Separation of Molecules, Macromolecules and Particles: Principles, Phenomena and Processes

924 Pages·2013·14.613 MB·English

by  Sirkar K.

Separation of Molecules, Macromolecules and Particles
Providingchemicalengineeringundergraduateandgraduatestudentswithabasicunderstandingofhowtheseparation
ofamixtureofmolecules,macromoleculesorparticlesisachieved,thistextbookisacomprehensiveintroductiontothe
engineeringscienceofseparation.
• Studentslearnhowtoapplytheirknowledgetodeterminetheseparationachievedinagivendeviceorprocess.
• Real-world examples are taken from biotechnology, chemical, food, petrochemical, pharmaceutical and pollution
controlindustries.
• Workedexamples,elementaryseparatordesignsandchapter-endproblemsgivestudentsapracticalunderstandingof
separation.
Thetextbooksystematicallydevelopsdifferentseparationprocessesbyconsideringtheforcescausingtheseparation,and
howthisseparationisinfluencedbythepatternsofbulkflowintheseparationdevice.Readerswillbeabletotakethis
knowledgeandapplyittotheirownfuturestudiesandresearchinseparationandpurification.
KamaleshK.SirkarisaDistinguishedProfessorofChemicalEngineeringandtheFoundationProfessorofMembrane
SeparationsatNewJerseyInstituteofTechnology(NJIT).Hisresearchareasaremembranesandnovelmembranebased
processes.
“Thefirstcomprehensivebookthattakesthefundamentals “This book provides a unique and in depth coverage of
ofseparationonamolecularlevelasthestartingpoint!The separation processes. It is an essential reference for the
benefit of this approach is that it gives you a thorough practicing engineer. Unlike more conventional textbooks
insight in the mechanisms of separation, regardless of thatfocusonrateandequilibriumbasedseparations,Prof
whichseparationisconsidered.Thismakesitremarkably Sirkarfocusesonhowagivenseparationtakesplaceand
easy to understand any separation process, and not only howthisisusedinpracticalseparationdevices.Thusthe
the classical ones. This textbook finally brings the walls bookisnotlimitedbyapplicatione.g.chemicalorpetro-
down that divide separation processes in classical and chemicalseparations.
non-classical.” “Aschemicalengineeringbecomesincreasinglymulti-
BartVanderBruggen,UniversityofLeuven,Belgium disciplinary,wherethebasicprinciplesofseparationsare
applied to new frontier areas, the book will become an
“Thisstrongtextorganizesseparationprocessesasbatchvs essentialguideforpractitionersaswellasstudents.
continuous and as staged vs differential. It sensibly “The unique layout of the text book allows the
includes coupled separation and chemical reaction. Sup- instructor to tailor the content covered to a particular
portedbystrongexamplesandproblems,thisnon-conven- course.Undergraduatecourseswillbenefitfromthecom-
tional organization reinforces the more conventional prehensiveandsystematiccoverageofthebasicsofsepar-
pictureofunitoperations.” ationprocesses.Whetherthefocusofagraduatecourseis
EdCussler,UniversityofMinnesota traditionalchemicalseparations,bioseparations,orsepar-
ationprocessesforproductionofrenewableresourcesthe
“Thisbookfillstheneedbyprovidingaverycomprehen- bookisanessentialtext.”
sive approach to separation phenomena for both trad- RanilWickramasinghe,UniversityofArkansas
itionalandemergingfields.Itiseffectivelyorganizedand
presentsseparations inaunique manner. This bookpre- “Thisadvancedtextbookprovidesstudentsandprofession-
sentstheprinciplesofawidespectrumofseparationsfrom als with a unique and thought-provoking approach to
classicaldistillationtomodernfield-inducedmethodsina learning separation principles and processes. Prof. Sirkar
unifying way. This is an excellent book for academic use hasleveragedhisyearsofexperienceasaseparationsci-
andasaprofessionalresource.” entistandmembraneseparationspecialist,toprovidethe
C.StewartSlater,RowanUniversity reader with a clearly written textbook full of multiple
examples pulled from all applications of separations,
“Thisbookisanexcellentresourceforthetopicofchem- including contemporary bioseparations. Compared to
icalseparations.Thetextstartsbyusingexamplestoclarify otherseparationstextbooks,Prof.Sirkar’stextbookishol-
concepts.Thenthroughoutthetext,examplesfrommany istically different in its approach to teaching separations,
differenttechnologyareasandseparationapproachesare yet provides the reader with a rich learning experience.
given. The book is framed around various fundamental Chemicalengineeringstudentsandpracticingprofession-
approaches to chemical separations. This allows one to alswillfindmuchtolearnbyreadingthistextbook.”
usethisknowledgeforbothcurrentandfutureneeds.” DanielLepek,TheCooperUnion
RichardD.Noble,UniversityofColorado
Separation of Molecules,
Macromolecules and Particles
Principles, Phenomena and Processes
Kamalesh K. Sirkar
NewJerseyInstituteofTechnology
UniversityPrintingHouse,CambridgeCB28BS,UnitedKingdom
PublishedintheUnitedStatesofAmericabyCambridgeUniversityPress,NewYork
CambridgeUniversityPressispartoftheUniversityofCambridge.
ItfurtherstheUniversity’smissionbydisseminatingknowledgeinthepursuitof
education,learningandresearchatthehighestinternationallevelsofexcellence.
www.cambridge.org
Informationonthistitle:www.cambridge.org/9780521895736
©K.Sirkar2014
Thispublicationisincopyright.Subjecttostatutoryexception
andtotheprovisionsofrelevantcollectivelicensingagreements,
noreproductionofanypartmaytakeplacewithoutthewritten
permissionofCambridgeUniversityPress.
Firstpublished2014
PrintedintheUnitedKingdombyTJInternationalLtd.PadstowCornwall
AcatalogrecordforthispublicationisavailablefromtheBritishLibrary
LibraryofCongressCataloging-in-PublicationData
Sirkar,KamaleshK.,1942-author.
Separationofmolecules,macromoleculesandparticles:principles,phenomenaand
processes/KamaleshSirkar,NewJerseyInstituteofTechnology.
pages cm.– (Cambridgeseriesinchemicalengineering)
isbn978-0-521-89573-6(Hardback)
1. Separation(Technology)–Textbooks. 2. Molecules–Textbooks. I. Title.
TP156.S45S572013
5410.22–dc23 2012037018
ISBN978-0-521-89573-6Hardback
Additionalresourcesforthispublicationatwww.cambridge.org/sirkar
CambridgeUniversityPresshasnoresponsibilityforthepersistenceoraccuracyof
URLsforexternalorthird-partyinternetwebsitesreferredtointhispublication,
anddoesnotguaranteethatanycontentonsuchwebsitesis,orwillremain,
accurateorappropriate.
Contents
Preface pagexi
Listofnotation xiii
Introductiontothebook 1
Introductiontochapters 2
Linkedfootprintsofaseparationprocess/technique 3
Classificationofseparationprocesses 6
Additionalcommentsonusingthebook 7
Textbooks,handbooksandmajorreferencesonseparationprocesses 7
1 Descriptionofseparationinaclosedsystem 19
1.1 Binaryseparationbetweentworegionsinaclosedvessel 19
1.2 Multicomponentseparationbetweentworegionsinaclosedvessel 22
1.3 Definitionsofcompositionforabinarysysteminaclosedvessel 24
1.4 Indicesofseparationforbinarysystems 25
1.5 Comparisonofindicesofseparationforaclosedsystem 29
1.6 Indicesforseparationofmulticomponentsystemsbetweentworegions 33
1.7 Somespecializednomenclature 35
Problems 35
2 Descriptionofseparationinopenseparators 39
2.1 Preliminaryquantitativeconsiderations 39
2.2 Binaryseparationinasingle-entryseparatorwithorwithoutrecycle 42
2.2.1 Examplesofseparationinsingle-entryseparators 45
2.2.2 Single-entryseparatorwithaproductrecycle 48
2.2.3 Separativepowerandvaluefunction 49
2.3 Binaryseparationinadouble-entryseparator 50
2.3.1 Examplesofseparationindouble-entryseparators 51
2.3.2 Separationinadouble-entryseparatorwithrecycle/reflux 53
2.4 Multicomponentsystems 53
2.4.1 Size-distributedparticlepopulation 54
2.4.2 Continuouschemicalmixtures 62
2.4.3 Multicomponentchemicalmixtures 64
2.5 Separationinanoutputstreamwithtime-varyingconcentration 66
Problems 70
3 Physicochemicalbasisforseparation 76
3.1 Displacements,drivingforces,velocitiesandfluxes 76
3.1.1 Natureofdisplacements 76
3.1.2 Forcesonparticlesandmolecules 77
3.1.3 Particlevelocity,molecularmigrationvelocityandchemicalspeciesflux 88
3.1.4 Integratedfluxexpressionsformoleculardiffusionandconvection:single-phasesystems 102
vi Contents
3.1.5 Fluxexpressionsinmulticomponentsystems 112
3.1.6 Additionaltopics 117
3.2 Separationdevelopmentandmulticomponentseparationcapability 118
3.2.1 Separationdevelopmentinaclosedsystem 119
3.2.2 Multicomponentseparationcapability 124
3.2.3 Particulatesystems 127
3.3 Criteriaforequilibriumseparationinaclosedseparator 128
3.3.1 Phaseequilibriumwithequalpressureinallphases 129
3.3.2 Phaseequilibriumwheredifferentphaseshavedifferentpressures 130
3.3.3 Single-phaseequilibriuminanexternalforcefield 132
3.3.4 Equilibriumbetweenphaseswithelectricalcharges 132
3.3.5 Equilibriumbetweenbulkandinterfacialphases 133
3.3.6 Curvedinterfaces 136
3.3.7 Solutedistributionbetweenphasesatequilibrium:someexamples 137
3.3.8 Particledistributionbetweentwoimmisciblephases 159
3.4 Interphasetransport:fluxexpressions 159
3.4.1 Interphasetransportintwo-phasesystems 160
3.4.2 Interphasetransport:membranes 170
3.4.3 Interphasetransportintwo-phasesystemswithphasebarriermembranes 189
Problems 192
Appendix:Diffusioncoefficientsindifferentsystems 202
4 Separationinaclosedvessel 205
4.1 Equilibriumseparationbetweentwophasesortworegionsinaclosedvessel 205
4.1.1 Gas–liquidsystems 206
4.1.2 Vapor–liquidsystems 208
4.1.3 Liquid–liquidsystems 217
4.1.4 Liquid–solidsystems 222
4.1.5 Interfacialadsorptionsystems 223
4.1.6 Liquid–ionexchangersystems 228
4.1.7 Supercriticalfluid–bulksolid/liquidphase 231
4.1.8 Bulkfluidphase–mesophasesystems 231
4.1.9 Partitioningbetweenabulkfluidphaseandanindividualmolecule/macromolecule
oracollectionofmoleculesfornoncovalentsolutebinding 234
4.1.10 Gas–solidparticle–liquidsysteminmineralflotation 245
4.2 Equilibriumseparationinasinglephaseinanexternalforcefield 245
4.2.1 Centrifugalforcefield 246
4.2.2 Electricalforcefield 253
4.2.3 Gravitationalforcefield 256
4.2.4 Particleseparationwithacousticforces 260
4.2.5 Externallyimposedtemperaturegradient:thermaldiffusion 261
4.3 Equilibriumseparationbetweentworegionsinaclosedvesselseparatedbyamembrane 262
4.3.1 Separationbydialysisusingneutralmembranes 262
4.3.2 Separationbetweentwocounterionsintwosolutionsseparatedbyanionexchange
membrane:Donnandialysis 264
4.3.3 Separationofagasmixturebygaspermeation 266
4.3.4 Separationofapressurizedliquidsolutionthroughamembrane 272
Problems 273
5 Effectofchemicalreactionsonseparation 280
5.1 Extentofseparationinaclosedvesselwithachemicalreaction 280
5.2 Changeinseparationequilibriaduetochemicalreactions 281
5.2.1 Gas–liquidandvapor–liquidequilibria 281
5.2.2 Liquid–liquidequilibrium 289
Contents vii
5.2.3 Stationary–mobilephaseequilibria 299
5.2.4 Crystallizationandprecipitationequilibrium 303
5.2.5 Surfaceadsorptionequilibrium 306
5.2.6 ComplexationinDonnandialysis 308
5.2.7 Enzymaticseparationofisomers 308
5.3 Rate-controlledequilibriumseparationprocesses:roleofchemicalreactions 309
5.3.1 Absorptionofagasinareactiveliquid 309
5.3.2 Solventextractionofaspecieswithchemicalreaction 315
5.4 Rate-governedmembraneprocesses:roleofchemicalreactions 318
5.4.1 Reverseosmosis:soluteionization 318
5.4.2 Ultrafiltration:complexation 319
5.4.3 Dialysis:reactionindialysate 323
5.4.4 Chemicalreactionsinliquidmembranepermeation–separation 324
5.4.5 Separationthroughsolidnonporousmembrane 337
Problems 338
6 Openseparators:bulkflowparalleltoforceandcontinuousstirredtankseparators 346
6.1 Sourcesandnatureofbulkflow 348
6.1.1 Hydrostaticpressureinducedbulkflow 348
6.1.2 Gravityinducedbulkflow 350
6.1.3 Freeconvection 350
6.1.4 Bulkmotionduetocapillarity 352
6.1.5 Electroosmoticflow 353
6.1.6 Centrifugalforcedrivenflow 354
6.1.7 Surfacetensiongradientbasedflow 354
6.1.8 Dragflow 355
6.1.9 Feedintroductionmodevs.bulkflow 356
6.2 Equationsofchange 358
6.2.1 Equationsofchangeforspeciesconcentrationinamixture 358
6.2.2 Equationofmotionofaparticleinafluid:trajectoryequation 368
6.2.3 Generalequationofchangeforaparticlepopulation 368
6.3 Bulkflowparalleltoforcedirection 372
6.3.1 Externalforces 373
6.3.2 Chemicalpotentialgradientdrivenphase-equilibriumsystems 390
6.3.3 Filtrationandmembraneseparationprocesses 412
6.4 Continuousstirredtankseparators 445
6.4.1 Well-mixedseparators–CSTSsandbatchseparators 445
6.4.2 Well-mixedseparators–membranebaseddevices 469
Problems 475
7 Separationinbulkflowoffeed-containingphaseperpendiculartothedirectionoftheforce 485
7.1 Chemicalpotentialgradientbasedforceinphaseequilibrium:fixed-bedprocesses 487
7.1.1 Fixed-bedadsorption/desorptionprocesses 487
7.1.2 Pressure-swingadsorptionprocessforgasseparation 511
7.1.3 Potential-swingadsorption 519
7.1.4 Parametricpumping 520
7.1.5 Chromatographicprocesses 527
7.1.6 Expandedbedadsorption(EBA)fromabroth/lysateaidedbygravitationalforce 550
7.1.7 Counteractingchromatographicelectrophoresisandelectrochromatography 551
7.2 Crossflowmembraneseparations,crossflowfiltrationandgranularfiltration 555
7.2.1 Crossflowmembraneseparations,crossflowfiltration 555
7.2.2 Granularfiltrationofhydrosols(andaerosols) 586
7.3 Externalforcefieldbasedseparation:bulkflowperpendiculartoforce 596
7.3.1 Electricalforcefield 596
viii Contents
7.3.2 Centrifugalforcefield 618
7.3.3 Gravitationalforcefield 634
7.3.4 Field-flowfractionationforcolloids,macromoleculesandparticles 640
7.3.5 Magneticforcefield 648
7.3.6 Radiationpressure–opticalforce 654
Problems 655
8 Bulkflowoftwophases/regionsperpendiculartothedirection(s)oftheforce(s) 670
8.1 Countercurrentbulkflowoftwophasesorregionsperpendiculartothedirection(s)oftheforce(s)
drivingspecies 670
8.1.1 Developmentofseparationincountercurrentflowsystems 670
8.1.2 Gas(vapor)absorption/stripping 683
8.1.3 Distillation 709
8.1.4 Countercurrentsolventextraction 736
8.1.5 Countercurrentmeltcrystallizationinacolumn 751
8.1.6 Countercurrentadsorptionandsimulatedmovingbedsystem 754
8.1.7 Membraneprocessesofdialysisandelectrodialysis 761
8.1.8 Countercurrentliquidmembraneseparation 767
8.1.9 Countercurrentgaspermeation 771
8.1.10 Countercurrentgascentrifuge 775
8.1.11 Thermaldiffusionandmassdiffusion 781
8.2 Cocurrentbulkmotionoftwophasesorregionsperpendiculartothedirection(s)oftheforce(s)
drivingspecies/particles 782
8.2.1 Cocurrenttwo-phaseflowdevices–generalconsiderations 783
8.2.2 Chromatographicseparationsincocurrenttwo-phaseflowdevices 785
8.2.3 Particleseparationincocurrentgas–liquidflow–Venturiscrubber 788
8.2.4 Cocurrentmembraneseparators 789
8.3 Crossflowoftwobulkphasesmovingperpendiculartothedirection(s)ofthedrivingforce(s) 794
8.3.1 Continuouschromatographicseparation 794
8.3.2 Crossflowplateinadistillationcolumn 799
Problems 804
9 Cascades 812
9.1 Typesofcascades 812
9.1.1 Countercurrentcascades,idealcascade 812
9.1.2 Othercascadeconfigurations 818
9.2 Cascadesformulticomponentmixtureseparationviadistillation 822
9.3 Cascadesformulticomponentmixtureseparationinvolvingotherseparationprocesses 824
Problems 824
10 Energyrequiredforseparation 827
10.1 Minimumenergyrequiredforseparation 827
10.1.1 Evaporationofwaterfromseawater 828
10.1.2 Recoveryofwaterbyreverseosmosis 828
10.1.3 Networkconsumption 830
10.1.4 Minimumenergyrequiredformembranegaspermeation,distillation,extraction,
andotherseparationprocesses 831
10.2 Reducingenergyrequiredforseparation 836
10.2.1 Evaporationofwaterfordesalination 836
10.2.2 Distillation 839
10.2.3 Freeenergyofmixing 843
10.2.4 Dilutesolutions 844
Problems 845