Chemical Reaction Engineering

Chemical Reaction Engineering

by L.K. Doraiswamy, Deniz Uner
Released July 2013
Publisher(s): CRC Press
ISBN: 9781482217964

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Book description

Filling a longstanding gap for graduate courses in the field, Chemical Reaction Engineering: Beyond the Fundamentals covers basic concepts as well as complexities of chemical reaction engineering, including novel techniques for process intensification. The book is divided into three parts: Fundamentals Revisited, Building on Fundamentals, and Beyon

Table of contents

  1. Cover
  2. Title Page
  3. Copyright Page
  4. Dedication
  5. Table of Contents
  6. Preface
  7. Notations
  8. Overview
  9. Part I - Fundamentals Revisited
    1. Objectives
    2. Introduction
    3. The essential minimum of chemical reaction engineering
    4. The skill development
    5. Getting started
    6. Warm-up questions
      1. Qualitative
      2. Quantitative
    7. Chapter 1: Reactions and reactors: Basic concepts Reactions and reactors: Basic concepts
      1. Chapter objectives
      2. Introduction
      3. Reaction rates
        1. Different definitions of the rate
        2. Basic rate equation
      4. Stoichiometry of the rate equation
        1. Basic relationships
        2. Conversion–concentration relationships
        3. Variable-density reactions
        4. Reactors
        5. Batch reactor
          1. Reactions without volume change
          2. Reactions with volume change
        6. Nonisothermal operation
          1. Optimal operating policies
        7. Plug-flow reactors
          1. Basic PFR equation
          2. Design equations
          3. Nonisothermal operation
        8. Perfectly mixed flow reactor (MFR)
          1. Basic CSTR equation
        9. Nonisothermal operation
      5. Multiple steady states
        1. MSS in a CSTR
        2. Adiabatic CSTR
          1. Stability of the steady states
        3. Comparison of BR, PFR, and MFR
      6. Explore yourself
      7. References
      8. Bibliography
    8. Chapter 2: Complex reactions and reactors
      1. Chapter objectives
      2. Introduction
      3. Reduction of complex reactions
        1. Stoichiometry of simple and complex reactions
        2. Mathematical representation of simple and complex reactions
        3. Independent reactions
      4. Rate equations
        1. The concept of extent of reaction
        2. Determination of the individual rates in a complex reaction
      5. Selectivity and yield
        1. Definitions
        2. Analytical solutions
          1. Maximizing selectivity in a complex reaction: Important considerations
        3. Multistep reactions
          1. Definitions
      6. Yield versus number of steps
      7. Reactor design for complex reactions
        1. Batch reactor design based on number of components
        2. Use of extent of reaction or reaction coordinates
        3. Plug-flow reactor
        4. Continuous stirred tank reactor
      8. Reactor choice for maximizing yields/selectivities
        1. Parallel reactions (nonreacting products)
          1. The general case
          2. Effect of reaction order
          3. One of the reactants undergoes a second reaction
        2. Parallel–consecutive reactions
      9. Plug-flow reactor with recycle
        1. The basic design equation
        2. Optimal design of RFR
        3. Use of RFR to resolve a selectivity dilemma
      10. Semibatch reactors
        1. Constant-volume reactions with constant rates of addition and removal: Scheme 1
        2. Variable-volume reactor with constant rate of inflow: Scheme 2
        3. Variable-volume reactor with constant rate of outflow of one of the products: Scheme 3
        4. General expression for an SBR for multiple reactions with inflow of liquid and outflow of liquid and vapor: Scheme 4
        5. Nonisothermal operation
      11. Optimum temperatures/temperature profiles for maximizing yields/selectivities
        1. Optimum temperatures
        2. Optimum temperature and concentration profiles in a PFR
          1. Parallel reactions
          2. Consecutive reactions
          3. Extension to a batch reactor
      12. Explore yourself
      13. References
      14. Bibliography
    9. Interlude I
      1. Reactive distillation
      2. Membrane reactors
        1. Inorganic membranes for organic reactions/synthesis
        2. Potentially exploitable features of membranes
          1. Equilibrium shift in membrane reactors
          2. Controlled addition of reactants
          3. Preventing excess reactant “slip” in reactions requiring strict stoichiometric feeds
          4. Mimicking trickle-bed operation with improved performance
          5. Coupling of reactions
          6. Hybridization
      3. Phase transfer catalysis
      4. References
    10. Chapter 3: Nonideal reactor analysis
      1. Chapter objectives
      2. Introduction
      3. Two limits of the ideal reactor
        1. Plug-flow reactors with recycle
        2. Tanks-in-series model
      4. Nonidealities defined with respect to the ideal reactors
        1. Nonidealities in tubular reactors
          1. Axial dispersion model
          2. Nonidealities in MFR
      5. Residence time distribution
        1. Theory
        2. Types of distribution
      6. Concept of mixing
        1. Regions of mixing
        2. Fully segregated flow
        3. Micromixing policy
        4. Models for partial mixing
          1. Axial dispersion model
          2. Tanks-in-series model
          3. Models for partial micromixing
          4. Degree of segregation defined by the age of the fluid at a point
      7. Turbulent mixing models
        1. Characteristic timescales
        2. Engulfment-deformation diffusion model
        3. Interaction by exchange with a mean
          1. Zone model
        4. Joint PDF
      8. Practical implications of mixing in chemical synthesis
        1. General considerations
        2. Dramatic illustration of the role of addition sequence of reagents
      9. Explore yourself
      10. References
      11. Bibliography
    11. Interlude II
      1. Limits of mean field theory
      2. The predator–prey problem or surface mixing
      3. Mixing problem addressed
        1. Short contact time reactors
        2. Microfluidic reactors
        3. Passive devices for mixing and pumping
          1. Knudsen pump
      4. Mixing
        1. Slug flow as a mixer
        2. Dean flow as a static mixer
        3. Elastic turbulence
      5. References
  10. Part II - Building on Fundamentals
    1. Introduction
    2. The different tools of the trade
      1. Relationship between thermodynamics and chemical reaction engineering
      2. Relationship between transport phenomena and chemical reaction engineering
      3. Relationship between chemical reaction engineering and kinetics
      4. Chemical reaction engineering as an experimental and theoretical science
    3. Chapter 4: Rates and equilibria: The thermodynamic and extrathermodynamic approaches
      1. Chapter objectives
      2. Introduction
      3. Basic thermodynamic relationships and properties
        1. Basic relationships
        2. Heats of reaction, formation, and combustion
        3. Implications of liquid phase reactions
        4. Free energy change and equilibrium constant
          1. Standard free energy change and equilibrium constant
          2. Equilibrium compositions in gas phase reactions
          3. Accounting for condensed phase(s)
        5. Complex equilibria
          1. Simultaneous solution of equilibrium equations
          2. Extension to a nonideal system
          3. Minimization of free energy
      4. Thermodynamics of reactions in solution
        1. Partial molar properties
        2. Medium and substituent effects on standard free energy change, equilibrium constant, and activity coefficient
          1. General considerations
          2. Solvent and solute operators
        3. Comments
      5. Extrathermodynamic approach
        1. Basic principles
        2. Group contributions or additivity principle
      6. Extrathermodynamic relationships between rate and equilibrium parameters
        1. Polanyi and Brønsted relations
        2. Hammett relationship for dissociation constants
        3. Extrathermodynamic approach to selectivity
          1. Theoretical analysis
      7. Thermodynamics of adsorption
        1. Henry’s law
        2. Langmuir isotherm
        3. Inhomogeneities expressed in terms of a site-energy distribution
        4. Two-dimensional equations of state and their corresponding adsorption isotherms
      8. Appendix
        1. Derivation of chemical equilibrium relationships for simple reactions
          1. Reactions in gas phase
          2. Reactions in liquid phase
      9. Explore yourself
      10. References
      11. Bibliography
    4. Interlude III
      1. Reactor design for thermodynamically limited reactions
        1. Kinetics
          1. Optimization of temperatures and pressures
      2. References
    5. Chapter 5: Theory of chemical kinetics in bulk and on the surface
      1. Chapter objectives
      2. Chemical kinetics
      3. Collision theory
      4. Transition state theory
      5. Proposing a kinetic model
      6. Brief excursion for the classification of surface reaction mechanisms
        1. Langmuir–Hinshelwood–Hougen–Watson models
          1. Langmuir isotherm
          2. Rate-determining step
          3. Basic procedure
        2. Eley–Rideal mechanism
        3. Mars–van Krevelen mechanism
        4. Michelis–Menten mechanism
        5. Influence of surface nonideality
          1. Paradox of heterogeneous kinetics
      7. Microkinetic analysis
        1. Postulate a mechanism
        2. Determine the kinetic parameters
        3. Simplify the mechanism
        4. Compare the model predictions with the kinetic data
      8. Explore yourself
      9. References
      10. Bibliography
    6. Chapter 6: Reactions with an interface
      1. Chapter objectives
      2. Introduction
        1. Diffusivity
          1. Diffusivities in gases
          2. Diffusivities in liquids
          3. Effective diffusivity
      3. Transport between phases
        1. General remarks
        2. Film theory
        3. Penetration theory
        4. Surface renewal theory
        5. Characteristic times for diffusion, reaction, and mass transfer
        6. Two-film theory of mass and heat transfer for fluid–fluid reactions in general
          1. Mass transfer
          2. Heat transfer
      4. Mass transfer across interfaces: Fundamentals
      5. Solid catalyzed fluid reactions
        1. Overall scheme
          1. Role of diffusion in pellets: Catalyst effectiveness
          2. First-order isothermal reaction in a spherical catalyst
        2. Weisz modulus: Practical useful quantity
        3. Nonisothermal effectiveness factors
          1. Multicomponent diffusion
          2. Miscellaneous effects
        4. Extension to complex reactions
      6. Noncatalytic gas–solid reactions
      7. Gas–liquid reactions in a slab
        1. Two-film theory
          1. Slow reactions
          2. Instantaneous reactions
        2. Effect of external mass and heat transfer
          1. External effectiveness factor
          2. Combined effects of internal and external diffusion
          3. Relative roles of mass and heat transfer in internal and external diffusion
            1. Gas phase reactants
            2. Liquid phase reactants
      8. Regimes of control
      9. Explore yourself
      10. References
    7. Chapter 7: Laboratory reactors
      1. Chapter objectives
      2. Chemical reaction tests in a laboratory
      3. A perspective on statistical experimental design
      4. Batch laboratory reactors
      5. Rate parameters from batch reactor data
        1. From concentration data
        2. From pressure data
      6. Flow reactors for testing gas–solid catalytic reactions
        1. Differential versus integral reactors
        2. Eliminating or accounting for transport disguises
          1. Eliminating the film mass transfer resistance
          2. Eliminating the pore diffusion resistances
          3. Eliminating axial dispersion effects
          4. Koros–Nowak criterion
          5. Catalyst dilution for temperature uniformity
        3. Gradientless reactors
      7. Transport disguises in perspective
        1. Guidelines for eliminating or accounting for transport disguises
      8. Analyzing the data
        1. Modeling of solid catalyzed reactions
          1. The overall scheme
          2. LHHW models
          3. Selection of the most plausible model
        2. Influence of surface nonideality
      9. Explore yourself
      10. References
  11. Part III - Beyond the Fundamentals
    1. Objectives
    2. Introduction
    3. The different tools of the trade
    4. Process intensification
      1. Microfluidics
      2. Membrane reactors
      3. Combo reactors
      4. Homogeneous catalysis
      5. Phase-transfer catalysis
    5. References
    6. Chapter 8: Fixed-bed reactor design for solid catalyzed fluid-phase reactions
      1. Chapter objectives
      2. Introduction
        1. Effect of catalyst packing in a tubular reactor
        2. Fixed-bed reactor
      3. Nonisothermal, nonadiabatic, and adiabatic reactors
        1. Design methodologies for NINA-PBR
          1. Quasi-continuum models
          2. Cell model
        2. Models based on the pseudo-homogeneous assumption
        3. Homogeneous, pseudo-homogeneous, and heterogeneous models
          1. 1D pseudo-homogeneous nonisothermal, nonadiabatic flow
          2. Reduction to isothermal operation
          3. Momentum balance
          4. The basic model: 2D pseudo-homogeneous nonisothermal, nonadiabatic with no axial diffusion
          5. Extension to nonideal models with and without heterogeneity
      4. Adiabatic reactor
        1. The approach
          1. A unique conversion–temperature relationship
          2. Single-bed reactor
          3. Multiple-bed reactor
        2. A simple graphical procedure
          1. Strategies for heat exchange
      5. Choice between NINA-PBR and A-PBR
        1. Some practical considerations
          1. Backmixing or axial dispersion
          2. Nonuniform catalyst distributions between tubes
        2. Scale-up considerations
      6. Alternative fixed-bed designs
        1. Radial-flow reactors
        2. Material, momentum, and energy balances
          1. Material balance
          2. Mass balance
          3. Momentum balance
          4. Some important observations
        3. Catalytic wire-gauze reactors
      7. Explore yourself
      8. References
      9. Bibliography
    7. Chapter 9: Fluidized-bed reactor design for solid catalyzed fluid-phase reactions
      1. Chapter objectives
      2. General comments
      3. Fluidization: Some basics
        1. Minimum fluidization velocity
      4. Two-phase theory of fluidization
      5. Geldart’s classification
        1. Classification of fluidized-bed reactors
        2. Velocity limits of a bubbling bed
          1. Fluid mechanical models of the bubbling bed
          2. Complete modeling of the fluidized-bed reactor
      6. Bubbling bed model of fluidized-bed reactors
        1. Bubbling bed
        2. Bubble rise velocity
        3. Main features
          1. Mass transfer between bubble and emulsion
      7. Solids distribution
        1. Estimation of bed properties
        2. Heat transfer
      8. Calculation of conversion
        1. End region models
          1. Dilute bed region
          2. Grid or jet region
        2. Practical considerations
        3. Recommended scale-up procedure
      9. Strategies to improve fluid-bed reactor performance
        1. Packed fluidized-bed reactors
          1. Reactor model for packed fluidized beds
        2. Staging of catalyst
      10. Extension to other regimes of fluidization types of reactors
        1. Turbulent bed reactor
        2. Fast fluidized-bed reactor
        3. Transport (or pneumatic) reactor
        4. Circulation systems
      11. Deactivation control
        1. Heat transfer controlled
        2. Reactor choice for a deactivating catalyst
          1. Basic equation
          2. Fixed-bed reactor
          3. Fluidized-bed reactor
          4. Moving bed reactor
      12. Some practical considerations
        1. Slugging
        2. Defluidization of bed: Sudden death
        3. Gulf streaming
        4. Effects of fines
        5. Start-up
      13. Fluidized-bed versus fixed-bed reactors
      14. Explore yourself
      15. References
    8. Chapter 10: Gas–solid noncatalytic reactions and reactors
      1. Chapter objectives
      2. Introduction
      3. Modeling of gas–solid reactions
        1. Shrinking core model
        2. Volume reaction model
        3. Zone models
        4. The particle–pellet or grain models
        5. Other models
      4. Extensions to the basic models
        1. Bulk-flow or volume-change effects
        2. Effect of temperature change
      5. Models that account for structural variations
        1. Effect of reaction
        2. Effect of sintering
      6. A general model that can be reduced to specific ones
      7. Gas–solid noncatalytic reactors
        1. Fixed-bed reactors
        2. Moving-bed reactors
        3. Fluidized-bed reactors
      8. References
    9. Chapter 11: Gas–liquid and liquid–liquid reactions and reactors
      1. Chapter objectives
      2. Introduction
      3. Diffusion accompanied by an irreversible reaction of general order
        1. Diffusion and reaction in series with no reaction in film: Regimes 1 and 2 (very slow and slow reactions), and regimes between 1 and 2
          1. Regimes 1 and 2: Very slow and slow reactions
          2. Regimes between 1 and 2
      4. Diffusion and reaction in film, followed by negligible or finite reaction in the bulk: Regime 3 (fast reaction), and regime covering 1, 2, and 3
        1. Reaction entirely in film
        2. Reactions both in film and bulk (regimes 1–2–3)
      5. Measurement of mass transfer coefficients
        1. Microfluidic devices
      6. Reactor design
      7. A generalized form of equation for all regimes
        1. Regime 1: Very slow reaction
        2. Regime 2 and regime between 1 and 2: Diffusion in film without and with reaction in the bulk
        3. Regime 3: Fast reaction
        4. Regime between 2 and 3
        5. Regime 4: Instantaneous reaction
      8. Classification of gas–liquid contactors
        1. Classification-1 (based on manner of phase contact)
        2. Classification-2 (based on the manner of energy delivery)
        3. Mass transfer coefficients and interfacial areas of some common contactors
        4. Role of backmixing in different contactors
      9. Reactor design for gas–liquid reactions
        1. The overall strategy
        2. Calculation of reactor volume
          1. Case 1: Plug gas, plug liquid, and countercurrent steady state
          2. Case 2: Same as case 1 but with cocurrent flow
          3. Case 3: Plug gas, mixed liquid, and steady state
          4. Case 4: Mixed gas, mixed liquid, and steady state
          5. Case 5: Mixed gas, batch liquid, and unsteady state
          6. Comments
        3. Reactor choice
          1. The criteria
          2. Volume minimization criterion
            1. General discussion
            2. Limitations of volume minimization
            3. Steps in volume minimization
          3. Energy minimization criteria
            1. Criterion 2(a): Homogeneous regime (regime 1)
            2. Criterion 2(b): Heterogeneous regime (regimes 2–4)
            3. Comparison of criteria
      10. Liquid–liquid contactors
        1. Classification of liquid–liquid reactors
        2. Values of mass transfer coefficients and interfacial areas for different contactors
        3. Calculation of reactor volume/reaction time
      11. Stirred tank reactor: Some practical considerations
      12. References
    10. Chapter 12: Multiphase reactions and reactors
      1. Chapter objectives
      2. Introduction
      3. Design of three-phase catalytic reactors
        1. The approach
        2. Semibatch reactors: Design equations for (1,0)- and (1,1)-order reactions
        3. Continuous reactors
      4. Types of three-phase reactors
        1. Mechanically agitated slurry reactors
          1. Mass transfer
          2. Minimum speed for complete suspension
          3. Gas holdup
          4. Controlling regimes in an MASR
        2. Bubble column slurry reactors
          1. Regimes of flow
          2. Mass transfer
          3. Minimum velocity for complete solids suspension
          4. Gas holdup
      5. Loop slurry reactors
        1. Types of loop reactors
          1. Mass transfer
      6. Trickle bed reactors (TBRs)
        1. Regimes of flow
        2. Mass transfer
        3. Controlling regimes in TBRs
      7. Collection and interpretation of laboratory data for three-phase catalytic reactions
        1. Experimental methods
        2. Effect of temperature
        3. Interpretation of data
      8. Three-phase noncatalytic reactions
        1. Solid slightly soluble
          1. Negligible dissolution of solid in the gas–liquid film
          2. Significant dissolution of solid in the gas–liquid film
          3. Solid insoluble
      9. References
      10. Bibliography
    11. Chapter 13: Membrane-assisted reactor engineering
      1. Introduction
      2. General considerations
        1. Major types of membrane reactors
      3. Modeling of membrane reactors
        1. Packed-bed inert selective membrane reactor with packed catalyst (IMR-P)
          1. Model equations
          2. Extension to consecutive reactions
        2. Fluidized-bed inert selective membrane reactor (IMR-F)
        3. Catalytic selective membrane reactor (CMR-E)
          1. Main features of the CMR-E
        4. Packed-bed catalytic selective membrane reactor (CMR-P)
        5. Catalytic nonselective membrane reactor (CNMR-E)
        6. Catalytic nonselective hollow membrane reactor for multiphase reactions (CNHMR-MR)
        7. Immobilized enzyme membrane reactor
      4. Operational features
        1. Combining exothermic and endothermic reactions
          1. Controlled addition of one of the reactants in a bimolecular reaction using an IMR-P
        2. Effect of tube and shell side flow conditions
      5. Comparison of reactors
        1. Effect (1)
        2. Effect (2)
        3. Combined effect
      6. Examples of the use of membrane reactors in organic technology/synthesis
        1. Small- and medium-volume chemicals
          1. Vitamin K
          2. Linalool (a fragrance)
        2. Membrane reactors for economic processes (including energy integration)
        3. References
    12. Chapter 14: Combo reactors: Distillation column reactors
      1. Distillation column reactor
      2. Enhancing role of distillation: Basic principle
        1. Batch reactor with continuous removal of product
          1. Case 1: Accumulation of S
          2. Case 2: S is not completely vaporized
        2. Packed DCR
      3. Overall effectiveness factor in a packed DCR
        1. Residue curve map (RCM)
          1. Design methodology
          2. Generating residual curve maps
      4. Distillation–reaction
        1. Dissociation–extractive distillation
          1. Basic principle
          2. Theory
      5. References
    13. Chapter 15: Homogeneous catalysis
      1. Introduction
        1. General
      2. Formalisms in transition metal catalysis
        1. Uniqueness of transition metals
        2. Oxidation state of a metal
        3. Coordinative unsaturation, coordination number, and coordination geometry
        4. Ligands and their role in transition metal catalysis
      3. Electron rules (“electron bookkeeping”)
        1. 18-electron rule
        2. 16–18-electron rule
      4. Operational scheme of homogeneous catalysis
      5. Basic reactions of homogeneous catalysis
        1. Reactions of ligands (mainly replacement)
        2. Elementary reactions (or activation steps)
          1. Coordination reactions
          2. Addition reactions
        3. Main reactions
          1. Insertion
          2. Elimination
      6. Main features of transition metal catalysis in organic synthesis: A summary
      7. A typical class of industrial reactions: Hydrogenation
        1. Hydrogenation by Wilkinson’s catalyst
        2. Wilkinson’s catalyst
          1. The catalytic cycle
          2. Kinetics and modeling
        3. A general hydrogenation model
      8. General kinetic analysis
        1. Intrinsic kinetics
          1. Multistep control
        2. Role of diffusion
        3. Complex kinetics—Main issue
        4. Reactions involving one gas and one liquid
          1. Regimes 1 and 2
          2. Regime between 1 and 2 (reaction in bulk)
          3. Regime 3 (reaction in film)
        5. Two gases and a liquid
      9. References
    14. Chapter 16: Phase-transfer catalysis
      1. Introduction
        1. What is PTC?
      2. Fundamentals of PTC
        1. Classification of PTC systems
        2. Phase-transfer catalysts
      3. Mechanism of PTC
        1. Liquid–liquid PTC
        2. Solid–liquid PTC
        3. Solid-supported PTC or triphase catalysis (TPC)
      4. Modeling of PTC reactions
        1. LLPTC models
        2. SLPTC models
          1. Interpretation of the role of diffusion: A cautionary note
        3. Supported PTC (TPC)
        4. Kinetic mechanism of TPC systems
        5. Methodology for modeling solid-supported PTC reactions
        6. Supported PTC with LHHW kinetics
      5. “Cascade engineered” PTC process
      6. References
    15. Chapter 17: Forefront of the chemical reaction engineering field
      1. Objective
      2. Introduction
      3. Resource economy
        1. Carbon and hydrogen
        2. Bio-renewables
      4. Energy economy
        1. Heat integration in microreactors
        2. Sonochemical reaction triggering
        3. Photochemical or photocatalytic systems
        4. Electrochemical techniques
        5. Microwaves
      5. Chemical reaction engineer in the twenty-first century
      6. In Closing
  12. Subject Index
  13. Author Index

Product information

  • Title: Chemical Reaction Engineering
  • Author(s): L.K. Doraiswamy, Deniz Uner
  • Release date: July 2013
  • Publisher(s): CRC Press
  • ISBN: 9781482217964