scan rates shows that both diffusioncontrolled insertion behavior and surface capacitive behavior contribute to the Zn2+storage performance of MnO2/MnO cathodes.And the capacitive behavior contributes more at high discharge rates,due to the short paths of ion diffusion and the rapid transfer of electrons.

Kinetics and Mechanism of Catalytic Reduction of U(Ⅵ)with Hydrazine on Platinum Catalysts in Nitric Acid Media

The kinetics of U(IV)produced by hydrazine reduction of U(VI)with platinum as a catalyst in nitric acid media was studied to reveal the reaction mechanism and optimize the reaction process.Electron spin resonance(ESR)was used to determine the influence of nitric acid oxidation.The effects of nitric acid,hydrazine,U(VI)concentration,catalyst dosage and temperature on the reaction rate were also studied.In addition,the simulation of the reaction process was performed using density functional theory.The results show that the influence of oxidation on the main reaction is limited when the concentration of nitric acid is below 0.5 mol/L.The reaction kinetics equation below the concentration of 0.5 mol/L is found as:−dc(UO_(2)^(2+))/dt=kc^(0.5323)(UO_(2)^(2+))c^(0.2074)(N_(2)H_(5)^(+))c^(−0.2009)(H^(+)).When the temperature is 50℃,and the solid/liquid ratio r is 0.0667 g/mL,the reaction kinetics constant is k=0.00199(mol/L)^(0.4712)/min.Between 20℃ and 80℃,the reaction rate gradually increases with the increase of temperature,and changes from chemically controlled to diffusion-controlled.The simulations of density functional theory give further insight into the influence of various factors on the reaction process,with which the reaction mechanisms are determined according to the reaction kinetics and the simulation results.

Hybrid Differential Evolution for Estimation of Kinetic Parameters for Biochemical Systems

Determination of the optimal model parameters for biochemical systems is a time consuming iterative process. In this study, a novel hybrid differential evolution （DE） algorithm based on the differential evolution technique and a local search strategy is developed for solving kinetic parameter estimation problems. By combining the merits of DE with Gauss-Newton method, the proposed hybrid approach employs a DE algorithm for identifying promising regions of the solution space followed by use of Gauss-Newton method to determine the optimum in the identified regions. Some well-known benchmark estimation problems are utilized to test the efficiency and the robustness of the proposed algorithm compared to other methods in literature. The comparison indicates that the present hybrid algorithm outperforms other estimation techniques in terms of the global searching ability and the con- vergence speed. Additionally, the estimation of kinetic model parameters for a feed batch fermentor is carried out to test the applicability of the proposed algorithm. The result suggests that the method can be used to estimate suitable values of model oarameters for a comolex mathematical model.

A Fuzzy-based Adaptive Genetic Algorithm and Its Case Study in Chemical Engineering

Considering that the performance of a genetic algorithm （GA） is affected by many factors and their rela-tionships are complex and hard to be described,a novel fuzzy-based adaptive genetic algorithm （FAGA） combined a new artificial immune system with fuzzy system theory is proposed due to the fact fuzzy theory can describe high complex problems.In FAGA,immune theory is used to improve the performance of selection operation.And,crossover probability and mutation probability are adjusted dynamically by fuzzy inferences,which are developed according to the heuristic fuzzy relationship between algorithm performances and control parameters.The experi-ments show that FAGA can efficiently overcome shortcomings of GA,i.e.,premature and slow,and obtain better results than two typical fuzzy GAs.Finally,FAGA was used for the parameters estimation of reaction kinetics model and the satisfactory result was obtained.

Methodology for Design of Reactive Distillation Column and Kinetics for Isoamylene Etherification Catalysed by Amberlyst 35

Isoamylene from the Fischer-Tropsch syncrude can be transformed to valuable fuel oxygenate additives through an equilibrium limited etherification reaction with methanol. A reactive distillation process is established to increase isoamylene conversion. Facing the challenge of improving product purity at the same time, an equilibrium stage model based design methodology is proposed and illustrated step-by-step for converting the Fischer-Tropsch C_5 olefins to tert-amyl methyl ether(TAME) process by using Aspen Plus. Under the guide of the proposed methodology, the design leads to a TAME product purity of higher than 95% and an isoamylene conversion of higher than 90%. The etherification kinetics over Amberlyst 35 is also studied within a temperature range of 60 ℃ to 75 ℃ to shed more light on the feasibility of process development. The methodology provides an effective reactive distillation column design to achieve the target reactant conversion and product purity simultaneously.

Pore structure effects on the kinetics of methanol oxidation over nanocast mesoporous perovskites

Mesoporous LaMnO3 perovskite catalysts with high surface area were synthesized by using the recently developed hard templating method designated as ＂nanocasting＂.Ordered mesoporous silica designated as SBA-15 was used as the hard template.It was found that the surface area of the nanocast perovskites can be tuned（80–190 m2/g）by varying the aging temperature of the SBA-15 template.Nanocast LaMnO3 catalysts showed high conversion efficiencies for the total oxidation of methanol under steady state conditions,the one with the highest value of surface area being the best catalysts,as expected.Kinetic studies were performed for all of the synthesized catalysts.Rate constants were found to vary in accordance with the specific surface area of the nanocast catalyst which depends on the aging temperature of the parent template.From the rate constants obtained from experimental conversions at various space velocities（19500 to 78200 h〈sup〉–1）,values of activation energy and pre-exponential factor for the three nanocast LaMnO3 catalysts were determined by the linear regression of the Arrhenius plot.It is observed that the activation energy for all the catalysts remain constant irrespective of the variation in specific surface area.Further,a linear relationship was found to exist between the pre-exponential factor and specific surface areas of the catalysts indicating that the rates per unit surface area remains the same for all the catalysts.

Non-adiabatic Couplings Induced Complex-Forming Mechanism in H+MgH^(+)→Mg^(+)+H_(2) Reaction

A chemical process may involve multiple adiabatic electronic states, and non-adiabatic couplings play an important role in the reaction mechanism. In this work, the effect of non-adiabatic couplings in the H+MgH;→Mg;+H;reaction are studied using the time-dependent wave packet method and trajectory surface hopping method. The calculated results show that the reaction follows a direct abstraction process when the non-adiabatic couplings are neglected. However, when non-adiabatic couplings are included in the calculations, a longlived excited state complex(MgH_(2)+)*can be formed during the reaction. These direct and complex-forming reaction pathways are revealed by trajectory surface hopping calculations.The non-adiabatic couplings induced complex-forming mechanism not only increases the reactivity but also has significant effect on the product vibrational state distribution.

Kinetics of water–isocyanate reaction in N,N-dimethylformamide

The uncatalyzed reaction of p-tolyl isocyanate(p-TI)with water in N,N-dimethylformamide(DMF)was investigated by high performance liquid chromatography(HPLC).The reactions were carried out at different temperatures from 293 K to 323 K,using various molar ratios of water to p-TI.DMF,as a special amide,was proved to be an efficient catalyst for water–isocyanate reaction.Under the reaction conditions in this study,substituted urea was the only final product observed.An appreciable amount of intermediate p-toluidine was detected.Concentrations of the isocyanate group as well as the amine and urea were determined as a function of time.New kinetic equations were deduced for each of the substance on the basis of a multistep mechanism,instead of a simple second order reaction as usual.Kinetic constants were calculated using the software MATLAB.Furthermore,the effects of temperature and concentrations of reactants on the reaction rate and amine content were discussed.The activation energy of each step was also determined.

Pyrolysis Characteristics and Kinetics of Municipal Solid Waste

Based on a systemic survey, the pyrolysis characteristics and apparent kinetics of the municipal solid waste （ MSW） under different conditions were researched using a special pyrolysis reactor, which could overcome the disadvantage of thermo-gravimetric analyzer. The thermal decomposition behaviour of MSW was investigated using thermo-gravimetric （ TG ） analysis at rates of 4.8,6.6,8.4, 12.0 and 13. 2 K/min. The pyrolysis characteristics of MSW were also studied in different function districts. The pyrolysis of MSW is a complex reaction process and three main stages are found according to the results. The first stage represents the degradation of cellulose and hemicellulose, with the maximum degradation rate occuring at 150℃ -200 ℃： the second stage represents dehydrochlorination and depolymerization of intermediate products and the differential thermogravimetric （ DTG ） curves have shoulder peaks at about 300℃： the third stage is the decomposition of the residual big molecular organic substance and lignin at 400 ℃- 600 ℃. Within the range of given experimental conditions, the results of non-linear fitting algorithm and experiment are in agreement with each other and the correlation coefficients are over0. 99. The kinetic characteristics are concerned with the material component and heating rate. The activation energy of reaction decreases with the increase of heating rate.

Aniline destruction by supercritical water oxidation and its reaction kinetics

Supercritical water oxidation （SCWO） is an effective method for wastewater treatment. In this study, a lot of experiments are carried out to study the influence of various factors on the aniline destruction rate in the SCWO process with a novel experiment setup. The experimental results show that the aniline destruction rate rises with the increase of the residence time, the reaction temperature and the reaction pressure. A dynamics analysis of the aniline SCWO reaction is conducted and the dynamic equation is obtained.

The XPK Package:A Comparison between the Extended Phenomenological Kinetic(XPK) Method and the Conventional Kinetic Monte Carlo(KMC) Method

Recently, we proposed the extended phenomenological kinetics (XPK) method, which overcomes the notorious timescale separation difficulty between fast diffusion and slow chemical reactions in conventional kinetic Monte Carlo (KMC) simulations. In the present work, we make a comprehensive comparison, based on the newly developed XPK package, between the XPK method and the conventional KMC method using a model hydrogenation reaction system. Two potential energy surfaces with different lateral interactions have been designed to illustrate the advantages of the XPK method in computational costs, parallel efficiency and the convergence behaviors to steady states. The XPK method is shown to be efficient and accurate, holding the great promise for theoretical modelling in heterogeneous catalysis, in particular, when the role of the lateral interactions among adsorbates is crucial.

Quasi-classical Trajectory Study of F-I-H20→HF-I-OH Reaction： Influence of Barrier Height, Reactant Rotational Excitation, and Isotopic Substitution

The reaction dynamics of the F＋H20/D20→HF/DF＋OH/OD are investigated on an accurate potential energy surface （PES） using a quasi-classical trajectory method. For both isotopomers, the hydrogen/deuterium abstraction reaction is dominated by a direct rebound mechanism over a very low ＂reactant-like＂ barrier, which leads to a vibrationally hot HF/DF product with an internally cold OH/OD companion. It is shown that the lowered reaction barrier on this PES, as suggested by high-level ab initio calculations, leads to a much better agreement with the experimental reaction cross section, but has little impact on the product state distributions and mode selectivity. Our results further indicate that rotational excitation of the H20 reactant leads to significant enhancement of the reactivity, suggesting a strong coupling with the reaction coordinate.

Progress in femtochemistry and femtobiology

Femtoscience offers a unique way to understand the dynamics in physics, chemistry and biology. This subject focuses on the process happening at femto-to pico-second time scale by femtosecond optical methods. Widely used in chemistry it reveals chemical reactions, including bond breaking, forming, and stretching, which happens at an ultrafast time scale. Femtoscience is also important in the biological system, for example, light harvesting system and vision system. Femtoscience in physics is also widely used, but it is not studied in this paper. Instead, we report new advances in femtochemistry and femtobiology, including structural dynamics, coherent control, enzyme function dynamics and hydration in the protein system. We also introduce attosecond science, focusing on electron dynamics at an extreme short time scale.

Thermochemical properties and thermokinetic behavior of energetic triazole ionic salts

The properties of dissolution in different solvents,the specific heat capacity and thermal decomposition process under the non-isothermal conditions for energetic triazole ionic salts 1,2,4-triazolium nitrate(1a),1,2,3-triazolium nitrate(1b),3,4,5triamino-1,2,4-triazolium nitrate(2a),3,4,5-triamino-1,2,4-triazolium dinitramide(2b)were precisely measured using a Calvet Microcalorimeter.The thermochemical equation,differential enthalpies of dissolution(△difH m ),standard molar enthalpies of dissolution(△difH m ),apparent activation energy(E),pre-exponential constant(A),kinetic equation,linear relationship of specific heat capacity with temperature over the temperature range from 283 to 353 K,standard molar heat capacity(C p,m)and enthalpy,entropy and Gibbs free energy at 283–353 K,taking 298.15 K as the benchmark for 1a,1b,2a and 2b were obtained with treating experimental data and theoretical calculation method.The kinetic and thermodynamic parameters of thermal decomposition reaction,critical temperature of thermal explosion(Tb),self-accelerating decomposition temperature(TSADT)and adiabatic time-to-explosion(t)of 1a,1b,2a and 2b were calculated.Their heat-resistance abilities were evaluated.Information was obtained on the relation between molecular structures and properties of 1a,1b,2a and 2b.

Mechanistic study and kinetic properties of the CF_3CHO+Cl reaction

Theoretical investigations have been carried out on the mechanism and kinetics for the reaction of CF 3 CHO + Cl using duallevel direct dynamics method. The potential energy surface information was obtained at the MCQCISD/3//MP2/cc-pVDZ level and the kinetic calculations were done using variational transition state theory with interpolated single-point energy (VTST-ISPE) approach. The calculated results show that the reaction proceeds primarily via the H-abstraction channel, while the Cl-addition channel is unfavorable due to the higher barriers. The improved canonical variational transition-state theory (ICVT) with the small-curvature tunneling correction (SCT) was used to calculate the rate constants. The theoretical rate constants at room temperature are in general agreement with the experimental values. A three-parameter rate constant expression was fitted over a wide temperature range of 200-2000 K.