Chemical Reaction Engineering

772 Pages·2021·13.715 MB·English

by  Martin Schmal (editor), José Carlos Pinto (editor)

Chemical Reaction Engineering
Second Edition

Chemical Reaction Engineering
Parameter Estimation, Exercises and Examples
Second Edition
Martin Schmal & José Carlos Pinto
Department of Chemical Engineering,Federal University of
Rio de Janeiro – COPPE/UFRJ,Brazil
CRCPress/BalkemaisanimprintoftheTaylor&FrancisGroup,aninformabusiness
FirstEnglishedition©2014Taylor&FrancisGroup,London,UK
OriginallypublishedinPortugueseas“CinéticaeReatores:AplicaçãoàEngenhariaQuímica’’
bySynergiaEditora
©2010MartinSchmal
Translators:
FabioSouzaToniolo
CarlosAlbertoCastorJr.
JoãoPauloBassin
MartinSchmal
SecondEnglishedition©2022Taylor&FrancisGroup,London,UK
AuthorisedtranslationfromthePortugueselanguageeditionpublishedbySynergiaEditora
Allrightsreserved
OriginallypublishedinPortugueseas:“CinéticaeReatores–AplicaçãonaEngenharia
Química-teoriaeexercícios–3aed.’’
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Publishedby: CRCPress/Balkema
Schipholweg107C,2316XCLeiden,TheNetherlands
e-mail:[email protected]
www.routledge.com–www.taylorandfrancis.com
ISBN:978-0-367-49446-9(Pbk)
ISBN:978-1-032-07060-5(Hbk)
ISBN:978-1-003-04660-8(eBook)
DOI:10.1201/9781003046608
Table of contents
Preface xi
Nomenclature xiv
Abouttheauthors xviii
I Basicnotions 1
1 Definitionsandstoichiometry 3
1.1 Measurementvariables 4
1.2 Calculationofmeasurementvariables 6
1.2.1 Extentofthereaction 6
1.2.2 Conversion 7
1.3 Continuoussystems 10
1.4 Partialpressures 11
1.5 Methodoftotalpressure 12
1.6 Generalproperties 13
1.7 Solvedproblems 14
1.8 Accuracyandprecision 17
1.9 Measurementerrorsandprecision 20
2 Chemicalequilibrium 27
3 Kineticsofreactions 37
3.1 Reactionrates—definitions 37
3.2 Reactionrate 41
3.2.1 Kineticequations 45
3.3 Influenceofthetemperatureonthereactionrate 54
3.3.1 Reversiblereactions 56
3.3.2 Interpretationremarks 58
3.3.3 ReparameterizationoftheArrheniusequation 60
4 Molarbalanceinopenandclosedsystemswithchemicalreaction 63
4.1 Batch 65
4.2 Continuousstirringtankreactor 66
4.3 Continuoustubularreactor 67
vi Table of contents
II Kinetics 69
5 Determinationofkineticparameters 71
5.1 Irreversiblereactionatconstantvolume 73
5.1.1 Kineticmodeloffirstorder 73
5.1.2 Kineticmodelofsecondorder(global) 74
5.2 Irreversiblereactionsatvariablevolume 76
5.2.1 Irreversibleoffirstorder 76
5.2.2 Irreversiblereactionsofsecondorder 77
5.3 Irreversiblereactionsofordern–Half-lifemethod 79
5.4 Reversiblereactionsatconstantvolume 85
5.4.1 Directandreversefirst-orderelementaryreaction 85
5.4.2 Directandreversesecond-orderelementaryreaction 87
5.5 Determinationofthekineticparametersbythedifferentialmethod 93
5.5.1 Differentialreactor 100
5.6 Uncertaintiesofkineticparameters 102
5.7 Reparameterizationofpower-lawrateequations 105
6 Kineticsofmultiplereactions 109
6.1 Simplereactionsinseries 109
6.2 Simpleparallelreactions 113
6.3 Continuoussystems 117
6.4 Kineticsofcomplexreactions 120
6.4.1 Decompositionreactions 120
6.4.2 Parallelreactions 121
6.4.3 Series–parallelreactions 124
7 Non-elementaryreactions 127
7.1 Classicalkineticmodel 130
7.2 Chainreactions 132
7.3 Theoryofthetransitionstate 133
7.4 Reactionsofthermalcracking 138
8 Polymerizationreactions 143
8.1 Fundamentalaspectsofsteppolymerizations 145
8.1.1 ThemostprobableSchulz-Florydistribution 148
8.2 Fundamentalaspectsofchainpolymerizations 153
8.2.1 Initiation 154
8.2.2 Propagation 155
8.2.3 Termination 156
8.2.4 Chaintransfer 157
8.2.5 Quasi-steadystatebalances 158
8.3 Diffusivelimitations 160
8.4 Depolymerization 162
8.5 Concludingremarks 163
Table of contents vii
9 Kineticsofliquid-phasereactions 167
9.1 Enzymaticreactions 167
9.1.1 Kineticmodel 168
9.1.2 Determinationofthekineticparameters 171
9.1.3 Effectofexternalinhibitors 175
9.1.4 Kineticsofbiologicalfermentation 180
9.1.5 Massbalance 182
9.2 Liquid-phasereactions 184
9.2.1 Liquidsolutions 185
9.2.2 Acid—basereactions 190
9.3 ReparameterizationoftheMichaelis-Mentenequation 191
10 Heterogeneousreactionkinetics 199
10.1 Externalphenomena 200
10.2 Internaldiffusionphenomena 202
10.3 Adsorption–desorptionphenomena 205
10.3.1 Physicaladsorptionorphysisorption 207
10.3.2 Chemicaladsorptionorchemisorption 208
10.3.3 Comparingphysicalandchemicaladsorptions 208
10.4 Adsorptionisotherms 209
10.5 Adsorptionmodels 211
10.5.1 Langmuirmodel 211
10.5.2 Otherchemisorptionmodels 215
10.6 Modelofheterogeneousreactions 215
10.6.1 Langmuir–Hinshelwood–Hougen–Watson-model
(LHHW) 216
10.6.2 Eley–Ridealmodel 219
10.6.3 Effectofthetemperatureandenergies 219
10.7 Determinationoftheconstants 220
10.8 Noncatalyticheterogeneousreactions 224
10.9 ReparameterizationoftheLHHWequation 229
III Parameterestimationandexperimentaldesign 235
11 Determinationofkineticparametersthroughparameter
estimation 237
11.1 Definitionoftheparameterestimationproblem 238
11.2 Theobjectivefunction 240
11.3 Errorpropagationandparameterizationoftheestimation
problem 248
11.4 Numericalminimizationoftheobjectivefunction 250
11.5 Statisticalcharacterizationofmodeladequacy 253
11.6 Theconfidenceregionofparameterestimates 256
11.7 Uncertaintiesofmodelpredictions 261
11.8 Parameterizationofthearrheniusequation 263
11.9 Concludingremarks 265
viii Table of contents
12 Experimentaldesign 267
12.1 Factorialexperimentaldesign 268
12.2 Optimalexperimentaldesignforparameterestimation 280
12.3 Sequentialexperimentaldesigns 283
12.3.1 Sequentialexperimentaldesignformodel
discrimination 284
12.3.2 Sequentialexperimentaldesignforparameter
estimation 286
12.4 Concludingremarks 289
13 Kineticexercises 291
13.1 Solutionofkineticexercises 291
13.2 Proposedexercises 336
IV Reactors 345
14 Idealreactors 347
14.1 Typesofreactors 351
14.2 Definitionsandconceptsofresidencetime 351
14.3 Idealreactors 359
14.3.1 Batchreactor 361
14.3.2 Continuoustankreactor 369
14.3.3 Continuoustubularreactor(PFR) 377
14.4 Idealnonisothermalreactors 392
14.4.1 Adiabaticcontinuousreactor 400
14.4.2 Nonadiabaticbatchreactor 401
14.4.3 Adiabaticbatchreactor 401
14.4.4 Analysisofthethermaleffects 402
15 Specificreactors 417
15.1 Semibatchreactor 417
15.2 Reactorwithrecycle 422
15.3 Pseudo-homogeneousfixed-bedreactor 426
15.4 Membranereactors 431
16 Comparisonofreactors 437
16.1 Comparisonofvolumes 437
16.1.1 Irreversiblefirst-orderreactionatconstantvolume 439
16.1.2 Irreversiblesecond-orderreactionatconstant
volume 440
16.1.3 Reactionsatvariablevolume 441
16.2 Productivity 444
16.3 Yield/Selectivity 446
16.4 Overallyield 448
16.4.1 Effectofreactionorder 449
Table of contents ix
16.4.2 Effectsofkineticconstants 450
16.4.3 Presenceoftworeactants 453
16.5 Reactionsinseries 456
17 Combinationofreactors 461
17.1 Reactorsinseries 463
17.1.1 Calculating the number of reactors in series to an
irreversiblefirst-orderreaction 466
17.1.2 Calculating the number of reactors in series for an
irreversiblesecond-orderreaction 467
17.1.3 Graphicalsolution 468
17.2 Reactorsinparallel 469
17.3 Productionrateinreactorsinseries 470
17.4 YIELDandselectivityinreactorsinseries 470
18 Transportphenomenainheterogeneoussystems 491
18.1 Intraparticlediffusionlimitation—pores 491
18.2 Effectivenessfactor 495
18.3 Effectsofintraparticlediffusionontheexperimentalparameters 499
18.4 Externalmasstransferandintraparticlediffusionlimitations 503
V Deactivation 509
19 Catalystdeactivation 511
19.1 Kineticsofdeactivation 513
19.2 Deactivationinpfrorcstrreactor 517
19.3 Forceddeactivation 520
19.4 Catalystregeneration 524
19.4.1 Differentialscanningcalorimetry 525
19.4.2 Temperatureprogrammedoxidation 526
19.4.3 Catalyticevaluation 526
19.5 Kineticstudyofregeneration 527
19.5.1 Balancewithrespecttosolid(carbon) 529
19.5.2 Particularcase 530
20 Exercisesreactorsandheterogeneousreactors 533
20.1 Solutionstoexercises:Reactors 533
20.2 Exercisesproposed:Reactors 615
21 Multiphasereactingsystems 623
22 Heterogeneousreactors 637
22.1 Fixedbedreactor 641
22.1.1 Reactorsinseries 646
22.2 Fluidizedbedreactor 649