活性炭中甲烷水合物的生成动力学

在温度275．75－279．95K和压力5．6－9．6MPa的静置条件下，测定了14组甲烷水合物在活性炭中的生成动力学数据（压力－时间关系），分析了甲烷水合物在活性炭中生成的物理过程，结合边界层理论和结晶学原理，提出了单液膜传质控制机理的生成动力学模型，并求得了解析解,使用Levenberg-Marquardt方法拟合模型参数，模型预测值与实验值符合良好。     

Prediction of cracking within early-age concrete due to thermal, drying and creep behavior

To predict potential early-age cracking after concrete placing, a numerical simulation procedure has been completed based on a micromechanical model and empirical formulas on the property development of young concrete. The numerical model could account for the effects of hydration, moisture transport and creep. Environmental influences, such as removal of formworks, curing conditions and variations of surrounding temperature and relative humidity, have been investigated. In calculating stress field with age caused by these synthetic physical-mechanical processes, three-dimensional finite element and finite difference (3D-FE-FD) methods are combined together.     

Residue curve maps for reactive distillation systems with liquid-phase splitting

A model has been developed to study the effects of chemical kinetics on the residue curve maps (RCM) for reactive distillation systems with liquid phase splitting. In the model, chemical reaction can occur in both or only one of the two liquid phases. The heating policy V/V₀=H/H₀ is applied so that the kinetic effect can be described by a single parameter, the Damköhler number Da. The effects of reaction kinetics on pseudohomogeneous and heterogeneous mixtures have been compared. The properties of their RCMs are the same outside, but are fully different inside the liquid-liquid (L-L) region if they have different chemical equilibrium curves. Inside the L-L region, the chemical equilibrium curve coincides to a unique reactive liquid-liquid tie line in case that the pseudohomogeneous chemical equilibrium curve intersects with the L-L envelope. When the reaction occurs in only one of the two liquid phases, the residue curves inside the L-L region are strongly affected by the L-L envelope, especially at high Da. In the present paper, first an illustrative arbitrary reaction system, and then the reaction of cyclohexene with water to cyclohexanol are analysed with respect to their RCMs.     

Development and characterization of magnetorheological polymer gels

Magnetorheological materials have been used in many applications in recent years. To develop new materials, polyurethane and silicone polymer gels were investigated. Rheology is qualitatively controlled for each system by controlling the concentration of reactants and diluents. The resulting polymers have solid, gel, or liquid states, depending on the crosslinking and dilution. The gels were characterized through kinetic analysis. Differential scanning calorimetry (DSC) was used with analysis methods to find the kinetic properties for diluted and undiluted polyurethane systems. Heat of reaction, order of reaction, preexponential constant, and activation energy were obtained from the experimental DSC data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2733–2742, 2002     

Modelling of a gas flow measurement: Application to nuclear containment vessels

The objective of this work is to simulate the gas flow across a concrete wall of a nuclear power plant internal enclosure. In the laboratory, permeability measurements are generally made on cylindrical samples (15 cm diameter×5 cm height: ∅ 15×5 cm) with a steady-state experiment. To be able to predict structural behaviour, we studied size effect and steady-state time with a modified CEMBUREAU permeability test. A statistical approach showed that there is no size effect on concrete permeability. Laboratory results found on cylindrical samples can be applied to tests in situ, where concrete specimens are thicker. A model based on the mass balance relation provided times to reach steady state and reproduced experimental flow kinetics for uniform water content across specimens.     

On the Direct Addition of Amine N–H to Ch≡C Triple Bonds with Late Transition Metal Catalysts

The kinetics of the transition metal-catalysed direct addition of amine NH bonds to carbon--carbon multiple bonds (hydroamination) has been explored by in situ spectroscopic techniques. From an open mass balance it was concluded that an intermediate species was formed during the cyclisation of 6-aminohex-1-yne. This species was identified as the enamine 2-methylene-piperidine, which is the primary hydroamination product.     

Energy Saving in Industrial Wood Drying Addressed by a Multiscale Computational Model: Board, Stack, and Kiln

This article proposes a multiscale computational model able to calculate energy consumption in a batch lumber kiln. A dual-scale computational model of wood drying deals with the boards/stack interaction and serves as a basis for the present work. A new module was added here that calculates heat losses through kiln walls (convection, condensation) and the energy used by each kiln component (fans, heating elements, humidifier, vacuum pump, etc.). The corresponding mathematical formulation is presented and then theoretical results are compared to those collected in an industrial vacuum kiln. As application example, the effect of air reversal, air velocity, and kiln insulation are exhibited, which depicts the great potential and prospects of this new tool for energy savings in relation to the product quality.     

Rates of Crystallization of Dried Lactose-sucrose Mixtures

The isothermal crystallization kinetics of glassy lactose/sucrose mixtures were studied at several storage temperatures (close to T_g and T_m). The kinetic parameters implicit in the Avrami equation were determined. Activation energies for transport (E_D) and surface nucleation (W*) were also found and correlated to the molar composition of the lactose/sucrose mixtures. A monotonic increase in the half crystallization time (t_1/z), Avrami index (n), % crystallization per day, activation energy for transport (E_D) and surface nucleation energy (W*) and a decrease in the crystallization velocity constants (K) were related to the increase in the lactose content of lactose/sucrose mixtures.     

Screening of supports for the immobilization of pectinmethylesterase from acerola (Malpighia glabra L)

A partially purified extract of pectinmethylesterase (PME) from acerola fruit was immobilized on various supports: glass, celite, chrysotile, agarose, concanavalin A Sepharose 4B, egg shell, polyacrylamide and gelatin. In addition, reticulation with glutaraldehyde was assessed, as well as the use of gelatin in the presence of celite, glass and silica. The highest immobilization yields were obtained when the pectinmethylesterase was immobilized in concanavalin A Sepharose 4B (81.7%) and in gelatin‐water (78.0%). Copyright © 2004 Society of Chemical Industry     

A NEW APPROACH FOR THE CLASSIFICATION AND ENUMERATION OF UNIQUE REACTION ROUTES AND UNIQUE OVERALL REACTIONS IN MULTIPLE CHEMICAL REACTION SYSTEMS

The methodology of response reactions (RERs) introduced earlier from thermodynamic and kinetic considerations is used in this work to develop a new algorithm for the classification and enumeration of unique/direct reaction routes (RRs) and overall reactions (ORs). According to the RERs approach, a unique set of both RRs and ORs may be generated starting from any conceivable set of linearly independent RRs and ORs. In particular, the direct ORs may be most conveniently enumerated starting from the formula matrix of the terminal species (reactants and products), i.e., without any relation to the elementary reactions comprising the detailed mechanism. Depending on the type of ORs produced by the RRs one can distinguish between two distinct types of direct RRs. Namely, one option is to define a direct RR by specifying the intermediate species that need to be eliminated. This type of RR is referred to as Milner RRs. The other option is to require the direct RRs to produce RERs, thus resulting in RRs referred to as Happel-Sellers RRs.