The Chemical Reactor from Laboratory to Industrial Plant: A Modern Approach to Chemical Reaction Engineering with Different Case Histories and Exercises

574 Pages·2018·22.53 MB·English

by  Elio Santacesaria

Elio Santacesaria · Riccardo Tesser
The Chemical
Reactor from
Laboratory to
Industrial Plant
A Modern Approach to Chemical
Reaction Engineering with Different
Case Histories and Exercises
The Chemical Reactor from Laboratory to Industrial
Plant
Elio Santacesaria Riccardo Tesser
(cid:129)
The Chemical Reactor
from Laboratory to Industrial
Plant
A Modern Approach to Chemical Reaction
Engineering with Different Case Histories
and Exercises
123
Elio Santacesaria Riccardo Tesser
Eurochem Engineerings.r.l. Dipartimento di ScienzeChimiche,
Milan,Italy Complesso diMonte Sant’Angelo
University of Naples FedericoII
Naples, Italy
ISBN978-3-319-97438-5 ISBN978-3-319-97439-2 (eBook)
https://doi.org/10.1007/978-3-319-97439-2
LibraryofCongressControlNumber:2018949875
©SpringerNatureSwitzerlandAG2018
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Preface
The contents of this book derive, first of all, from lessons lectured by both of the
authors to students of the course, “Principles of Industrial Chemistry and Related
Exercises,”takenfortheMaster’sDegreeofIndustrialChemistryattheUniversity
Federico II of Naples, Italy. The content is also the result of many years of
experimentalandtheoreticalresearchworkconductedbytheauthorsinthefieldof
chemical-reaction engineering. During their 30 years of research and teaching,
science and technology have made an enormous progress, in particular after the
advent of very powerful personal computers. In the old textbooks, many problems
of industrialchemistry had approximated analytical or graphicalsolutions toavoid
long and tedious hand-made calculations. The first computers—which were slow,
expensive, and bulky—allowed for more rigorous calculations but were accessible
only to specialists using a rigid software language, such as FORTRAN. The large
diffusion of personal computers that are fast, cheap and small—combined with a
flexible and powerful software, such as MATLAB—allow everybody to solve
many complicated problems with a numerical approach that is simpler, faster, and
more satisfactory as to precision. Therefore, in this book, together with the theo-
retical approach to different topics, which is necessary to know for understanding
the chemical reactor behaviour (e.g., thermodynamics of physical and chemical
transformation,catalysis,kinetics,andmasstransfer),manyexercisesareproposed
inside the chapters devoted to the mentioned topics. The solutions to the exercises
are described in detail inside the text, but the reader can find (at the Springer
website)theMATLABcodesrelatedtoanysingleexerciseandcaninteractdirectly
with the proposed mathematical models and related solutions. The solutions are
based on a numerical approach. A brief description of the main algorithm used,
along with simple examples, is also reported on the Springer website with the
MATLAB codes for the exercises.
The book is organized into seven chapters. Chapter 1 is a brief introduction
describingwhatisimportanttoknowfordevelopingindustrialprocesses.Chapter2
isdevotedtothethermodynamicsofchemicalandphysical equilibrium.Chapter3
deals with the role of catalysis in promoting chemical reactions. Chapters 4 and 5
are related to the kinetics in, respectively, the homogeneous and heterogeneous
v
vi Preface
phase and the relation between kinetics and the reaction mechanism. The last two
chaptersdescribetheeffectofmassandheattransferin,respectively,gas‒solidand
multi-phase reactors. In our opinion, this book could be useful for master’s and
doctoralstudentsofchemical-engineeringscienceandindustrialchemistrybutalso
for researchers working in the field of catalysis, kinetics, reactor design, and
simulation.
Milan, Italy Elio Santacesaria
Naples, Italy Riccardo Tesser
Contents
1 Introduction to the Study of Chemical Industrial Processes . . . . . . . 1
1.1 Structure and Characteristics of Chemical Industrial Plants . . . . . . 1
1.2 Thermodynamics,Catalysis,Kinetics,andTransportPhenomena:
Their Role in Modeling and Conducting Chemical Industrial
Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 Material and Energy Balances. . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.4 Introduction to the Numerical Solution of the Most Frequently
Employed Algorithms with Examples Developed in Matlab . . . . . 8
Reference. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2 Thermodynamics of Physical and Chemical Transformations. . . . . . 9
2.1 Introduction to Physical and Chemical Equilibrium . . . . . . . . . . . 9
2.2 Thermodynamic Properties and Equilibrium Conditions of
Physical Tranformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.1 The First Thermodynamic Law. . . . . . . . . . . . . . . . . . . . 10
2.2.2 Transformations at Constant Pressure . . . . . . . . . . . . . . . 12
2.2.3 Transformations at Constant Volume. . . . . . . . . . . . . . . . 13
2.2.4 Transformations at Constant Temperature . . . . . . . . . . . . 14
2.2.5 Adiabatic Transformations . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.6 The Second Thermodynamic Law. . . . . . . . . . . . . . . . . . 16
2.2.7 CriteriaforDefiningtheThermodynamicEquilibriumof
Physical Transformations . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 Thermodynamic Equilibrium in Chemical-Reacting Systems . . . . . 19
2.3.1 Introduction to the Thermodynamics of Chemical
Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.3.2 Equilibrium of Reactions Between Ideal Gases . . . . . . . . 22
2.3.3 Generalities About Chemical Equilibrium for Reactions
Between Real Gases. . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.3.4 The Van der Waals EOS and the Corresponding State
Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
vii
viii Contents
2.3.5 Alternative Equations of State. . . . . . . . . . . . . . . . . . . . . 43
2.3.6 Fugacity Evaluation from an EOS. . . . . . . . . . . . . . . . . . 47
2.3.7 Evaluation of Critical Parameters with Semi-Empirical
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.3.8 Chemical Equilibrium in Liquid Phase . . . . . . . . . . . . . . 58
2.3.9 Equilibrium Constants and the Reference Systems . . . . . . 59
2.3.10 Heterogeneous Equilibrium. . . . . . . . . . . . . . . . . . . . . . . 60
2.3.11 Dependence of the Chemical Equilibrium Constant on
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.3.12 Estimation of Thermodynamic Properties Starting from
Molecule Structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2.3.13 Heat of Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.3.14 Heat-Capacity Calculation . . . . . . . . . . . . . . . . . . . . . . . 64
2.3.15 Gibbs Free Energy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.3.16 Simultaneous Chemical Equilibria. . . . . . . . . . . . . . . . . . 67
2.3.17 AnExampleCalculationofEquilibriumCompositionin
a Complex System Characterized by the Presence
of Multiple Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.3.18 Influence of Operative Conditions on the Yields
of a Process: A Qualitative Approach . . . . . . . . . . . . . . . 71
2.3.19 Thermodynamics of Some Hydrocarbons
Transformations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.3.20 ProceduresforCalculatingtheComponentsActivitiesof
a Liquid-Phase Mixture and Related Coefficients . . . . . . . 74
2.4 Calculations Related to Physical Equilibria . . . . . . . . . . . . . . . . . 81
2.4.1 Physical Equilibria. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.4.2 VLE of a Single Pure Component. . . . . . . . . . . . . . . . . . 82
2.4.3 Vapour–Liquid Equilibrium (VLE) for a Multi-
component System at Moderate Equilibrium
Pressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.4.4 The Equilibrium of Solubility at Moderate Pressures . . . . 91
2.4.5 Vapour–LiquidEquilibriaandGasSolubilityinLiquids
at Elevated Pressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2.4.6 The Flash Unit. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
2.4.7 Vapour–Liquid Equilibrium and Distillation . . . . . . . . . . 101
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
3 The Role of Catalysis in Promoting Chemical Reactions . . . . . . . . . 117
3.1 Introduction to Catalytic Phenomena . . . . . . . . . . . . . . . . . . . . . . 117
3.2 Catalyst Classification and Generalities . . . . . . . . . . . . . . . . . . . . 120
3.3 Homogeneous Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
3.3.1 Acid–Base Homogeneous Catalysis. . . . . . . . . . . . . . . . . 122
3.3.2 Catalysis Promoted by Metal-Transition Complexes. . . . . 123
Contents ix
3.3.3 Enzymatic Catalysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3.3.4 Heterogenization of Homogeneous Catalysts . . . . . . . . . . 130
3.4 Heterogeneous Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
3.4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
3.4.2 Physical Adsorption, Specific Surface-Area
Measurement, and Porosity. . . . . . . . . . . . . . . . . . . . . . . 134
3.4.3 Chemical Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
3.4.4 Factors Determining Catalyst Deactivation:
Poisoning, Aging, and Sintering . . . . . . . . . . . . . . . . . . . 153
3.4.5 A Brief Survey on Catalyst- and Support-Preparation
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.4.6 Acid–Base Heterogeneous Catalysts . . . . . . . . . . . . . . . . 156
3.4.7 Surface Acidity of Binary Mixed Oxides. . . . . . . . . . . . . 159
3.4.8 Zeolites, Structures, Properties, and Synthesis . . . . . . . . . 160
3.4.9 Templating Mesoporous Zeolites. . . . . . . . . . . . . . . . . . . 164
3.4.10 Catalytic Properties of Metal Oxides
as Semiconductor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
3.5 Preparation and Characterization of the Most Common Catalytic
Supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
3.5.1 Alumina . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
3.5.2 Silica. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
3.5.3 Silica–Alumina . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
3.5.4 Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
3.5.5 Monolithic Supports. . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3.5.6 Metal Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3.6 Catalyst Forming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
3.6.1 Forming Micro Granules . . . . . . . . . . . . . . . . . . . . . . . . 183
3.6.2 Forming Grains . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
4 Kinetics of Homogeneous Reactions and Related Mechanisms . . . . . 191
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
4.2 Relation Between the Kinetic Law and the Reaction
Mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
4.3 Elementary Background of Kinetics. . . . . . . . . . . . . . . . . . . . . . . 196
4.3.1 Reaction-Rate Definition: Relation with Mass Balance
Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
4.3.2 Reaction Order and Formal Kinetics . . . . . . . . . . . . . . . . 198
4.3.3 Laboratory Reactors for Studying Single Fluid-Phase
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
4.3.4 Hints on the Factorial Programming of Kinetic Runs . . . . 207
4.3.5 Exercises on the Evaluation of Reaction Order
and the Simulation of Kinetic Runs. . . . . . . . . . . . . . . . . 209
x Contents
4.3.6 Complex Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
4.3.7 Complex Reaction Scheme: A Unified Approach. . . . . . . 251
4.4 DescriptionoftheReactionMechanismsandTheirRelationwith
Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
4.4.1 Heterolytic Mechanisms and Kinetics . . . . . . . . . . . . . . . 254
4.4.2 Nucleophilic Substitutions of Type S 1. . . . . . . . . . . . . . 255
N
4.4.3 Nucleophilic Substitutions of Type S 2. . . . . . . . . . . . . . 255
N
4.4.4 Substitution with Electrophilic Attack . . . . . . . . . . . . . . . 256
4.4.5 Nucleophilic Additions. . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.4.6 Electrophilic Additions. . . . . . . . . . . . . . . . . . . . . . . . . . 257
4.4.7 Nucleophilic Eliminations—E (Monomolecular) . . . . . . . 257
1
4.4.8 Nucleophilic Eliminations—E (Bimolecular) . . . . . . . . . 257
2
4.4.9 Electrophilic Eliminations. . . . . . . . . . . . . . . . . . . . . . . . 258
4.4.10 Molecular Rearrangement. . . . . . . . . . . . . . . . . . . . . . . . 258
4.4.11 Description of Catalytic Cycles. . . . . . . . . . . . . . . . . . . . 259
4.4.12 TheWackerProcess:AnExampleofHeterolyticRedox
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
4.4.13 Kinetics of Reaction Catalysed by Acid–Base . . . . . . . . . 261
4.4.14 Radical-Chain Reactions: Homolytic Mechanisms
and Related Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.4.15 Kinetics of Enzymatic Reactions. . . . . . . . . . . . . . . . . . . 274
4.5 Comparison of the Performances of CSTRs and PFRs . . . . . . . . . 281
4.6 Gas-Phase Reactions and Kinetic Theory. . . . . . . . . . . . . . . . . . . 284
4.7 Flash with Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
5 Kinetics of Heterogeneous Reactions and Related Mechanisms. . . . . 291
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
5.2 Definition and Evaluation of Reaction Rate, Mass Balance,
and Kinetic Equations in Heterogeneous Fluid–Solid Systems. . . . 293
5.3 Reaction Scheme, Stoichiometry, Thermodynamic Constraints,
and Analysis of Reaction Networks. . . . . . . . . . . . . . . . . . . . . . . 294
5.4 Kinetic Equations Based on the Mechanisms of Chemical
Adsorption and Chemical Surface Reaction: The Langmuir–
Hinshelwood Kinetic Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
5.4.1 Dual-Site Mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . 300
5.4.2 Eley–Rideal Mechanism. . . . . . . . . . . . . . . . . . . . . . . . . 301
5.4.3 Redox Mechanism According to Mars and
van Krevelen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
5.4.4 Adsorption on Non-uniform Surfaces . . . . . . . . . . . . . . . 302
5.4.5 The Kinetics for Heterogeneous Complex Reaction
Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
5.4.6 The Collection and Processing of Kinetic Data with the
Scope of Determining the Kinetic Equation. . . . . . . . . . . 308