一个改进的随机动力学水平衡模型及其应用研究Ⅱ.应用

本文用黄土高原长武农业生态试验站的冬小麦长期定位试验资料对改进的随机动力学水平衡模型进行了准确性检验 .从模型对参数反映的敏感性分析和模型计算值与数值模型WAVES的比较 ,以及模型对黄土区旱作高生产力的水分环境效应的评价结果 ,均证明改进的随机动力学水平衡模型能比较准确地预测一定生产力水平、特定生态系统平衡体系水均衡要素的定量分配和土壤含水量的动态变化 .

一个改进的随机动力学水平衡模型及其应用研究Ⅰ.模型

本文在Eagleson随机动力学水平衡模型的基础上 ,改进了原模型中蒸腾、蒸发量等项的计算方法 ;并根据黄土区降水分布特点 ,将全年分为 1 6个时间长度不等的降水时段 ,分别统计降水特征参数 ,利用质量守衡定律和逐步校正演算法 ,可计算出水文生态系统平衡体系水均衡要素的定量分配和活动层土壤含水量的年动态变化 ,代表了原模型中确定土壤含水量的简单统计法 ,从而可提高模型计算精度和实用性 .

气-固流化床中颗粒碰撞压力的研究

通过对床中物体表面与碰撞颗粒流之间的动量衡算，将颗粒流动量通量与颗粒的碰撞压力相关联，建立了流化床中颗粒碰撞压力的理论模型。计算表明，在浓相鼓泡区，颗粒的向上碰撞压力随颗粒密度及操作气速增加而迅速增加。理论计算值与实测结果基本吻合。

高线吐丝机共振问题分析

对国内引进高线吐丝机的横向振动与扭转振动进行了理论分析与计算，建立了吐丝机横向振动与扭转振动的力学和数学模型；经过计算机模态分析，排除了两种共振的说法，确定吐丝机的强烈振动属于一阶受迫振动非共振响应。解决了高线吐丝机所存在的实际振动问题，提高了生产速度，为企业增创了很大的经济效益。

Dynamic behavior of rock during its post failure stage in SHPB tests

In order to investigate the micro-process and inner mechanism of rock failure under impact loading, the laboratory tests were carried out on an improved split Hopkinson pressure bar （SHPB） system with synchronized measurement devices including a high-speed camera and a dynamic strain meter. The experimental results show that the specimens were in the state of good stress equilibrium during the post failure stage even when visible cracks were forming in the specimens. Rock specimens broke into strips but still could bear the external stress and keep force balance. Meanwhile, numerical tests with particle flow code （PFC） revealed that the failure process of rocks can be described by the evolution of micro-fractures. Shear cracks emerged firstly and stopped developing when the external stress was not high enough. Tensile cracks, however, emerged when the rock specimen reached its peak strength and played an important role in controlling the ultimate failure during the post failure stage.

Kinetics Study on O2 Adsorption and OHad Desorption at Pt（111）, Its Implication to Oxygen Reduction Reaction Kinetics

Kinetics of dissociative O2 adsorption, OHad desorption, and oxygen reduction reaction （ORR） at Pt（111） electrode in 0.1 mol/L HClO4 has been investigated. Reversible OHad adsorption/desorption occurs at potentials from 0.6 V to 1.0 V （vs. RHE） with the exchange current density of ca. 50 mA/cm^2 at 0.8 V, the fast kinetics of OHad desorption indicates that it should not be the rate determining step for ORR. In the kineticor kinetic-mass transport mix controlled potential region, ORR current at constant potential displays slight decrease with reaction time. ORR current in the positive-going potential scan is slightly larger than that in the subsequent negative-going scan with electrode rotation speed （〉800 r/min） and slow potential scan rate （〈100 mV/s）. The open circuit potential of Pt/0.1 mol/L HClO4 interface increases promptly from 0.9 V to 1.0 V after switch from O2 free- to O2-saturated solution. The increase of open circuit potential as well as ORR current decays under potential control due to the accumulation of OHad from dissociative adsorption of O2. It indicates that at Pt（111） the net rate for O2 decomposition to OHad is slightly faster than that for OHad removal, one cannot simply use the assumption of rate determining step to discuss ORR kinetics. Instead, the ORR kinetics is determined by both the kinetics for O2 decomposition to OHad as well as the thermo-equilibrium of OHad＋H^＋＋e→←H2O.

Comparison of Accuracy and Convergence Rate between Equilibrium and Nonequilibrium Alchemical Transformations for Calculation of Relative Binding Free Energy

Estimation of protein-ligand binding affinity within chemical accuracy is one of the grand challenges in structure-based rational drug design. With the efforts over three decades, free energy methods based on equilibrium molecular dynamics （MD） simulations have become mature and are nowadays routinely applied in the community of computational chemistry. On the contrary, nonequilibrinm MD simulation methods have attracted less attention, despite their underlying rigor in mathematics and potential advantage in efficiency. In this work, the equilibrium and nonequilibrium simulation methods are compared in terms of accuracy and convergence rate in the calculations of relative binding free energies. The proteins studied are T4-lysozyme mutant L99A and COX-2. For each protein, two ligands are studied. The results show that the noneqnilibrium simulation method can be competitively as accurate as the equilibrium method, and the former is more efficient than the latter by considering the convergence rate with respect to the cost of wall clock time. In addition, Bennett acceptance ratio, which is a bidirectional post-processing method, converges faster than the unidirectional Jarzynski equality for the nonequilibrium simulations.

Non-equilibrium Molecular Dynamics Simulation on Pure Gas Permeability Through Carbon Membranes

The permeation of various pure gas （H2, He, Ne, CH4 and At） through carbon membranes is investigated using a dual control volume grand canonical molecular dynamics method. A two-dimensional slit pore is employed instead of the one-dimensional pore. Compared with the experiments, simulation results show that the improvement of pore model is very necessary. The effects of membrane thickness, pore width and temperature on gas permeance and ideal separation factor are also discussed. Results show that gas permeates through membrane according to Knudsen diffusion in large pore, while Knudsen diffusion is accompanied by molecular sieving in small pore. Moreover, methane is easily adsorbed on the membrane surface due to strong attractive interactions of membrane and shows higher permeance than that of Knudsen flow. In addition, it is noted that when membrane thickness is thin enough the permeance of gas does not decrease with the increase of membrane thickness due to the strong adsorption until membrane resistance becomes dominant.

Removal of aqueous Ni(Ⅱ) with carbonized leaf powder: Kinetics and equilibrium

Nickel is a heavy metal which has the potential threaten to human＇s health and attracts public concern recently. The carbonized leaf powder is expected as suitable adsorbent for Ni（II） removal became of the composition of some beneficial groups. In this work, carbonized leaf powder was evaluated for its adsorption performance towards Ni（II）. According to the results, adsorbent component, dosage, initial solute concentration, solution pH, temperature and contact time can significantly affect the efficiency of Ni（II） removal. Sips model fits the test results best, and the adsorption capacity towards Ni（II） is determined around 37.62 mg/g. The thermodynamic behaviors reveal the endothermic and spontaneous nature of the adsorption. The free adsorption energy （fluctuate around 8 kJ/mol） predicted by D-R model indicates that the adsorption capacity originated from both physical and chemical adsorption. Room temperature （15-25 ℃） is suitable for Ni（II） removal as well as low energy consumption for temperature enhancement. Further conclusions about the mechanism of chemical adsorption are obtained through analysis of the FT-IR test and XRD spectra, which indicates that the adsorption process occurs predominantly between amine, carbonate, phosphate and nickel ions.

Effect of Heavy Metals on Phosphorus Retention by Typic Udic Ferrisols: Equilibrium and Kinetics

A study was conducted to examine the effect of heavy metals (Cu,Pb, Zn and Cd in combination or alone) on the equilibrium andkinetics of phosphorus (P) retention in typic udic ferrisols by usingboth equilibrium and flow techniques. Fourteen soil samples withvarying artificial contamination of Cu, Pb, Zn and Cd were prepared.Heavy metal pollution led to increases in retention capacity andmaximum buffering capacity (MBC) of soil P. The rate of P retentionwas also increased and the time to reach equilibrium was advanced byheavy metals addition.

Adsorption Isotherm and Kinetics of Dibenzofuran on Granular Activated Carbons

The adsorption of dibenzofuran on three commercial granular activated carbons (ACs) was investigated by dynamic experiment to correlate the adsorption equilibrium and kinetics with the structure of activated carbons.Physical properties including surface area, average pore diameter, micropore area and micropore volume of the activated carbons were characterized by N2 adsorption experiment on ASAP2010. To calculate the adsorption parameters, adsorption isotherm data were fitted to the Langmuir equation, and adsorption kinetic data were fitted to the linear driving force (LDF) diffusion model. From the correlation results, it is concluded that the adsorption equilibrium and diffusion coefficient of dibenzofuran on activated carbon are controlled respectively by the total adsorbent surface area and the adsorbent pore diameter.

Sorbitol Hydrogenolysis to Glycols over Baisic Additive Promoted Ni-based Catalysts

A series of Ni based catalysts with different supports and basic additives were prepared by sequential impregnation method. The catalysts were characterized by XRD, BET, H2-TPR and CO2-TPD techniques. It was found that the introduction of basic additives enhanced the basicities of catalyats and promoted the dispersities of Ni particles by strong interaction between Ni2＋ and basic additives. Among the Ni based catalysts, 10%Ni/10%La203/ZrO2 showed the superior performance in sorbitol hydrogenolysis. The synergistic effect of Ni and La203 was proven to play an essential role in selective synthesis of EG and 1,2-PG. In the optimal reaction condition, the catalyst presented 100% sorbitol conversion and over 48% glycols （EG and 1,2-PG） yield. The kinetics study of polyols （sorbitol, xylitol and glycerol） hydrogenolysis showed that polyols with more hydroxyl number have higher activity and products distribution was final results of kinetic balance, which could give us some inspiration abeut how to change the products selectivity.

Human-machine compatibility and dynamic analysis of a novel unpowered and self-adaptive shoulder rehabilitation exoskeleton

To reduce the complexity of the configuration and control strategy for shoulder rehabilitation exoskeleton,a 2R1R1P2R serial of shoulder exoskeleton based on gravity balance is proposed.Based on three basic rotatory shoulder joints,an exact kinematic constraint system can be formed between the exoskeleton and the upper arm by introducing a passive sliding pair and a center of glenohumeral(CGH)unpowered compensation mechanism,which realizes the human-machine kinematic compatibility.Gravity balance is used in the CGH compensation mechanism to provide shoulder joint support.Meanwhile,the motion of the compensation mechanism is pulled by doing reverse leading through the arm to realize the kinematic self-adaptive,which decreases control complexity.Besides,a simple and intuitive spring adjustment strategy is proposed to ensure the gravity balance of any prescribed quality.Furthermore,according to the influencing factors analysis of the scapulohumeral rhythm,the kinematic analysis of CGH mechanism is performed,which shows that the mechanism can fit the trajectory of CGH under various conditions.Finally,the dynamic simulation of the mechanism is carried out.Results indicate that the compensation torques are reduced to below 0.22 N·m,and the feasibility of the mechanism is also verified.

Thermal Equilibrium Reached by Interaction Between Two Identical Systems

In this work we show that tending to thermal equilibrium in one system, at least in certain cases, is associated with the coherent dynamical evolution of this system in interaction with another identical system. The temperature varying effect with time is manifestly shown in our analyses.

Equilibrium and kinetic data of adsorption and separation for zirconium and hafnium onto MIBK extraction resin

The equilibrium and kinetics of methyl isobutyl ketone(MIBK) extraction resin for adsorption and separation of zirconium and hafnium were studied under the different conditions of acidity,initial total concentrations of zirconium and hafnium and temperature.The equilibrium data of both zirconium and hafnium are found to follow the Freundlich adsorption isotherm,and the Freundlich isotherm constants(KF) are 3.53 and 0.64 mg/g,respectively.The equilibrium data of zirconium also fit the Langmuir adsorption isotherm,and the saturation adsorption capacity(Qmax) and the Langmuir isotherm constant(KL)are 75.93 mg/g and-0.012 7 L/g,respectively.The obtained kinetic data of both zirconium and hafnium are found to fit the HO pseudo-second-order kinetic model,and the rate constants of pseudo-second-order equation(k2) are-0.019 and 0.41 g/(mg·min),respectively.Column tests show that the MIBK extraction resin could be used as efficient adsorbent material for separating hafnium from zirconium.

Numerical Simulation of Direct-contact Condensation from a Supersonic Steam Jet in Subcooled Water

The phenomenon of direct-contact condensation,used in steam driven jet injectors,nuclear reactor emergency core cooling systems and direct-contact heat exchangers,was investigated computationally by introducing a thermal equilibrium model for direct-contact condensation of steam in subcooled water.The condensation model presented was a two resistance model which takes care of the heat transfer process on both sides of the interface and uses a variable steam bubble diameter.The injection of supersonic steam jet in subcooled water tank was simulated using the Euler-Euler multiphase flow model of Fluent 6.3 code with the condensation model incorporated. The findings of the computational fluid dynamics（CFD） simulations were compared with the published experimental data and fairly good agreement was observed between the two,thus validating the condensation model.The results of CFD simulations for dimensionless penetration length of steam plume varies from 2.73-7.33,while the condensation heat transfer coefficient varies from 0.75-0.917 MW·（m ^2 ·K）^ -1 for water temperature in the range of 293-343 K.

Removal of Cd(Ⅱ)and Pb(Ⅱ)from soil through desorption using citric acid:Kinetic and equilibrium studies

The desorption test was conducted to evaluate the desorption behavior of Pb(Ⅱ)and Cd(Ⅱ)using citric acid.The influential factors that were considered included initial Pb(Ⅱ),Cd(Ⅱ)contamination levels in soil,concentration of citric acid,reaction time,soil pH value and ionic strength.The test results indicated that the desorption was a rapid reaction(less than 6 h),and the removal percentages of Cd(Ⅱ)and Pb(Ⅱ)increased with the increasing contamination levels,concentration of citric acid and the addition of Na^+,Ca^(2+),Na^+, Cl~– and the chelating of organic ligands.

CFD-PBE simulation of a bubble column in OpenFOAM

A general CFD-PBE(computational fluid dynamics-population balance equation) solver for gas–liquid poly-dispersed flows of both low and high gas volume fractions is developed in OpenFOAM(open-source field operation and manipulation) in this work. Implementation of this solver in OpenFOAM is illustrated in detail. The PBE is solved with the cell average technique. The coupling between pressure and velocity is dealt with the transient PIMPLE algorithm, which is a merged PISO-SIMPLE(pressure implicit split operator-semi-implicit method for pressure-linked equations) algorithm. Results show generally good agreement with the published experimental data, whereas the modeling precision could be improved further with more sophisticated closure models for interfacial forces, the models for the bubble-induced turbulence and those for bubble coalescence and breakage.The results also indicate that the PBE could be solved out the PIMPLE loop to save much computation time while still preserving the time information on variables. This is important for CFD-PBE modeling of many actual gas–liquid problems, which are commonly high-turbulent flows with intrinsic transient and 3 D characteristics.

Biosorption Equilibrium and Kinetics of Au（Ⅲ） and Cu（Ⅱ） on Magnetotactic Bacteria

Magnetotactic bacteria （MTB） as biosorbents for the adsorption of Au（Ⅲ） and Cu（Ⅱ） ions from aqueous solution have been investigated. The optimum adsorption conditions for both metal ions were the initial pH scope of 1-5.5 for Au（Ⅲ） and 2.0-4.5 for Cu（Ⅱ）, room temperature, biomass concentration of 10.0g.L^-1 and sorotion du-ration more than 10 min. When the initial metal concentration were within 500mg.L^-1, the maximum biosorption capacity of 1.0g of MTB （dry mass basis） for Au（Ⅲ） and Cu（Ⅱ） were calculated as 505.2mg of Au（Ⅲ） and 493.1mg of.Cu（Ⅱ） by Langmuir model in single system, respectively. The isotherm equilibrium of Au（Ⅲ） and Cu（Ⅱ） ions in the Au-Cu binary system reflected a unique phenomenon that the adsorption of Au（Ⅲ） was rein-forced and that of Cu（Ⅱ） prohibited, compared respectively-with their performances in the single metal system.When the,concentration of-Au（Ⅲ） and Cu（Ⅱ）. were below 80mg.L^-1, the waste waterafter MTB treating, wasbelow 1.0mg.L^-1, which is in conformity with Environmental Performance Standards （EPS） of Canada. Besides, all the kinetic data were fitted well to the pseudo second-order kinetic model with a high correlation coefficient （R^2〉0.999）.

Study of Isothermal Equilibrium,Kinetics and Thermodynamics of Adsorptive Desulfurization on Synthesized Cu~ⅠY~ⅢY Zeolite

Deep adsorptive desulfurization of low sulfur content gasoline via zeolite is a promising process.Herein,the Cu~ⅠY~ⅢY zeolite was prepared and the effect of adsorption conditions and aromatics on the performance of adsorptive desulfurization was studied.And the isothermal equilibrium and kinetics were also investigated.The results showed that upon using 10 m L of model oil and 0.2 g of the Cu~ⅠY~ⅢY adsorbent during the adsorption reaction,which was carried out at 323 K for 60 min,the benzothiophene(BT) desulfurization rate reached 98.4%.The impact of aromatics on the adsorptive desulfurization over the Cu~ⅠY~ⅢY zeolite decreased in the following order:ortho-xylene > meta-xylene > para-xylene.The equilibrium isotherm shows that the adsorption of benzothiophene over the as-prepared CuIYIIIY zeolite can be represented by the Langmuir model.And the kinetics can be more perfectly represented by the pseudo-second-order model than that of the pseudo-first-order one.The thermodynamic parameters(ΔG,ΔH) were both negative,which suggested that the adsorption process is monostratal,mass transfer controlled,spontaneous,and exothermic.