燃煤锅炉SNCR脱硝对于SO_3生成的研究

利用化学反应动力学计算研究燃煤锅炉的选择性非催化还原(SNCR)对于气相中SO_3生成过程的影响,并进一步考虑喷氨位置、氨氮比与SO_3脱除率的关系。结果表明:SNCR对于SO_3具有一定脱除作用,这主要是由于喷氨后,通过相关基元反应使得自由基H和HO_2的浓度变大,进而抑制或分解SO_3的缘故。随着氨氮比增加,SO_3脱除率升高,当氨氮比为1.2,在烟气温度约1 000℃位置处喷氨时SO_3脱除效果最佳。

水合肼净化烟气NO_x过程的影响因素分析

采用反应动力学和计算流体力学软件对水合肼还原高温烟气中NOx过程进行了模拟计算。根据模拟结果分析了烟气温度、N2H4/NO摩尔比、烟气中氧含量、停留时间、烟气中NO初始浓度以及水合肼溶液的浓度对NO净化效率的影响。分析结果发现:N2H4/NO摩尔比取0.8,使用质量分数为5%浓度的水合肼溶液喷加到1023K的烟气中并且保证停留时间尽量长,可以取得最好的NO净化效果。分析结果可以为实际操作提供指导。

航空煤油/甲烷混合燃料航空发动机燃烧室燃烧与排放特性分析

为了阐明双燃料航空发动机的燃烧与排放特性,选用正癸烷作为航空煤油的模拟替代燃料,采用该替代燃料的燃烧反应简化机理对某型航空发动机分别燃用航空煤油、50%航空煤油/50%甲烷混合燃料时燃烧室的燃烧过程进行了反应动力学计算,并对比分析了该型航空发动机燃用两种不同燃料时燃烧室的燃烧特性与主要排放物的生成特性。结果表明,与燃用航空煤油相比,燃用50%航空煤油/50%甲烷混合燃料时,火焰筒内流场分布特性基本一致,但主燃区高温区域明显缩短;同时,火焰筒内温度峰值与火焰筒出口平均温度分别下降15 K与11 K;火焰筒内燃料摩尔分数分布特性基本相似,但燃料摩尔分数峰值急剧升高,中间裂解组分C_(2)H_(2)、C_(2)H_(4)、C_(4)H_(4)摩尔分数峰值下降幅度较大;火焰筒出口CO_(2)与CO的平均摩尔分数分别降低12%、33%,H_(2)O的平均摩尔分数升高13%。

Digestion mechanism and crystal simulation of roasted low-grade high-sulfur bauxite

Low-grade high-sulfur bauxite was pretreated via suspension roasting and muffle furnace roasting to remove sulfur and enhance digestion properties.The results show that sulfur can be efficiently removed,and the alumina digestion properties are significantly improved after suspension roasting.Under optimal conditions(t=70 min,T=280°C,w(CaO)=8%and Nk=245 g/L),the digestion ratios are 94.45%and 92.08%for the suspension-roasted and muffle-roasted ore,respectively,and the apparent activation energies are 63.26 and 64.24 kJ/mol,respectively.Two crystal models were established by Materials Studio based on the XRD patterns.The DFT simulation shows that the existing Al—O bands after suspension roasting can improve alumina digestion.The(104)and(113)planes of Al2O3 after suspension roasting are found to combine with NaOH more easily than those of Al2O3 treated in a muffle furnace.

Reaction thrust characteristics of high-pressure submerged water jet of cylinder nozzles

The shapes and geometrical parameters of nozzles are key factors for fluidics. The relationship among the reaction thrust, flow rate pressure, diameter do and length L of a cylinder nozzle is analyzed theoretically. The simulation of the flow field characteristics was conducted via the FLUENT computational fluid dynamics package. Effects of the inlet conditions and the nozzle dimensions on the reaction thrust of a water jet were addressed particularly. The reaction thrust experiments were performed on a custom-designed test apparatus. The experimental results reveal that a） the nozzle diameter and the inlet conditions exert great influence on the water jet reaction thrust; and b） for L≤4d0, where the nozzle is treated as a thin plate-orifice, the reaction thrust is independent of nozzle length; for L〉4d0, where the nozzle is treated as a long orifice, the reaction thrust can reach maximum under the condition of a certain flow rate. These findings lay a theoretical foundation for the design of nozzles and have significant value, especially for the future development of high-oressure water-let orooulsion technology.

Modeling of Soot Formation in Gas Burner Using Reduced Chemical Kinetics Coupled with CFD Code

A computational study of soot formation in ethylene/air coflow jet diffusion flame at atmospheric pres-sure was conducted using a reduced mechanism and soot formation model. A 20-step mechanism was derived from the full mechanism using sensitivity analysis,reaction path analysis and quasi steady state(QSS) approximation. The model in premixed flame was validated and with computing savings in diffusion flame was applied by incor-porating into a CFD code. Simulations were performed to explore the effect of coflow air on flame structure and soot formation. Thermal radiation was calculated by a discrete-ordinates method,and soot formation was predicted by a simple two-equation soot model. Model results are in good agreement with those from experiment data and detailed mechanism at atmospheric conditions. The soot nucleation,growth,and oxidation by OH are all enhanced by decrease in coflow air velocity. The peak soot volume fraction region appears in the lower annular region be-tween the peak flame temperature and peak acetylene concentration locations,and the high soot oxidation rate due to the OH attack occurs in the middle annular region because of high temperature.

Quasi-classical Trajectory Study on the H^＋＋H2 Reaction

Quasi-classical trajectory （QCT） calculations on the H^＋＋H2 reaction system were carried out on a new potential energy surface （PES）. Theoretical calculations show that the angular distribution of the forward and backward products is roughly symmetric for the title reaction. The product rotational state distribution was also determined at a few collision energies. In t, he collision energy range from 0.124 eV to 1.424 eV, the integral cross section for this system monotonically decreases with the collision energy. A comparison with the experimental result of the ion-molecule reaction was also made, the agreement is generally good.

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.

Lattice Boltzmann Simulation for the Spiral Wave Dynamics

We investigated the dynamics of the simple spiral waves of the Se/kov reaction-diffusion system with the Lattice Boltzmann method. The results of computer simulation lead to the conclusion that the trajectory of the spiral tip is a small circle, the wavelength and the period decay exponentially when the value of parameter b increases; and the relation between the wavelength and the period is λ ∝ T1/2, which is qualitatively the same as that obtained by Ou-Yang Qi from Belousov-Zhabotinsky reaction system.

New ab initio Potential Energy Surfaces for Cl（^2P3/2,^2P1/2）＋H2 Reaction

New global three dimensional potential energy surfaces for the Cl＋H2 reactive system have been constructed using accurate multireference configuration interaction calculations with a large basis set. The three lowest adiabatic potential energy surfaces correlating asymptotically with Cl（^2p）＋H2 have been transformed to adiabatic representation, which leads to a fourth coupling potential for non-linear geometries. In addition, the spin-orbit coupling surfaces have also been computed using the Breit-Pauli Hamiltonian. Properties of the new potential are described. Reaction dynamics based on the new potential agrees with the recent experimental results quite well.

CFD Simulation of Reactor Internal Flow in the Scaled APR＋

A series of 1/5 scale reactor flow model tests have been conducted in order to determine the hydraulic characteristics of the APR＋ （advanced power reactor plus）. The objective of test was to determine the core inlet flow field of the model reactor in order to provide input information required by the open core thermal margin analysis code such as TORC. In this study, in order to examine the validity of the results of reactor flow model tests and the applicability of CFD （computational fluid dynamics） in the simulation of reactor internal flow, CFD simulation was conducted with the commercial multi-purpose CFD software, ANSYSCFX V. 14. It was found that the velocity field in the downcomer had the inhomogeneous feature. Relative high velocity region was located in the core region. This result was different from measurement and this difference may result from the fact that some internal structures were not modeled with the real geometry but treated as the porous domain.

A computational analysis of the impact of mass transport and shear on three-dimensional stem cell cultures in perfused micro-bioreactors

In this study, Computational Fluid Dynamics(CFD) is used to investigate and compare the impact of bioreactor parameters(such as its geometry, medium flow-rate, scaffold configuration) on the local transport phenomena and, hence, their impact on human mesenchymal stem cell(hM SC) expansion. The geometric characteristics of the TissueFlex174;(Zyoxel Limited, Oxford, UK) microbioreactor were considered to set up a virtual bioreactor containing alginate(in both slab and bead configuration) scaffolds. The bioreactor and scaffolds were seeded with cells that were modelled as glucose consuming entities. The widely used glucose medium, Dulbecco's Modified Eagle Medium(DMEM), supplied at two inlet flow rates of 25 and 100 μl·h^(-1), was modelled as the fluid phase inside the bioreactors. The investigation, based on applying dimensional analysis to this problem, as well as on detailed three-dimensional transient CFD results, revealed that the default bioreactor design and boundary conditions led to internal and external glucose transport, as well as shear stresses, that are conducive to h MSC growth and expansion. Furthermore, results indicated that the ‘top-inout' design(as opposed to its symmetric counterpart) led to higher shear stress for the same media inlet rate(25 μl·h^(-1)), a feature that can be easily exploited to induce shear-dependent differentiation. These findings further confirm the suitability of CFD as a robust design tool.

RANS （Reynolds Averaged Navier-Stokes） and LES （Large Eddy Simulations） of the Air-Water TOPFLOW-PTS Experiment

The occurrence of a PTS （pressurized thermal shock） in a reactor vessel is an important phenomenon for assessing nuclear reactor safety. New experiment was conducted at HZDR （Helmholtz-Zentrum Dresden-Rossendorf）, focused on thermal mixing processes in the cold leg and the downcomer of two-phase PTS case. Present work reports CFD （computational fluid dynamics） ana｜ysis of steady-state air-water case. CFD analysis was conducted with two turbulence-modeling approaches, RANS （Reynolds Averaged Navier-stokes） and LES （large eddy simulations）. Multiphase situation was modeled with VOF （volume of fluid） approach. Simulations were performed using the FLUENT 12 package. Comparison of computed temperatures results and measurements along the thermo-couple lines revealed results depend on the turbulence model used.

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.

A study on the catalytic performance of carbide slag in transesterification and the calculation of kinetic parameters

The catalytic performance of carbide slag in transesterification is investigated and the reaction kinetic parameters are calculated. After being activated at 650℃, calcium compounds of carbonate and hydroxide in the carbide slag are mainly transformed into calcium oxide. The activated carbide slag utilized as the transesterification catalyst is characterized by X-ray diffraction （XRD）, attenuated total reflectance-Fourier transform infrared spectroscopy （ATR-FTIR）, nitrogen adsorption-desorption and the Hammett indicator method. Compared with the carbide slag activated at 700 and 800℃, the largest surface area of 22.63 m2g^-1, the smallest particle size of 265.12 nm and the highest catalytic efficiency of the carbide slag activated at 650℃ guarantee its capacity in catalyzing transesterification. Then, the influences of activated temperature （Ta）, molar ratio of methanol to oil （γ）, catalyst added amount （ζ）, reaction temperature （Tr） and reaction time （τ） on the catalytic performance are investi- gated. Under the optimal transesterification condition of Ta=650℃, γ=15, ζ=3%, Tr=60℃ and τ=-110 rain, the catalytic efficiency of 92.98% can be achieved. Finally, the kinetic parameters of transesterification catalyzed by the activated carbide slag are calculated, where activation energy （E） is 68.45 kJ mol^-1 and pre-exponential factor （k0） is 1.75×10^9 min^-1. The activated carbide slag shows better reused property than calcium hydroxide.

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.

Computation of kinetic isotope effects for enzymatic reactions

We describe a computational approach,incorporating quantum mechanics into enzyme kinetics modeling with a special emphasis on computation of kinetic isotope effects.Two aspects are highlighted:(1) the potential energy surface is represented by a combined quantum mechanical and molecular mechanical(QM/MM) potential in which the bond forming and breaking processes are modeled by electronic structure theory,and(2) a free energy perturbation method in path integral simulation is used to determine both kinetic isotope effects(KIEs).In this approach,which is called the PI-FEP/UM method,a light(heavy) isotope is mutated into a heavy(light) counterpart in centroid path integral simulations.The method is illustrated in the study of primary and secondary KIEs in two enzyme systems.In the case of nitroalkane oxidase,the enzymatic reaction exhibits enhanced quantum tunneling over that of the uncatalyzed process in water.In the dopa delarboxylase reaction,there appears to be distinguishable primary carbon-13 and secondary deuterium KIEs when the internal proton tautomerism is in the N-protonated or in the O-protonated positions.These examples show that the incorporation of quantum mechanical effects in enzyme kinetics modeling offers an opportunity to accurately and reliably model the mechanisms and free energies of enzymatic reactions.