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Industrial Chemistry ÜD no er ra i s w CCHHEEMMIICCAALL a m y RREEAACCTTIIOONN CHEMICAL REACTION ENGINEERING Beyond the Fundamentals EENNGGIINNEEEERRIINNGG C Filling a longstanding gap for graduate courses in the field, Chemical H Reaction Engineering: Beyond the Fundamentals covers basic concepts as well as complexities of chemical reaction engineering, E BBeeyyoonndd tthhee FFuunnddaammeennttaallss including novel techniques for process intensification. The book is divided M into three parts: Fundamentals Revisited, Building on Fundamentals, and Beyond the Fundamentals. I BC Part I: Fundamentals Revisited reviews the salient features of an eA undergraduate course, introducing concepts essential to reactor design, y L such as mixing, unsteady-state operations, multiple steady states, and o complex reactions. nR Part II: Building on Fundamentals is devoted to “skill building,” particu- dE larly in the area of catalysis and catalytic reactions. It covers chemical A t thermodynamics, emphasizing the thermodynamics of adsorption and hC complex reactions; the fundamentals of chemical kinetics, with special e emphasis on microkinetic analysis; and heat and mass transfer effects in T LL..KK.. DDoorraaiisswwaammyy catalysis, including transport between phases, transfer across interfaces, FI and effects of external heat and mass transfer. It also contains a chapter uO DDeenniizz ÜÜnneerr that provides readers with toolsfor making accurate kinetic measurements n N and analyzing the data obtained. d a Part III: Beyond the Fundamentals presents material not commonly E m covered in textbooks, addressing aspects of reactors involving more N than one phase. It discusses solid catalyzed fluid-phase reactions in e G fixed-bed and fluidized-bed reactors, gas–solid noncatalytic reactions, n reactions involving at least one liquid phase (gas–liquid and liquid–liquid), tI and multiphase reactions. This section also describes membrane-assisted aN l reactor engineering, combo reactors, homogeneous catalysis, and sE phase-transfer catalysis. The final chapter provides a perspective on E future trends in reaction engineering. R I N G K11525 CHEMICAL REACTION ENGINEERING Beyond the Fundamentals CHEMICAL REACTION ENGINEERING Beyond the Fundamentals L.K. Doraiswamy Deniz Üner Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business MATLAB® is a trademark of The MathWorks, Inc. and is used with permission. The MathWorks does not warrant the accuracy of the text or exercises in this book. This book’s use or discussion of MATLAB® software or related products does not constitute endorsement or sponsorship by The MathWorks of a particular pedagogical approach or particular use of the MATLAB® software. 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Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Dedicated to my former students and colleagues at Iowa State University (USA) and National Chemical Laboratory (India), from whom I learned so much. L.K. Doraiswamy Dedicated to L.K. Doraiswamy (1927–2012) and his continuing legacy in Chemical Reaction Engineering. D. Uner © 2009 Taylor & Francis Group, LLC Contents Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxv Notations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxxi Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxxvii PART I FUNDAMENTALS REVISITED Objectives 1 Introduction 1 The essential minimum of chemical reaction engineering 2 The skill development 2 Getting started 2 Warm-up questions 3 Qualitative 3 Quantitative 3 1 Reactions and reactors: Basic concepts . . . . . . 5 Chapter objectives 5 Introduction 5 Reaction rates 5 Different definitions of the rate 6 Basic rate equation 8 Stoichiometry of the rate equation 9 Basic relationships 9 Conversion–concentration relationships 10 Variable-density reactions 11 Reactors 12 Batch reactor 13 Reactions without volume change 14 Reactions with volume change 14 Nonisothermal operation 16 Optimal operating policies 18 vii © 2009 Taylor & Francis Group, LLC Chemical Reaction Engineering Plug-flow reactors 19 Basic PFR equation 20 Design equations 21 Nonisothermal operation 21 Perfectly mixed flow reactor (MFR) 23 Basic CSTR equation 23 Nonisothermal operation 24 Multiple steady states 26 MSS in a CSTR 26 Adiabatic CSTR 27 Stability of the steady states 28 Comparison of BR, PFR, and MFR 29 Explore yourself 30 References 31 Bibliography 31 2 Complex reactions and reactors . . . . . . . . . . . 33 Chapter objectives 33 Introduction 33 Reduction of complex reactions 34 Stoichiometry of simple and complex reactions 34 Mathematical representation of simple and complex reactions 35 Independent reactions 36 Rate equations 38 The concept of extent of reaction 38 Determination of the individual rates in a complex reaction 39 Selectivity and yield 39 Definitions 40 Analytical solutions 40 Maximizing selectivity in a complex reaction: Important considerations 43 Multistep reactions 46 Definitions 46 Yield versus number of steps 47 Reactor design for complex reactions 48 Batch reactor design based on number of components 48 Use of extent of reaction or reaction coordinates 50 Plug-flow reactor 52 Continuous stirred tank reactor 53 Reactor choice for maximizing yields/selectivities 56 viii © 2009 Taylor & Francis Group, LLC