Evidence of dual mobility in sulfur dioxide-polyarylate system: An integral sorption analysis

Integral sorption/desorption measurements were carried out for the sulfur dioxide-glassy polyarylate polymer system at 25°C, 40°C, 55°C, and 63°C. The transport of sulfur dioxide in the glassy polyarylate polymer was governed by Fickian diffusion. The effective diffusion coefficient of sulfur dioxide increased with increasing penetrant concentration. The concentration dependence of the effective diffusion coefficient is explained on the basis of the partial-immobilization model developed by Paul and Koros. The mobility of the molecules sorbed in the Langmuir mode is shown to be significantly lower than the mobility of the molecules in Henry's law dissolution mode. The predictions of permeability values as a function of upstream gas pressure are presented. The equilibrium sorption isotherms for this system are well represented by the dualmode sorption model. The eltergetics and the temperature dependence of the dual-mode parameters are also discussed.     

Chemical storage of solar energy—kinetics of heterogeneous NH3 and H2SO4 reactions II. Process and reactor design

An important energy recovery step in the ammonium hydrogen sulfate (AHS) cycle is the recombination reaction producing NH₄HSO₄. It has been determined that the optimum way to accomplish this, and prevent side reactions, is by the heterogeneous gas-liquid reaction of H₂SO₄ and NH₃. A mathematical model is presented and applied to the two reaction zones and a method of numerical solution is discussed. Three horizontal pilot-scale configurations, 0.17 × 10⁶ to 4.2 × 10⁶ kJ/h energy release, are discussed and sizing is presented. The most important conclusion from the work is that the energy can be released most effectively by carrying out the reaction in a double pipe tubular reactor operating in the annular flow regime with both gas and liquid in turbulent flow.     

FLOW GENERATED BY PITCHED BLADE TURBINES II: SIMULATION USING κ-ε MODEL

Experimental data on average velocity and turbulence intensity generated by pitched blade downflow turbines (PTD) were presented in Part I of this paper. Part II presents the results of the simulation of flow generated by PTD

The standard κ-ε model along with the boundary conditions developed in the Part 1 have been employed to predict the flow generated by PTD in cylindrical baffled vessel. This part describes the new software FIAT (Flow In Agitated Tanks) for the prediction of three dimensional flow in stirred tanks. The basis of this software has been described adequately. The influence of grid size, impeller boundary conditions and values of model parameters on the predicted flow have been analysed. The model predictions successfully reproduce the three dimensionality and the other essential characteristics of the flow. The model can be used to improve the overall understanding about the relative distribution of turbulence by PTD in the agitated tank     

Hysteresis in cloud heights during solid suspension in stirred tank reactor: Experiments and CFD simulations

Solid suspension in stirred tank reactor is widely used in process industries for catalytic reactions, dissolution of solids, crystallization, and so on. Suspension quality is a key issue in design and operation of stirred reactor and its determination is not straight forward. Cloud height measurements of solid suspension provide a relatively simple way to quantify quality of suspension. In this work, experiments were carried out to quantify variation of cloud heights with impeller speed and particle characteristics. These measurements were carried out using visual observations, image analysis, and ultrasound velocity profiler techniques. The obtained data demonstrated the existence of hysteresis in cloud heights with respect to impeller speed. Apart from possible applications in reducing power required for achieving desired solid suspension quality, the existence of hysteresis also provides a new way to evaluate computational fluid dynamics (CFD) simulations of solid–liquid flows in stirred vessels. An attempt was made to capture observed hysteresis in cloud heights in CFD simulations. The simulated results were compared with the experimental data. The presented models and results (experimental and computational) will be useful for simulating complex solid–liquid flows in stirred reactors. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Interaction between micro- and macro-mixing during reactions in agitated tanks

The present investigation focusses on the interactions between micro-and macro-mixing in a stirred tank reactor, operated in the semi-batch mode. With long feed times only micromixing controls reaction, but below a critical feed time macroscopic gradients also become important. Experiments generated a coherent data set which can be used as a design guide and also for model validation. A competitive, consecutive azocoupling reaction was carried out, whereby imperfect mixing produces finite values of X_S (yield of secondary product) which can be conveniently used as a mixing index. The influences of feed location, feed rate, stirrer speed, concentrations and vessel size on selectivity were studied. The micromixing model of Baldyga and Bourne (1989) was extended to include interactions between macro-and micro-mixing and should be valid for feed times below the critical value, although not so short as the macromixing time in the vessel. Model predictions were compared with the experimental results.     

Analysis and evaluation of permeability techniques for characterizing fine particles Part II. Measurement of specific surface area

The performance of both steady-state and transient permeameters has been evaluated. A number of standard powders was chosen and their surface areas determined by gas adsorption techniques for comparison with surface areas obtained using permeameters. The powders were chosen to cover a wide range o density (0.92 – 18.7 g/cm³) and surface area (0.06 – 350 m²/g).The effect of particle shape, i.e. needles, spherical particles, flakes and irregularly shaped particles on surface area determined by permeametry has also been studied. A linear relationship between BET surface area and that obtained by using a simple U-tube transient flow permeameter has been obtained over a wide range of particle size and macroporosity.The Fisher Subsieve Sizer was chosen as a typical example of a steady-state permeameter, and a number of shortcomings in this instrument have been found. A simple steady-state permeameter was constructed to evaluate the theoretical model as developed in Part I for atmospheric pressure permeametry, and the model has been found to give good values of external surface areas for powders having an average particle size greater than 2 μm. The effect of slip flow for particles less than 1 μm in diameter has been established for atmospheric pressure permeametry.This paper also presents measurements of specific surface area determined by using a more recent permeameter, namely the Permaran. This instrument performed within a reproducibility of ±7% and produced data in agreement with that taken on similar devices and also with the theoretical analysis presented in Part I.The performance of a Knudsen-flow permeameter has been evaluated, and the instrument has been found to give accurate values of external surface area of fine as well as coarse powders.     

Comparative evaluation of tolerance control chart models

A comparative evaluation of two widely used tolerance stack up models is carried out. Experimental metal cutting tests of resultant dimensions obtained under one and two fixturing set-ups are used to test the underlying assumptions behind the Wade and Bourdet tolerance chart models. Resultant dimensions obtained under a single fixturing set up are found to be highly correlated and free of fixturing error; their treatment under the Wade model can thus lead to overly conservative tolerance allocation which may reject an otherwise feasible process plan. The results of the experimental evaluation lend support to the Bourdet deterministic treatment of such resultant dimensions. However, the probabilistic approach proposed by Bourdet does not guarantee a solution.     

Rotary Cement Kiln Simulator (RoCKS): Integrated modeling of pre-heater, calciner, kiln and clinker cooler

This paper presents an integrated reaction engineering based mathematical model for clinker formation in cement industry. Separate models for pre-heater, calciner, rotary kiln and cooler were initially developed and coupled together to build an integrated simulator. Appropriate models for simulating gas-solid contact and heat transfer in pre-heaters were developed. Calciner was modeled by considering simultaneous combustion of coal particles and calcination of raw meal. Complex heat transfer and reactions (solid-solid, gas-solid and homogeneous reactions in gas phase) in rotary kiln were modeled using three sub-models coupled to each other. Solid-solid reactions in the bed region of the kiln were modeled using pseudo-homogeneous approximation. Melting of solids in the bed and formation of coating within the kiln were accounted. Clinker cooler was simulated by developing a two-dimensional model to capture cross-flow heat transfer between air and hot clinkers. The individual models were coupled with each other via mass and energy communication through common boundaries. The coupled model equations were solved iteratively. The model predictions agree well with the observations and experience from cement industry. The model was used to gain better understanding of influence of operating conditions on energy consumption in cement plant. Several ways for reducing energy consumption were computationally investigated. The integrated model, the developed software RoCKS (for Rotary Cement Kiln Simulator) and results presented here will be useful for enhancing our understanding and for enhancing the performance of clinker manufacturing.     

Modeling of bubble column slurry reactor for reductive alkylation of p-phenylenediamine

A bubble column slurry reactor (BCSR) model has been developed for the reductive alkylation of p-phenylenediamine (PPDA) with methyl ethyl ketone (MEK) to N,N^′-di-secondary-alkyl-p-phenylenediamine (Di-amine). This particular reaction system is commercially relevant and involves a combination of parallel and consecutive reactions comprising equilibrium non-catalytic (homogeneous) and catalytic (heterogeneous) steps. The proposed model is based on the ‘mixing cell approach’. In this work the mixing cell approach has been extended by including a liquid backflow stream from all but the bottommost mixing cell. The model incorporates the contributions of gas-liquid and liquid-solid mass transfer, heat effects, and complex multistep reaction kinetics. CFD model is used to estimate the extent of backflow among mixing cells and its dependence on operating parameters. The effect of gas and liquid velocities, catalyst loading, inlet PPDA concentration, and temperature on the conversion, selectivity, global rate of hydrogenation, and temperature rise is discussed. The comparison of the current approach with the traditional mixing cell model is discussed. The BCSR model presented here will be useful to provide guidelines for designing and improving overall performance of bubble column reactors.