Scientific Computing in Chemical Engineering II Computational Fluid Dynamics, Reaction Engineering, and Molecular Properties Springer Berlin Heidelberg New York Barcelona Hong Kong London Milan Paris Singapore Tokyo Keil . Mackens . V 08 . Werther (Eds.) Scientific COlTIputing in Chetnical Engineering II Computational Fluid Dynamics, Reaction Engineering, and Molecular Properties With 189 Figures and 29 Tables Springer Editors: Prof. Dr. Frerich Keil Technical University ofHamburg-Harburg Chair of Chemical Reaction Engineering EiBendorfer StraBe 38 D-2I071 Hamburg / Germany Prof. Dr. Wolfgang Mackens Technical University ofHamburg-Harburg Section of Mathematics SchwarzenbergstraBe 95 D-21073 Hamburg / Germany Prof. Dr. Heinrich VoB Technical University of Hamburg-Harburg Section of Mathematics SchwarzenbergstraBe 95 D-21073 Hamburg / Germany Prof. Dr.-Ing. Joachim Werther Technical University ofHamburg-Harburg Chemical Engineering I DenickestraBe 15 D-2I071 Hamburg / Germany ISBN-13: 978-3-642-64295-1 Springer-Verlag Berlin Heidelberg New York Cataloging-in-Publication Data applied for Die Deutsche Bibliothek -CIP-Einheitsaufuahme Scientific computing in chemical engineering / F. Keil ... (ed.). -Berlin; Heidelberg; New York; Barcelona; Hong Kong; London; Milan; Paris; Singapore; Tokyo: Springer, 1999 1. Computational fluid dynamics, reaction engineering, and molecular properties: with tables. - 1999 ISBN-13: 978-3-642-64295-1 e-ISBN-13: 978-3-642-60185-9 DOl: I 0.1 007/978-3-642-60185-9 This work is subject to copyright. All rights are reserved, whether the whole or part ofthe material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law. © Springer-Verlag Berlin Heidelberg 1999 Softcover reprint of the hardcover 1st edition 1999 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Camera-ready by authors Cover-design: E. Kirchner, Heidelberg SPIN: 10673740 02/3020 -5 432 I 0 -Printed on acid-free paper Preface The present proceedings assemble the contributions to the second work shop on "Scientific Computing in Chemical Engineering". The two volumed edition covers the wide spectrum of computational activities in chemical pro cess engineering encompassing tasks from process development, process de sign and optimization to process operations and control. The increasing per formance of computers and the rapid advancement of numerical techniques encourages the employment of more sophisticated models. Quantum chemical approaches, molecular dynamics and Monte Carlo methods penetrate engi neering design of catalysts and the calculation of phase transfer phenomena. Computational fluid dynamics of multi-phase flow is now a standard tool in chemical plant design. Numerical simulations replace time consuming and, therefore, expensive experiments to an ever increasing extent. The present workshop reflects these developments. The large number of contributions made it necessary to split the proceed ings into two volumes. We grouped the contributions into ten sections with the headings Simulation of Reactive Flows, Reaction Engineering, Reaction Diffusion Problems, Molecular Properties, Computer Aided Process Design, Combustion and Flame, Image Processing, Optimization, Control and Neural Networks. The present volume deals with the first four of them including the invited presentations related to these topics. The companion volume deals with the remaining six. The workshop was organized by the Collaborative Research Center (Son derforschungsbereich) 238 of the Deutsche Forschungsgemeinschaft "In-situ measuring techniques and dynamic modelling of multiphase flow systems" at the Technical University of Hamburg-Harburg in cooperation with the Ger man Society for Chemical Apparatus, Chemical Engineering and Biotechnol ogy e.V. (DECHEMA), the special interest groups "Scientific Computing" and "Industrial Mathematics" of the Deutsche Mathematiker Vereinigung (DMV), the joint special interest group "Numerical Software" of the DMV, the Gesellschaft fUr Angewandte Mathematik und Mechanik (GAMM), and the Gesellschaft fUr Informatik (GI), as well as the GAMM special interest group "Scientific Computing". We thank all the people from these societies and groups who helped to realize both these proceedings and the workshop. We are grateful to our large number of referees for their careful inspection of the contributed papers and their valuable comments which increased the quality of the proceedings considerably. Last but not least it is a pleasure for us to thank Dipl.-Phys. Ing. Vera Lochmann and Margitta Janssen for their untiring efforts in collecting all contributions and adapting them to the Springer g\1EX conventions. The Editors Contents Preface....................................................... V 1 Invited Presentations.............................. 1 Molecular Simulation: Phase Equilibria and Confined Systems............................................... .... ... 2 Keith E. Gubbins Efficient Bifurcation Analysis of Forced Periodic Processes 12 Dan Luss, Johannes Khinast Mathematical Modeling of the Coupling of Chemical Kinetics With Flow and Molecular Transport 26 Ulrich Maas Non-Adiabatic Effects in Quantum-Classical Molecular Dynamics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 42 Christof Schutte, Peter Nettesheim 2 Molecular Properties .............................. 57 Molecular Dynamics Simulation of Penetrant Transport in Organic/Inorganic Composite Membrane Materials. . . . . . .. 58 Martin Bohning, Dieter Hofmann, Dieter Paul ParaGauss: A Density Functional Approach to Quantum Chemistry on Parallel Computers. . . . . . . . . . . . . . .. 66 Th. Belling, Th. Grauschopf, S. Kruger, F. Nortemann, M. Staufer, M. Mayer, V. A. Nasluzov, U. Birkenheuer, N. Rosch Mathematics for Combinatorial Chemistry. . . . . . . . . . . . . . . . . . .. 74 Th. Gruner, A. Kerber, R. Laue M. Meringer Monte Carlo Simulation of Diffusion within Three-dimensional Pores with Irregular Walls 82 Xiang-yun Guo Frerich J. K eil Molecular Modeling of Polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 90 Reinhard Hentschke Thomas Flebbe, Ewald Aydt Extension of Modified UNIFAC to Refrigerant Mixtures. . . . .. 98 Michael Kleiber, Joachim K. Axmann VIII Simulation of Transport and Diffusion on the Voronoi Network ............................................. 106 V.A. Luchnikov, N.N. Medvedev, V.P. Voloshin, A. Geiger Monte Carlo Modeling of Surface Diffusion in Interacting Systems with Phase Transitions ................ 114 F. Nieto, A.A. Tarasenko, C. Uebing Hydrophobic Aggregation of Nonionic Surfactants in Aqueous Solution: An MD Simulation Study ............... 126 Dietmar Paschek, Thomas Engels, Wolfgang v. Rybinski, Alfons Geiger Molecular Dynamics Simulations of Polymer-Membrane/Solvent Interfaces ....................... 134 Claudia Schepers, Dieter Hofmann, Dieter Paul 3 Reaction Diffusion Problems .................... 143 A Continuation Framework for Invariant Subspaces and Its Application to Traveling Waves ....................... 144 Wolf-Jurgen Beyn, Winfried Kieft, Vera Thummler Sensitivity Analysis of Multicomponent Mass Transport in Porous Solids Described by Partial Differential Equations .. 152 Pavel Capek, Andreas Seidel-Morgenstern Simulation of the Diffusant Distribution in the Diffuse Furnace with Wafers ........................... 160 Orest Korbetsky, Victoria Kotchubey Modelling and Simulation of Transient Transport Processes Using Axial Dispersion Model ...................... 167 Xing Luo,jBernd Niemeyer A New Sparse Matrix Storage Method for Adaptive Solving of Reaction-Diffusion-Transport Equations ............ 175 Nicolas Neuss The Numerical Simulation of Annular Chromatography by Adaptive Finite Element Method .......................... 183 A. Thiele, L. Tobiska 4 Reaction Engineering .............................. 191 Modeling of Thermal Degradation of Polymers ............... 192 Henning Bockhorn, Andreas Hornung, Ursel Hornung, Petra Jakobstroer, Michael Wulkow Contents IX Influence of Occupancy and Pore Network Topology on Tracer and Transport Diffusion in Zeolites ................. 200 Marc-Olivier Coppens, Alexis T. Bell, Arup K. Chakraborty Modeling of Pressure Fields in Fluids in Various Environlllents Including DalllPing Effects and Change of Wave Velocity Due to the Elllergence of Cavitation Bubbles ......................................... 208 Sascha Dahnke, Frerich J. Keil On the Solution of Nonlinear Fractional-Order Differential Equations Used in the Modeling of Viscoplasticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 Kai Diethelm, Alan D. Freed Stability Analysis of Chelllical Reactors ...................... 225 M. A. Efendiev, A. Schuppert Silllulation of the Non-Stationary Behaviour of Fixed-Bed Reactors for the Deterlllination of Kinetic Expressions in Consideration of Inholllegeneous Concentration Profiles Inside the Catalyst Pellets ........................... 231 Abdul Garayhi, Frerich Keil A Dynalllic Model for the Venturi Loop Reactor .............. 239 Robbert de Graaf, Remco Reinstra, M aurits Wieberdink, Michiel Kreutzer NUlllerical Modelling of Multiphase-Multicolllponent Systellls in Porous Media .................................... 247 R. Huber, R. Helmig Efficient COlllPutation of Singularities of Chelllical Reactor Models ............................................... 255 Johannes Khinast, Dan Luss COlllPutational N ulllerical Approaches in the Silllulation of 5MB Process .... . . . . . . . . . . . . . . . . . . . . . . . . 263 Celina P. Leao, Diana Azevedo, Alirio E. Rodrigues A Two Dilllensional Population Model for a Continuous Crystallizer ................................. 271 A. Mitrovic, S. Motz, A. Gerstlauer, C. Gahn, E.-D. Gilles PE - a Scientific COlllputer Progralll for the Calculation of Fluid-Phase Equilibria ......................... 279 Oliver Pfohl, Stanimir Petkov, Gerd Brunner x Solving Chemical Engineering Problems with Front Propagation Using an Adaptive Moving Grid Method ........ 287 A. Salden, J. Frauhammer, G. Eigenberger Dynamic Simulation of Reactive Absorption Processes for the Purification of Coke Oven Gases ... . . . . . . . . . . . . . . . . . . . 295 R. Schneider, E. Y. Kenig A. G6rak Remarks on the Numerical Treatment of Polymerization Processes .................................. 303 Peter Seifert Direct Determination of Cyclic Steady States of Cyclically Operated Packed Bed Reactors .................. 311 T.L. van Noorden, S.M. Verduyn Lunel, A. Bliek 5 Simulation of Reactive Flows ................... 319 On Error Control for Reactive Flow Problems ................ 320 Roland Becker, Malte Braack, Rolf Rannacher Numerical Simulation of a Silicon Floating Zone with a Free Capillary Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328 Eberhard Biinsch, Burkhard Hohn Prediction of Pressure Losses in Porous Media Using the Lattice Boltzmann Method ......................... 336 Jorg BemsdorJ, Francis Delhopital, Gunther Brenner, Franz Durst Simulation and Analysis of Mixing in Two-Dimensional Turbulent Flows Using Fourier and Wavelet Techniques ...... 344 Henning Bockhom, Wolfgang Gerlinger, Kai Schneider, Jorg Ziuber Direct Numerical Simulation of Marangoni Convection in a Twofluid System ......................................... 352 Thomas Boeck, Andre Thess Computation of Flows with Free Surfaces ..................... 360 Ismet Demirdzic, Samir Muzaferija, Milovan Peric, Eberhard Schreck, Volker Seidl Simulation of Reactive Flow in a Partial Oxidation Reactor with Detailed Gas Phase and Surface Chemistry Models ............................................ 368 Olaf Deutschmann, Lanny D. Schmidt, Jiirgen Warnatz Contents XI Generalized Multiresolution Analysis on Unstructured Grids ....................................... 376 Oliver Friedrich, Friederike Schroder-Pander, Thomas Sonar Computational Fluid Dynamics Applied to Chemical Reaction Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383 J.A.M. Kuipers, W.P.M. van Swaaij CFD Simulation Tool for the Systematic Examination of Effects on Band Spreading in Large Radial Columns ....... 391 M. Lisso, G. Wozny, Y. Beste, W. Arlt On Projection-Based Time-Splitting Schemes for Computing Chemically Reacting Flows ....................... 401 A ndreas Prahl Chemical Partial Equilibrium Model in Gasdynamics Problems ......................... ........... 409 Vladimir 1. Sakharov, Elena Fateeva Modelling Transient Irradiation Intensities of Pool Flames . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417 Steffen Staus, Axel Schonbucher Index ....................................................... 425 Index of Complementary Volume ................ 431 Author's Index ................................... ....... 437 Author's Index of Complementary Volume ... 441