Development of a comprehensive free radical photopolymerization model incorporating heat and mass transfer effects in thick films

A comprehensive kinetic model describing photopolymerization is developed which allows variation of temperature, species concentrations, and light intensity through the thickness of a photopolymerized film. Heat and mass transfer effects are included, as is the generation of heat by both reaction and light absorption. In addition to initiation, propagation, and termination mechanisms, both primary radical termination and inhibition are incorporated into the model. The possible presence and diffusion of an inert solvent are also accounted for. Thus, the model is useful for examining complex polymerization kinetics and behavior in industrially and commercially important thick film photopolymerizations, such as the curing of contact lenses, dental restorative materials, photolithographic resists, and optoelectronic coatings. The comprehensive model is used to predict polymerization rate, temperature, and conversion profiles in a variety of systems. The effects of heat generation and the thermal boundary conditions are explored, with the result that heat generation in thick samples leads to greatly increased conversions approaching 100 percent. Increased temperature in these samples also may lead to the appearance of two rate maxima, with the first due to the temperature increase and the second caused by the autoacceleration process. The magnitude of the temperature increase, along with the resultant effects, is more pronounced in insulated systems.     

An analytic solution to the transient diffusion-reaction problem in particles dispersed in a slurry reactor

In this work, we present the solution of the equations that govern the reactant transport in a well mixed system that contains particles where diffusion and first-order reaction occur. The transport equations are coupled by an interfacial boundary condition that includes mass transfer resistance. The statement of the problem allows arbitrary time depending feed functions. The evaluation of the solution obtained by the Laplace method requires the solution of an eigenvalue problem. We discuss the evaluation of the solution, and typical results for three different feed functions: step, pulse and oscillatory functions are presented. The resulting equations are able to show the effect of internal and external mass transfer limitations on the particle and fluid concentrations and on kinetic experimental results.     

Modelling of batch fluidised bed drying of pharmaceutical granules

This paper presents a mathematical model based on a three-phase theory, which is used to describe the mass and heat transfer between the gas and solids phases in a batch fluidised bed dryer. In the model, it is assumed that the dilute phase (i.e., bubble) is plug flow while the interstitial gas and the solid particles are considered as being perfectly mixed. The thermal conductivity of wet particles is modelled using a serial and parallel circuit. The moisture diffusion in wet particles was simulated using a numerical finite volume method. Applying a simplified lumped model to a single solid particle, the heat and mass transfer between the interstitial gas and solid phase is taken into account during the whole drying process as three drying rate periods: warming-up, constant rate and falling-rate. The effects of the process parameters, such as particle size, gas velocity, inlet gas temperature and relative humidity, on the moisture content of solids in the bed have been studied by numerical computation using this model. The results are in good agreement with experimental data of heat and mass transfer in fluidised bed dryers. The model will be employed for online simulation of a fluidised bed dryer and for online control.     

LIQUID PHASE TRANSPORT PROPERTIES IN A HIGH PRESSURE PACKED COLUMN

A mathematical model of fluid flow and mass transfer in a packed bed was derived and used to evaluate the liquid phase axial dispersion and mass transfer coefficients under high pressure conditions. The least-squares method was used to evaluate the rate parameters from experimental breakthrough curves, and the agreement between the concentration curves predicted from rate parameters and those measured experimentally was good. Experiments were performed at 20 and 200°C with water as a solvent and nonporous soda-lime glass beads as packing. Although the axial dispersion coefficient was independent of temperature and pressure, the mass transport parameters were found to be pressure dependent.     

OXIDATION OF SULFUR DIOXIDE IN DIFFERENT TYPES OF THREE PHASE REACTORS

Five different types of three-phase reactors are compared with each other by using oxidation of sulfur dioxide on activated carbon. The kinetic measurements were carried out by changing concentrations of sulfur dioxide from 0.04 to 0.17% (volume) and those of oxygen from 2 to 21%. The reaction rate was 0.2 order with respect to sulfur dioxide and 0.5 order with respect to oxygen. The catalytic effectiveness factor and intraparticle diffusivity were evaluated by changing particle sizes of activated carbon from 0.03 to 1.6 mm. Resistances of gas-liquid, liquid-solid mass transfer and intraparticle diffusion were estimated for individual reactors. The optimum reactor was dependent on operating conditions such as gas flow rates, rotating speeds and particle sizes.     

Errors associated with swelling in the analysis of polymer-solvent diffusion measurements

Sorption curves are generated from a mathematical model which includes the influence of the polymer swelling for unsteady-state sorption of a vapor or liquid by a polymer. To investigate the simultaneous effects of the specific volumes of the polymer-penetrant pair and the difference between the final and initial equilibrium concentrations on the sorption curves, statistical experimental design approach is used. Simulation results obtained from the numerical solution of model equations are utilized to estimate the error that would occur if one simply evaluates the diffusion coefficient using the traditional formulas derived from the analytical solution of the sorption equation. An empirical expression is developed that describes the effects of the difference between the final and initial equilibrium concentrations and the specific volumes of the polymer and the penetrant on the magnitude of error in diffusivity associated with the use of one of these traditional formulas so called the initial slope method. The predictive ability of the regression model is tested by performing additional simulations not used in the regression analysis.     

微孔膜气体分布器对气液传质的影响

本文开发了一种新型微孔膜气体分布器,并对使用该分布器时鼓泡塔反应器内气液传质性能进行了研究。实验结果表明,使用这种新型膜气体分布器可以得到细小均匀的气泡,较大幅度地增大了气液传质比表面积,从而大大强化了反应器的传质能力。     

Mass transfer from Taylor bubbles rising in single capillaries

Gas-liquid mass transfer from Taylor bubbles rising in 1, 2 and 3 mm diameter capillaries of circular and square cross-sections was investigated for air-water system. The liquid-phase volumetric mass transfer coefficient k_La was obtained from experimental oxygen absorption dynamics. The experimental k_La values are in good agreement with the model developed by van Baten and Krishna (2004. Chemical Engineering Science 59, 2535-2545), with the additional assumption that the dominant mass transfer contribution is to the film surrounding the bubble.     

氯醇化管道反应新工艺的压降和传质的研究

氯醇化管道反应新工艺是环氧丙烷生产过程中关键步骤，该反应属气液非均相系统，但装有Ｋｅｎｉｃｓ型静态混合构件的管道反应器用于气液系统还缺乏大量的基础数据。研究以Ｎ２－Ｈ２Ｏ２作为实验系统，测定了不同工况下压降和氧含量，并应用一心均相模型救是了相应的摩擦系数和传质系数。     

Gas-liquid mass transfer in a circulating jet-loop nitrifying MBR

Based on airlift configuration, a novel circulating jet-loop submerged membrane bioreactor (JLMBR) adapted to ammonium partial oxidation has been developed. Membrane technology and combined air and water forced circulation are adopted to obtain a high biomass retention time and to achieve a separate control of mixing and aeration. This study is intended to determine how gas-liquid mass transfer is affected by operating conditions. In a first approximation, liquid was assumed to be perfectly mixed. A classical non-steady state clean water test, known as the “gas out-gas in” method, was used to determine the gas-liquid mass transfer coefficient k_La. Air and recirculated liquid superficial velocities were gradually increased from 0.013 to and 0.0056 to , respectively. Subsequently, the gas-liquid mass transfer coefficient k_La varied from 0.01 to . It appears to be influenced by the combined action of air and recirculated liquid flowrates in the range and , respectively, for air and liquid. Correlations are proposed to describe this double influence. Experiments were performed on tap water and a culture medium used for the autotrophic growth of nitrifying bacteria, respectively. Oxygen transfer appeared to be not significantly affected by the mineral salt encountered in this medium.