Chemical Reactor Design and Operation, 2nd EditionISBN: 978-0-471-91730-4
Paperback
800 pages
January 1991
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Preface to the First Edition
Preface to the Second Edition
Preface to the Student Edition
List of Symbols
Chapter I Fundamentals of chemical reactor calculations
1.1 Introduction
1.2 The material, energy and economic balance
Material balance
Energy balance
Economic balance
1.3 Thermodynamic data: heat of reaction and chemical equilibrium
Heat of reaction
Chemical equilibrium
1.4 Conversion rate, chemical reaction rate and chemical reaction rate equations
Influence of temperature on kinetics
Influence of concentration on kinetics
1.5 The degree of conversion
Relation between conversion and concentration expressions
1.6 Selectivity and yield
Selectivity and yield in a reactor section with recycle of non-converted reactant
1.7 Classification of chemical reactors
References
Chapter II Model reactors: single reactions, isothermal single phase reactor calculations
II.1 The well-mixed batch reactor
II.2 The continuously operated ideal tubular reactor
II.3 The continuously operated ideal tank reactor
11.4 The cascade of tank reactors
II.5 The semi-continuous tank reactor
II.6 The recycle reactor
II.7 A comparison between the different model reactors
Batch versus continuous operation
Tubular reactor versus tank reactor
II.8 Some examples of the influence of reactor design and operation on the economics of the process
The use of one of the reactants in excess
Recirculation of unconverted reactant
Maximum production rate and optimum load with intermittent operation
References
Chapter III Model reactors: multiple reactions, isothermal single phase reactors
III.1 Fundamental concepts
Differential selectivity and selectivity ratio
The reaction path
III.2 Parallel reactions
Parallel reactions with equal order rate equations
Parallel reactions with differing reaction order rate equations
A cascade of tank reactors
III.3 The continuous cross flow reactor system
III.4 Consecutive reactions
First order consecutive reactions in a plug flow reactor
First order consecutive reactions in a tank reactor
General discussion
III.5 Combination reactions
Graphical methods
Optimum yield in a cascade of tank reactors
Algebraic methods
III.6 Autocatalytic reactions
Single biochemical reactions
Multiple autocatalytic reactions
References
Chapter IV Residence time distribution and mixing in continuous flow reactors
IV.1 The residence time distribution (RTD)
The E and the F diagram
The application of the RTD in practice
IV.2 Experimental determination of the residence time distribution
Input functions
IV.3 Residence time distribution in a continuous plug flow and in a continuous ideally stirred tank reactor.
IV.4 Models for intermediate mixing
Model of a cascade of N equal ideally mixed tanks
The axially dispersed plug flow model
IV.5 Conversion in reactors with intermediate mixing
IV.6 Some data on the longitudinal dispersion in continuous flow systems
Flow through empty tubes
Packed beds
Fluidized beds
Mixing in gas-liquid reactors
References
Chapter V Influence of micromixing on chemical reactions
V.1 Nature of the micromixing phenomena
Macro or gross overall mixing as characterized by the residence time distribution
The state of aggregation of the reacting fluid
The earliness of the mixing
V.2 Boundaries to micromixing phenomena
The model tubular and tank reactors
Boundaries for micromixing for reactors with arbitrary RTDs
V.3 Intermediate degree of micromixing in continuous stirred tank reactors
Formal models
Agglomeration models
Model for micromixing via exchange of mass between agglomerates and their average environment, the IEM model
V.4 Experimental results on micromixing in stirred vessels
V.5 Concluding remarks on micromixing
References
Chapter VI The role of the heat effect in model reactors
VI.1 The energy balance and heat of reaction
VI.2 The well-mixed batch reactor
Batch versus semi-batch operation
VI.3 The tubular reactor with external heat exchange
Maximum temperature with exothermic reactions; para-metric sensitivity
VI.4 The continuous tank reactor with heat exchange
VI.5 Autothermal reactor operation
The tank reactor
An adiabatic tubular reactor with heat exchange between reactants and products
A multi-tube reactor with internal heat exchange between the reaction mixture and the feed
Determination of safe operating conditions
VI.6 Maximum permissible reaction temperatures
VI.7 The dynamic behaviour of model reactors
The autothermal tank reactor
Tubular reactor
References
Chapter VII Multiphase reactors, single reactions
VII.1 The role of mass transfer
VII.2 A qualitative discussion on mass transfer with homogeneous reaction
Concentration distribution in the reaction phase
VII.3 General material balance for mass transfer with reaction
VII.4 Mass transfer without reaction
Stagnant film model
Penetration models of Higbie and Danckwerts
VII.5 Mass transfer with homogeneous irreversible first order reaction
Penetration models
Stagnant film model
General conclusion on mass transfer with homogeneous irreversible first order reaction
Applications
VII.6 Mass transfer with homogeneous irreversible reaction of complex kinetics
VII.7 Mass transfer with homogeneous irreversible reaction of order (1.1) with Al » 1
Slow reaction
Fast reaction
Instantaneous reaction
General approximated solution
VII.8 Mass transfer with irreversible homogeneous reaction of arbitrary kinetics with Al »1
VII.9 Mass transfer with irreversible reaction of order (1, 1) for a small Hinterland coefficient
VII.10 Mass transfer with reversible homogeneous reactions
VII.11 Reaction in a fluid-fluid system with simultaneous mass transfer to the non-reaction phase (desorption)
VII.12 The influence of mass transfer on heterogeneous reactions
Heterogeneous reaction at an external surface
Reactions in porous solids
VII.13 General criterion for absence of mass transport limitation
VII.14 Heat effects in mass transfer with reaction
Mass transfer with reaction in series
Mass transfer with simultaneous reaction in a gas-liquid system
Mass transfer with simultaneous reaction in a porous pellet
VII.15 Model reactors for studying mass transfer with chemical reaction in heterogeneous systems
Model reactors for gas-liquid reactions
Model reactors for liquid-liquid reactions
Model reactors for fluid-solid reactions.
VII.16 Measurement techniques for mass transfer coefficients and specific contact areas in multi-phase reactors
Measurement of the specific contact area a
Measurement of the product kLa
Measurement of the product kGa
Measurement of mass transfer coefficients kL, kG
VII.17 Numerical values of mass transfer coefficients and specific contact areas in multi-phase reactors
Fluid-solid reactors
Fluid-fluid (-solid) reactors
References
Chapter VIII Multi-phase reactors, multiple reactions
VIII.1 Introduction
VIII.2 Simultaneous mass transfer of two reactants A and A with independent parallel reactions A → P and A → X (Type I Selectivity)
Mass transfer and reaction in series
Mass transfer and reaction in parallel
VIII.3 Mass transfer of one reactant (A) followed by two dependent parallel reactions
A(+B) → P A(+B,B) → X
(Type II Selectivity)
Mass transfer and reaction in series
Mass transfer and reaction in parallel
VIII.4 Simultaneous mass transfer of two reactants (A and A) followed by dependent parallel reactions with a third reactant: A + B → P, A + B → X
Complete mass transfer limitation in non-reaction phase
One reactant mass transfer limited in non-reaction phase
One reaction instantaneous
Both reactions instantaneous
No diffusion limitation of reactant originally present in reaction phase
More complex systems
VIII.5 Simultaneous mass transfer of two reactants (A and A) which react with each other
VIII.6 Mass transfer with consecutive reactions A → P → X (Type III Selectivity)
Mass transfer and reaction in series
Mass transfer and reaction in parallel
VIII.7 Mass transfer with mixed consecutive parallel reactions
The system: A(1) → A(2); A(2) + B(2) → P(2); P(2) + B(2) →X(2)
The system: A(1) → A(2); A(2) + B(2) → P(2); A(2) + P(2) →X(2)
Complex systems
References
Chapter IX Heat effects in multi-phase reactors
IX.1 Gas-liquid reactors
General
Column reactors
Bubble column reactors
Agitated gas-liquid reactors
IX.2 Gas-solid reactors
Single particle behaviour
Catalytic gas-solid reactors
The moving bed gas-solid reactor
Thermal stability and dynamic behaviour of gas solid reactors
IX.3 Gas-liquid-solid reactors
References
Chapter X The optimization of chemical reactors
X.1 The object and means of optimization
The objective function
The optimization variables
Relation between technical and economic optima
X.2 Optimization by means of temperature
The optimization of exothermic equilibrium reactions
Temperature optimization with complex reaction systems
X.3 Some mathematical methods of optimization
Geometric programming
The Lagrange multiplier technique
Numerical search routines
Dynamic programming
Pontryagins maximum principle
References
Author index
Subject Index
Preface to the Second Edition
Preface to the Student Edition
List of Symbols
Chapter I Fundamentals of chemical reactor calculations
1.1 Introduction
1.2 The material, energy and economic balance
Material balance
Energy balance
Economic balance
1.3 Thermodynamic data: heat of reaction and chemical equilibrium
Heat of reaction
Chemical equilibrium
1.4 Conversion rate, chemical reaction rate and chemical reaction rate equations
Influence of temperature on kinetics
Influence of concentration on kinetics
1.5 The degree of conversion
Relation between conversion and concentration expressions
1.6 Selectivity and yield
Selectivity and yield in a reactor section with recycle of non-converted reactant
1.7 Classification of chemical reactors
References
Chapter II Model reactors: single reactions, isothermal single phase reactor calculations
II.1 The well-mixed batch reactor
II.2 The continuously operated ideal tubular reactor
II.3 The continuously operated ideal tank reactor
11.4 The cascade of tank reactors
II.5 The semi-continuous tank reactor
II.6 The recycle reactor
II.7 A comparison between the different model reactors
Batch versus continuous operation
Tubular reactor versus tank reactor
II.8 Some examples of the influence of reactor design and operation on the economics of the process
The use of one of the reactants in excess
Recirculation of unconverted reactant
Maximum production rate and optimum load with intermittent operation
References
Chapter III Model reactors: multiple reactions, isothermal single phase reactors
III.1 Fundamental concepts
Differential selectivity and selectivity ratio
The reaction path
III.2 Parallel reactions
Parallel reactions with equal order rate equations
Parallel reactions with differing reaction order rate equations
A cascade of tank reactors
III.3 The continuous cross flow reactor system
III.4 Consecutive reactions
First order consecutive reactions in a plug flow reactor
First order consecutive reactions in a tank reactor
General discussion
III.5 Combination reactions
Graphical methods
Optimum yield in a cascade of tank reactors
Algebraic methods
III.6 Autocatalytic reactions
Single biochemical reactions
Multiple autocatalytic reactions
References
Chapter IV Residence time distribution and mixing in continuous flow reactors
IV.1 The residence time distribution (RTD)
The E and the F diagram
The application of the RTD in practice
IV.2 Experimental determination of the residence time distribution
Input functions
IV.3 Residence time distribution in a continuous plug flow and in a continuous ideally stirred tank reactor.
IV.4 Models for intermediate mixing
Model of a cascade of N equal ideally mixed tanks
The axially dispersed plug flow model
IV.5 Conversion in reactors with intermediate mixing
IV.6 Some data on the longitudinal dispersion in continuous flow systems
Flow through empty tubes
Packed beds
Fluidized beds
Mixing in gas-liquid reactors
References
Chapter V Influence of micromixing on chemical reactions
V.1 Nature of the micromixing phenomena
Macro or gross overall mixing as characterized by the residence time distribution
The state of aggregation of the reacting fluid
The earliness of the mixing
V.2 Boundaries to micromixing phenomena
The model tubular and tank reactors
Boundaries for micromixing for reactors with arbitrary RTDs
V.3 Intermediate degree of micromixing in continuous stirred tank reactors
Formal models
Agglomeration models
Model for micromixing via exchange of mass between agglomerates and their average environment, the IEM model
V.4 Experimental results on micromixing in stirred vessels
V.5 Concluding remarks on micromixing
References
Chapter VI The role of the heat effect in model reactors
VI.1 The energy balance and heat of reaction
VI.2 The well-mixed batch reactor
Batch versus semi-batch operation
VI.3 The tubular reactor with external heat exchange
Maximum temperature with exothermic reactions; para-metric sensitivity
VI.4 The continuous tank reactor with heat exchange
VI.5 Autothermal reactor operation
The tank reactor
An adiabatic tubular reactor with heat exchange between reactants and products
A multi-tube reactor with internal heat exchange between the reaction mixture and the feed
Determination of safe operating conditions
VI.6 Maximum permissible reaction temperatures
VI.7 The dynamic behaviour of model reactors
The autothermal tank reactor
Tubular reactor
References
Chapter VII Multiphase reactors, single reactions
VII.1 The role of mass transfer
VII.2 A qualitative discussion on mass transfer with homogeneous reaction
Concentration distribution in the reaction phase
VII.3 General material balance for mass transfer with reaction
VII.4 Mass transfer without reaction
Stagnant film model
Penetration models of Higbie and Danckwerts
VII.5 Mass transfer with homogeneous irreversible first order reaction
Penetration models
Stagnant film model
General conclusion on mass transfer with homogeneous irreversible first order reaction
Applications
VII.6 Mass transfer with homogeneous irreversible reaction of complex kinetics
VII.7 Mass transfer with homogeneous irreversible reaction of order (1.1) with Al » 1
Slow reaction
Fast reaction
Instantaneous reaction
General approximated solution
VII.8 Mass transfer with irreversible homogeneous reaction of arbitrary kinetics with Al »1
VII.9 Mass transfer with irreversible reaction of order (1, 1) for a small Hinterland coefficient
VII.10 Mass transfer with reversible homogeneous reactions
VII.11 Reaction in a fluid-fluid system with simultaneous mass transfer to the non-reaction phase (desorption)
VII.12 The influence of mass transfer on heterogeneous reactions
Heterogeneous reaction at an external surface
Reactions in porous solids
VII.13 General criterion for absence of mass transport limitation
VII.14 Heat effects in mass transfer with reaction
Mass transfer with reaction in series
Mass transfer with simultaneous reaction in a gas-liquid system
Mass transfer with simultaneous reaction in a porous pellet
VII.15 Model reactors for studying mass transfer with chemical reaction in heterogeneous systems
Model reactors for gas-liquid reactions
Model reactors for liquid-liquid reactions
Model reactors for fluid-solid reactions.
VII.16 Measurement techniques for mass transfer coefficients and specific contact areas in multi-phase reactors
Measurement of the specific contact area a
Measurement of the product kLa
Measurement of the product kGa
Measurement of mass transfer coefficients kL, kG
VII.17 Numerical values of mass transfer coefficients and specific contact areas in multi-phase reactors
Fluid-solid reactors
Fluid-fluid (-solid) reactors
References
Chapter VIII Multi-phase reactors, multiple reactions
VIII.1 Introduction
VIII.2 Simultaneous mass transfer of two reactants A and A with independent parallel reactions A → P and A → X (Type I Selectivity)
Mass transfer and reaction in series
Mass transfer and reaction in parallel
VIII.3 Mass transfer of one reactant (A) followed by two dependent parallel reactions
A(+B) → P A(+B,B) → X
(Type II Selectivity)
Mass transfer and reaction in series
Mass transfer and reaction in parallel
VIII.4 Simultaneous mass transfer of two reactants (A and A) followed by dependent parallel reactions with a third reactant: A + B → P, A + B → X
Complete mass transfer limitation in non-reaction phase
One reactant mass transfer limited in non-reaction phase
One reaction instantaneous
Both reactions instantaneous
No diffusion limitation of reactant originally present in reaction phase
More complex systems
VIII.5 Simultaneous mass transfer of two reactants (A and A) which react with each other
VIII.6 Mass transfer with consecutive reactions A → P → X (Type III Selectivity)
Mass transfer and reaction in series
Mass transfer and reaction in parallel
VIII.7 Mass transfer with mixed consecutive parallel reactions
The system: A(1) → A(2); A(2) + B(2) → P(2); P(2) + B(2) →X(2)
The system: A(1) → A(2); A(2) + B(2) → P(2); A(2) + P(2) →X(2)
Complex systems
References
Chapter IX Heat effects in multi-phase reactors
IX.1 Gas-liquid reactors
General
Column reactors
Bubble column reactors
Agitated gas-liquid reactors
IX.2 Gas-solid reactors
Single particle behaviour
Catalytic gas-solid reactors
The moving bed gas-solid reactor
Thermal stability and dynamic behaviour of gas solid reactors
IX.3 Gas-liquid-solid reactors
References
Chapter X The optimization of chemical reactors
X.1 The object and means of optimization
The objective function
The optimization variables
Relation between technical and economic optima
X.2 Optimization by means of temperature
The optimization of exothermic equilibrium reactions
Temperature optimization with complex reaction systems
X.3 Some mathematical methods of optimization
Geometric programming
The Lagrange multiplier technique
Numerical search routines
Dynamic programming
Pontryagins maximum principle
References
Author index
Subject Index