Quantifying temperature and flow rate effects on the performance of a fixed-bed chromatographic reactor

Chromatographic reactors are based on coupling chemical reactions with chromatographic separation in fixed-beds. Temperature and flow rate are important parameters for the performance of such reactors. Temperature affects mainly adsorption, chemical equilibria, mass transfer and reaction kinetics, whereas flow rate influences residence time and dispersion. In order to evaluate the mentioned effects, the hydrolysis reactions of methyl formate (MF) and methyl acetate (MA) were chosen as case studies. These reactions were performed experimentally in a lab-scale fixed-bed chromatographic reactor packed with a strong acidic ion exchange resin. The chosen reactions can be considered to represent a relative fast (MF) and a relative slow (MA) reaction. The processes which take place inside the reactor were described and simulated using an isothermal equilibrium dispersive model. The essential model parameters were determined experimentally at different temperatures and flow rates. The performance of the chromatographic reactor was evaluated at several discrete constant temperature levels by quantifying product purity, productivity and yield. The work provides insight regarding the influence of temperature and flow rate on values of the model parameters and the performance criteria.     

Direct dynamics study on mechanism and kinetics of the biradical self‐reaction of HOO

A theoretical study of the mechanism and the kinetics for the hydrogen abstraction reaction of the biradical hydroperoxy radical has been presented at the CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G(d,p) level of theory. Our theoretical calculations suppose a stepwise mechanism involving the formation of a postreactant complex in the triplet and singlet entrance channels. Four transition states of the six‐membered chain complexes (³TS1 and ¹TS1) and six‐membered ring complexes (³TS2 and ¹TS2) are located at the high dual level CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G(d,p) method. The rate constants of Path 1 ～ Path 4 at the CCSD(T)/6‐311++G(3d,2p)//CCSD/6‐31+G (d,p) level are calculated by means of the conventional transition state theory (TST) and canonical variational TST without and with small‐curvature tunneling (SCT) correction within the temperature range of 200–2,500 K. The calculated results show that the triplet channel is the dominating reaction channel and Path 2 is found to be the most favorable pathway. The rate constants of Path 2 are in good agreement with the experimental values at the experimentally measured temperatures. Moreover, the variational effect is not obvious in the low temperature range but is not neglectable in the high temperature range. The SCT plays an important role particularly in the low temperature range. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Photo-acoustic detection on electronic quenching rate constants of NO excited states

The electronic quenching rate constants of NO A(2)Σ (υ'=0, 1), E(2)Σ (υ'=2, 3, 4) and F(2)Δ (υ'=1, 2, 3) states by gas air are reported. The experiments were carried out by measuring the total fluorescence intensity of A(2)Σ (υ'=0, 1)→X(2)Π (υ″) transition at various air pressures. It gives the Stern-Volmer plots. The quenching rate constants of A(2)Σ (υ'=0, 1) states are obtained from the slope of Stern-Volmer plots and the known radiative lifetime. Based on the primary results of the work, we have measured the quenching rate constants of high excited E(2)Σ (υ'=2, 3, 4), F(2)Δ (υ'=1, 2, 3) states for the first time with the technique of photo-acoustic (PA) spectroscopy. It is shown that the electronic quenching rate constants of NO E (υ') and F (υ') states are in the order of 10(-10)cm(3)/molecules. They are much larger than those of A(2)Σ (υ') state, whose rate constants are in the order of 10(-13)cm(3)/molecules. For E (υ') and F (υ') states, it is also found that the quenching rate constants increase with the vibrational energy levels. Similar result has been reported also for A(2)Σ (υ'≥2) states in existing literatures. The agreement indicates the potential use of PA spectroscopy for measuring the electronic quenching rate.     

Pseudo global energy released locally by crack extension involving multiscale reliability

The energy release rate criterion, being mono scale by definition, is incompatible with the failure behavior of solids that are inherently dual, if not, multiscale. Time span of reliability is scale sensitive and can be addressed with consistency only by use of transitional functions that are designed to transform a function from one scale to another. A pseudo transitional energy release rate G^∗ is defined to address the cross-scaling properties of energy release rate. The reliability of such a function is found to fall quickly when the scale range deviates from that of micro-macro. In general, the time span of reliability based on G^* shortens considerably within the nano-micro and pico-nano scale ranges, resulting in fast turnover of system usability. Prediction accuracy tends to be scale range specific. Stress or strain based criteria are also mono scale. They may be adequate for some situations at the macroscopic scale, but can be ambiguous for multiscale problems. These situations are analyzed by application of the principle of least variance in conjunction with the R-integrals.Accelerated test data for the equivalent of 20 years’ fatigue crack growth in 2024-T3 aluminum panels were analyzed using the mutliscale reliability model. A time span plateau within the micro-macro range is from 8 to 17 years. This corresponds to the reliable portion of prediction, while the terminal 3 years are regarded as unreliable. A similar time span plateau were also found from 4 to 6 years within the nano-micro scale range. And an even smaller plateau hovering around 1.2 years were found for the pico-nano scale range. Time span of reliable prediction narrows with down sized scale range. The overlapping ends of the scale ranges are rendered unreliable as anticipated. These regions can be suppressed by the addition of meso scale ranges. Reference can be made to past discussions related to multiscaling and mesomechanics.     

Energy density and release rate study of an elliptic-arc interface crack in piezoelectric solid under anti-plane shear

The anti-plane problem of an elliptical inhomogeneity with an interfacial crack in piezoelectric materials is investigated. The system is subjected to arbitrary singularity loads (point charge and anti-plane concentrated force) and remote anti-plane mechanical and in-plane electrical loads. Using the complex variable method, the explicit series form solutions for the complex potentials in the matrix and the inclusion regions are derived. The electroelastic field intensity factors, the corresponding energy release rates and the generalized strain energy density at the cracks tips are then provided. The influence of the aspect ratio of the ellipse, the crack geometry and the electromechanical coupling coefficient on the energy release rate and the strain energy density is discussed and shown in graphs. The results indicate that the energy release rate increases with increment of the aspect ratio of the ellipse and the influence of electromechanical coupling coefficient on the energy release rate is significant. The strain energy density decreases with increment of the aspect radio of the ellipse and it is always positive for the cases discussed. The energy release rate, however, can be negative when both mechanical and fields are applied.     

Analysis of dynamic stress intensity factors of three-point bend specimen containing crack

A new formula is obtained to calculate dynamic stress intensity factors of the three-point bending specimen containing a single edge crack in this study. Firstly, the weight function for three-point bending specimen containing a single edge crack is derived from a general weight function form and two reference stress intensity factors, the coefficients of the weight function are given. Secondly, the history and distribution of dynamic stresses in uncracked three-point bending specimen are derived based on the vibration theory. Finally, the dynamic stress intensity factors equations for three-pointing specimen with a single edge crack subjected to impact loadings are obtained by the weight function method. The obtained formula is verified by the comparison with the numerical results of the finite element method (FEM). Good agreements have been achieved. The law of dynamic stress intensity factors of the three-point bending specimen under impact loadings varing with crack depths and loading rates is studied.     

Anti-plane analysis of semi-infinite crack in piezoelectric strip

Using the complex variable function method and the technique of the conformal mapping, the fracture problem of a semi-infinite crack in a piezoelectric strip is studied under the anti-plane shear stress and the in-plane electric load. The analytic solutions of the field intensity factors and the mechanical strain energy release rate are presented under the assumption that the surface of the crack is electrically impermeable. When the height of the strip tends to infinity, the analytic solutions of an infinitely large piezoelectric solid with a semi-infinite crack are obtained. Moreover, the present results can be reduced to the well-known solutions for a purely elastic material in the absence of the electric loading. In addition, numerical examples are given to show the influences of the loaded crack length, the height of the strip, and the applied mechanical/electric loads on the mechanical strain energy release rate.     

复合功能布的动态力学性能及本构关系

针对复合功能布的物理特性,利用材料试验机和分离式Hopkinson压杆装置,展开了准静态和动态条件下单层和双层复合功能布材料的单轴抗压实验,获得了两种材料在不同应变率下的应力应变曲线和材料的失效应力、应变.实验结果表明:复合功能布的动态失效强度明显高于准静态失效强度,而且随着应变率的增加其动态失效强度呈现增加的趋势,即该材料具有明显的应变率硬化效应.对应力应变曲线进行拟合,给出了材料的动静态粘弹性本构关系.并对复合功能布在不同应变率下的失效应变及材料的损伤结果进行了初步的分析.     

THE USE OF VISCO-ELASTOPLASTIC DAMAGE CONSTITUTIVE MODEL TO SIMULATE NONLINEAR BEHAVIOR OF CONCRETE

A visco-elastoplastic damage constitutive model is proposed for simulating nonlinear behavior of concrete. Based on traditional plastic theory, the irreversible deformation is simulated in effective stress space. In order to reflect different stiffness degradation mechanism of concrete under tensile and compressive loading conditions, both tensile and compressive damage variables are introduced, and then on the basis of energy release rate, the model is firmly derived within the concept of irreversible thermodynamics. The rate-dependent model is considered by introducing viscous regularization into the inelastic strain and damage variable, and combined with an additional elastic condition. Fully implicit backward-Euler algorithm is used to perform constitutive integration. Results of numerical examples using the proposed model agree well with test results for specimens under uniaxial tension and compression, biaxial loading and triaxial loading. Failure processes of single-edge-notched (SEN) beam and double-edge-notched (DEN) specimen are also simulated to further validate the proposed model.     

Effect of moisture content on conveying characteristics of pulverized coal for pressurized entrained flow gasification

During the pneumatic conveying, pulverized coal with different moisture contents may develop substantial difference in flow characteristics, whose cause is not fully understood. This study focused on influence of moisture content on conveying characteristics in an experimental test facility with the conveying pressure up to 4 MPa. The experiments included soft coal and lignite with similar density and particle size. With the increase in moisture content, the mass flow rate decreased for lignite (3.24% < M < 8.18%) but increased at first and then decreased for soft coal (0.4% < M < 6.18%) at same operating parameters. The flowability of soft coal was worse than that of lignite at similar operating parameters and external moisture content. The extremal conveying moisture contents of two coal types were obtained. The particle charge and surface moisture content were investigated to indicate influence mechanism of moisture content on mass flow rate in pneumatic conveying at high pressure. Pressure drop of soft coal was greater than that of lignite for same test section. The conveying phase diagram of dense-phase pulverized coal at high pressure was obtained and the pressure drops through different test sections were compared and analyzed. The bend loss factor rose with the increase in moisture content and was independent of conveying velocity and solid-gas ratio in dense-phase pneumatic conveying at high pressure.