Solid/Liquid Separations

Understanding
Crystallization and
Crystallizers
Ketan D. Samant

Lionel OYoung

ClearWaterBay Technology,
Inc.

This article offers qualitative insight

into the basic mechanisms of
crystallization and the principles of
crystallizer operation,

and the ways in which these

concepts relate to the various
crystallizer configurations in industrial
use today.

rystallizationisanimportantseparationprocessintheproductionofcommodityandspecialtychemicals.

Severaldifferenttypesandconfigurationsofcontinu

ouscrystallizershavebeendevelopedfortheseapplications.Thedesignandoperationofanindustrial
crystallizerare

optimizedbasedupontheconditionsneededfor:

producinglargerandmoreuniformcrystalsofthedesiredproduct

reducingtheformationofagglomerates

reducingtheamountofliquidimpuritiesincludedineachcrystal

reducingtheamountofliquidimpuritiesincludedincrystalagglomerates

reducingtheliquidretainedbythecrystalcakeaftersolidliquidseparationandwashing.

Letsfirstconsiderhowvariouscrystallizationmechanismsaffecttheseobjectives.

Thermodynamics.Figure1illustratesthegeneralthermodynamicphasebehaviorofasolutesolvent
systemandtheconceptsofthermodynamicequilibriumandthermodynamicstabilityforsolidliquid
systems.

Thesolidlineisthesolubilitycurve,whichrepresentsthermodynamicequilibriumbetweentheliquidandsolid
phases.Anyliquidwithacompositionandtemperatureabovethesolubilitycurveexistsasstableunsaturated
liquid.

Anyliquidwithacompositionandtemperaturebelowthesolubilitycurveisnotinthermodynamicequilibrium
withrespecttoformationofasolidphasei.e.,itissupersaturated.However,itisnotalways
thermodynamicallyunstable.

Theregionbetweenthesolubilitycurveandthelimitofstability(thedashedline)iscalledthemetastable
zone.Inthisregion,nucleationsitesarenecessarytoinitiatetheformationofasolidphasefroma
supersaturatedliquid.Theoretically,ifonecouldsuppressallnucleationsites,theliquidcouldexistasa
stablesupersaturatedliquideventhoughitwouldnotbeinequilibrium.

Beyondthemetastablezoneboundary,however,thepresenceofnucleationsitesisnotarequirementforthe
formation

Stable

Zone

Temperature
Metastable

Zone

Unstable

Solubility
Zone

Curve

Stability

Limit

Solute Composition

Figure 1. Solid-liquid phase behavior is characterized by thermodynamic equilibrium and thermodynamic stability.

28 www.aiche.org/cep

October 2006

CEP

ofasolidphase.Thisistheunstableregion,in
whichanysupersaturatedliquidisneitherstable
norinequilibriumandthereforeissubjectto
spontaneousnucleationandtheformationofa
solidphase.

Clearly,anindustrialcrystallizermustoperate
belowthesolubilitycurveinordertoproducea
solidphase.However,sincetheobjectiveisto
avoidthecreationofalargenumberofsmall
particles,thecrystallizermustnotbeoperatedin
theunstablezone;ratheritsoperationmustbe
restrictedtothemetastablezone.

Nucleationandgrowth.Materialtransferfromthe
liquidphasetothesolidphaseoccursviatwo
mechanismsthatgohandinhandnucleationand
growth.Growthreferstodepositionofsolidmaterial
onexistingcrystals,whilenucleationrefersto
formationofnewcrystals(whichsubsequentlygrow).
Thenumberofcrystalsandtheirsizesinanyindustri
aloperationwilldependprimarilyonthesetwo
mechanisms.

Inthemetastablezone,nucleationandgrowthcantake
placethroughseveralmechanisms,andtheirrates,in
general,canbeconsidereddirectlyrelatedtothedegree
ofsupersaturation(1,2).Theparticlesizedistributionin
anindustrialcrystallizerdependsontherelativeratesof
nucleationandgrowthandonhowtheyrelatetotherate
ofproductremoval(whichdependsonresidencetime).
Ingeneral:

promotinggrowthovernucleationleadstosmall
numbersofmoreuniformcrystals

promotingbothmaterialtransfermechanismsover
productremovalleadstolargercrystals

lowersupersaturationspromotegrowthover
nucleation

higherresidencetimespromotebothnucleation
andgrowthoverproductremoval.

Agglomeration.Particlesizesinindustrial
crystallizersmayalsobeaffectedbyagglomeration
andbreakage.Agglomeratesformwhengrowing
crystals(ofthesamesizeorofdifferentsizes)collide
witheachotherinaperfectlyinelasticwayi.e.,the
particlessticktogethertoformanewparticle.
Agglomerationwillbemoreextensiveifthereare
moreparticles,whichincreasestheprobabilityof
collision,orifthecollidingparticlestendtostick
together.

Ingeneral,agglomerationisassociatedwithhigher
supersaturation,andevenoperationintheunstablezone
conditionsthatresultintheformationoflarge
numbersofsmallparticles.Tominimizeagglomeration,
supersaturationshouldbelimited.

Liquidinclusioninindividualcrystals.Thereare
severalmechanismsbywhichliquidgetstrappedinside
growingcrystals.Althoughtherearenouniversally
acceptedtheories,highergrowthratesareconsideredto
increasetheamountofliquidincludedinindividual
crystals.Highersupersaturationresultsinhighergrowth
rates,andthusisaconditionthattypicallyincreasesthe
amountofliquidimpuritiesinindividualcrystals.

Liquidinclusionincrystalagglomerates.Liquid
gets

liquidtrappedwithinthecrystals.Downstreamofthe
crystallizer,thecrystalsarefirstseparatedfromthe
motherliquorduringthesolidliquidseparationstep,
andthentheliquidretainedbythecrystalcakeis
removedduringthewashingstep.

Theresidualliquidcontentinthecrystalcakeafter
thissolidliquidseparationis,ingeneral,inversely
proportionaltothesquarerootofthemeancrystal
particlesize(assumingallotherthingsarethesame).
Thesmallertheparticlesinthecrystalcake,themore
liquidthecakewillretainafterthesamesolidliquid
separationoperation.Asaresult,theamountofwash
liquidrequiredtoachievethesamewashing
efficiencywillalsobehigherforcakescontaining
smallparticlesthanforcakeswithlargerparticles.

Largercrystals,therefore,aredesired.Lower
supersaturationsandhigherresidencetimesinthe
crystallizerarebeneficialforthesolidliquid
separationaswell.

Crystallizer operating mechanisms

Foranycontinuouscrystallizationapplication,
industrialcrystallizersshouldbedesignedtooperate
inthemetastablezone,atlowersupersaturations,and
withhigherresidencetimes,inordertomeetthe
statedobjectives.Thissectiondescribesthe
mechanismsofcrystallizeroperation.

Everycontinuousindustrialcrystallizermusthave:

amechanismtogeneratesupersaturation
trappedbetweencollidingparticlesduring
agglomeration.Here,too,therearenouniversally
acceptedtheories,butitissafetoassumethatthe
amountoftrappedliquidincreaseswithincreased
agglomeration.Thus,highersupersaturationresultsin
largervolumesofliquidtrappedincrystalagglomerates.

Liquidimpuritiesoutsidethecrystals.Typically,in
industrialoperations,theamountofliquidretained
outsidethecrystalsismuchlargerthantheamountof

amechanismtorelievethesupersaturation

amechanismtocontrolsupersaturationgeneration.

Inaddition,tomanageproductcrystalsize,itis
usefulforthecrystallizertohave:

astroubleshootingandimprovingtheoperationof
existingsystems.

amechanismforfinesdissolution

amechanismforremovingclassifiedproduct.
Differentcrystallizerconfigurationsemploydifferent

choicesforthesemechanisms.Knowledgeofthese
choicesandtheoperatingprinciplesbehindthem
willguidetheselectionanddesignofthemost
suitableconfigurationfornewinstallations,aswell

CEP

October 2006 www.aiche.org/cep

29

Generating supersaturation

Themechanismsforgeneratingsupersaturation
relyonthechangesinsolubilityofthecrystallizing
componentasafunctionoftemperatureand
composition.Suchchangesaremeasuredthrough
solubilityexperimentsandquanti

Solid/Liquid Separations
Cooler

Metastable

M
ML

SP

Active

FF*

Zone

FF

FF
Volume

T*
M*

Temperature

supersaturation
generation.

ML
P,M
SP

fiedusing
solubilitycurves
andphase
diagrams(3,6).In
mostcases,
supersaturationis
generatedbya
decrease

Unstable

intemperature
and/ordecreasein
solvent
composition.
Therearethree
mechanismsfor
creating
supersaturation:
Zone

Solute Composition

Figure 2.
Control of

Cooling(typically
bysurfacecooling,
orinsomecases
bydirectcontact
witharefrigerant)
generates
supersaturation
throughadecrease
intemperature.
Thismechanismis
bestsuitedfor
systemsinwhich
thesolubilityofthe
crystallizing
component
decreasessteeply
ormoderatelywith
decreasing
temperature.Itis
notsuitedfor
systemswithflat
orinverted
solubility
temperature
relationships.

Evaporation
generates
supersaturation
throughadecrease
insolvent
composition,which
isachievedwhen
heatisaddedto
evaporatethe
solvent.Itisthe
onlymechanism
thatcanbeused
wherethesolubility
ofthecrystallizing
componenteither
increaseswith
decreasing
temperatureor
remainsessentially
unchanged.For
suchsystems,
supersaturationcan
begeneratedfar
moreeffectivelyby
decreasingthe
solvent
composition.For
systemswithsteep
ormoderate
solubility,theother
twomechanisms
arebetteroptions
thanevaporation.

Adiabatic
evaporative
coolinggenerates
supersaturation
throughadiabatic
solvent
evaporation.
Ratherthanadding
heattothesystem,
itreliesonbotha
decreaseinsol
ventcomposition
andadecreasein
temperature
broughtaboutby
theadiabatic
evaporation.As
withsurfaceor
directcontact
cooling,this
mechanismisbest

usedwhenthe
solubilityofthe
crystallizing
component
decreasesmod
eratelyorsteeply
withdecreasing
temperature.
Adiabatic
evaporative
coolingmaynotbe
appropriatewhen
thebubblepoint
temperature
decreasesvery
slowlywith
pressure;insuch
cases,evenhigh
vacuumscannot
bringaboutasuf
ficientreductionin
temperature.

Thesolubility
characteristicsof
thecrystallizing
component
dictatewhat
mechanismsare
neededfor
creatingsuper
saturation.
Criteriasuchas
cost,operability
andcompatibility
withcrystallizer
configurations
shouldbeusedto
furtherrefinethe
selection.

Relieving the
supersaturatio
n

Inallcrystallizers,
themechanismfor
relievingthesuper
saturationissimply
theexistenceofan
active
crystallization
volume.This
volumecontainsa
suspensionof
growingcrystals.
Theinputtothis
active
crystallization
volumeisthe
supersaturated
liquidorslurry,
andtheoutputis
theproductslurry.
Theinputand
outputratesand
theactivevolume
determinethe
residencetime
provided.

Thesuspensionin
theactive
crystallization
volumemay
exhibitvarying
degreesof
mixedness.Atone
extreme,itmaybe
completelymixed
intermsof
compositions,
solidscontents,
andparticlesizes.
Attheother
extreme,itmaybe
fullyclassified,
withclearliquidat
thetopand
progressively
largersolids
concentrationsand

particlesizes
below.Thechoice
ofthedegreeof
mixednessis
usuallyadirect
consequenceofthe
mechanismused
forcontrolof
supersaturation
generation.

Control of
supersaturatio
n generation

Figure2shows
schematicallythe
operationofa
simplecooling
crystallizer.
Supersaturationis
generatedby
coolingthefresh
feedstream
(streamFF),
resultingina
streamthatis
(arbitrarily)
designatedstream
M.StreamMis
senttothe
crystallizertank,
whichprovidesthe
activevolumefor
relievingthe
supersaturation.
Insidethe
crystallizertank
andintheproduct
stream(streamP),
theliquidphase
compositionis
representedbyML
andthesolids
compositionbySP.

Bothnucleation
andgrowthare

drivenbythe
amountof
supersaturation
(thecomposition
differencebetween
MLandthe
solubilitycurveat
thecrystallizer
temperature)inthe
activevolume.If
sufficientresidence
timeisprovided,
theliquidphase
MLwillbewithin
themetastable
zone,andthe
supersaturation
willbelow.
However,the
crystallizertank
doesnotgenerate
supersaturation
itsimplyprovides
themechanism,
i.e.,theactive
crystallization
zone,torelieveit.

Supersaturationis
generatedby
coolingthefresh
feedstream(from
FFtoM).Butas
showninFigure
2,streamMlies
intheunstable
zone.Asaresult,
nucleationoccurs
spontaneously,
generatingalarge
numberofsmall
particlesinside
thecoolereven
beforestreamM

30 www.aiche.org/cep

reachesthe
crystallizertank.
Thisis
undesirable,andit
impliesthatthe
supersaturation
generationneeds
tobecontrolledso
thatstreamMis
alsointhe
metastablezone.

Figure2also
illustratestwo
waysinwhich
suchcontrolcan
beexercised:

thetemperature
canbereduced
onlytoT*,at
whichpointthe
cooledstreamM*
liesonthelimitof
stabilitycurve

theamountof
solventcanbe
increasedsuch
thattheoperating
temperatureisthe
limitofstability
forthenewfresh
feedstreamFF*.

Inmost
applications,the
widthofthe
metastablezone,

October 2006

CEP

M
ML

Metastable

SP
Active

FF

Volume

Zone

Cooler

Zone

FF
Temperature
ML
M
P
SP
Solute Composition

Figure 3. In liquor
recirculation, liquid is
removed from the
active volume without
entraining any
crystals and is
recirculated.

Unstable

whichisvery
narrow,isnot
known.Asaresult,
therestrictionson
temperatureand
amountofsolvent
requiredinthese
methodsarequite
severe.Both
methodsarehighly

undesirable
becausethey
adverselyaffect
productrecovery
higher
temperatureand
highersolvent
contentmean
lowerrecovery.

Theonlyother
optionis
recirculation.This
involves
removingastream
fromtheactive
crystallization
volume,mixingit
withthefresh
feed,andthen
sendingthe
combinedstream
throughthe
supersaturation
generatorand
backtotheactive
crystallization
volume.Two
typesof
recirculation
mechanismsmay
beused:

liquorrecirculation,
whichinvolves
recirculatingonly
theliquid(or
motherliquor)from
theactive
crystallization
volume

magma
recirculation,
whereintheslurry
fromtheactive
crystallization
volumeis
recirculated.

Figure3showsthe
operationofa
coolingcrystallizer
withliquor
recirculation.Itis
assumedthata
liquidstream(which
hasacomposition
correspondingto
ML)canbe
removedfromthe
activevolume.This
streamismixed
withfreshfeed
streamFFtoform
streamLpriortothe
generationof
supersaturationby
cooling.The
locationofstreamL
onthetemperature
vs.compositionplot
issuchthatthe
cooledstreamM
liesinsidethe
metastablezone.
Thereareno
changestooperating
temperature,feed
compositionor
residencetime.
Thus,inthisconfig
uration,
recirculationhelps
avoidhigh
supersaturationsat
thepointof
supersaturation
generationwithout
affectingtherecov
eryofcrystallized
product.

Forliquor
recirculation,itis
assumedthatonly
themotherliquor
isrecirculated
whilethecrystals
remaininthe
activevolume.As
aresult,streamsL
andMare
supersaturated,
butstable,liquids.

Volume

Ifthesuspensionin
theactivevolume
ismixed,itisnot
possibleto
recirculateonlythe
liquor.The
recirculationflow,
knownasmagma,
willinclude
crystalsaswell.
Operationwith
magma
recirculatonis
depictedinFigure
4.PointsLandM
representtheliquid
compositionsof
therecirculating

Cooler

SP
M,M'
ML
Metastable

L,L'

Active
Zone

FF

FF
Temperature
ML

L
L'

Solute Composition

P,M'
SP

Unstable

Zone

Figure 4. In magma
recirculation, a mixed
stream containing
liquid and crystals is
removed from the
active volume and is
recirculated.

streams,and
pointsLandM
representthetotal
compositions
(includingthe
solids).Notethat
here,too,the
liquidportionof
therecirculating
stream(pointsL
andM)liesinside
themetastable
zone.

Fromamaterial
balancepointof
view,magma

recirculation
accomplishesthe
sameobjectivesas
liquor
recirculation.
However,froman
operationalpoint
ofview,thereare
twokey
differences
betweenliquorand
magma
recirculation.

Thefirstconcerns
thepresenceof
solidsatthesiteof
supersaturation
generation.In
liquor
recirculation,no
solidsarepresent,
whereasinmagma
recirculation,
solidsarepresent.
Inessence,liquor
recirculation
createsastable
supersaturated
liquidandbringsit
intocontactwith
growingcrystals;
magma
recirculationbrings
growingcrystals
intocontactwitha
liquidthatbecomes
supersaturated.
Therefore,thepar
ticlesize
distributions
resultingfrom
liquorandmagma
recirculationwill
bedifferent.Ifthe
liquorrecirculation
liquidcanbe
maintainedinthe
stable
supersaturated
conditionbeforeit
comesintocontact
withgrowing

crystals,itwill
generallyproduce
largercrystals.

Thesecond
differencerelates
tothedegreeof
mixednessofthe
active
crystallization
volumerequired.
Liquorrecircu
lationrelieson
beingableto
maintainfluidized
classificationinthe
activevolume.The
recirculation
streamisdrawn
fromthetopofthe
activevolume,
whichcontains
clearliquid,and
thesupersaturated
liquidisreturned
fromthebottom
upwardsothat
largercrystalsare
incontactwith
highersupersatura
tions.Magma
recirculation,on
theotherhand,
doesnotrequire
product
classification.

Theabilityto
maintaina
classified
suspensioninthe
active
crystallization
volumeisvery
sensitiveto
changesin
operating
conditions,
especiallyto
changesinthe
recirculationrate.

Liquor
recirculationcan
easilyturninto
magma
recirculationin
responsetominor
changesin
operatingcon

ditions.Therefore,
froman
operabilitypoint
ofview,magma
recirculationis
preferred.

CEP

October 2006 www.aiche.org/cep 31

Solid/Liquid Separations

Table 1. Choosing a crystallization operating mechanism.

Mechanism

Should Be Considered When

Supersaturation Generation

Cooling

Should Not Be Considered When

Evaporative
decreases steeply to
moderately with decreasing

The solubility of the crystallizing component

Cooling

temperature

decreases steeply to moderately with

The solubility of the crystallizing component
stays flat or increases with decreasing
temperature
decreasing temperature

Very low crystallization temperatures are required

(direct-contact cooling should be considered)

Evaporation
component stays

The solubility of the crystallizing component

decreases steeply to moderately with
decreasing temperature

The solubility of the crystallizing

The solubility of the crystallizing component
stays flat or increases with decreasing
temperature

flat or increases with decreasing temperature

The bubble point temperature decreases very
slowly with pressure
Adiabatic The solubility of the crystallizing component

Relieving the Supersaturation

Mixed
Magma recirculation is the mechanism of choice
Liquor recirculation is the mechanism of choice for
Suspension

for control of supersaturation generation

control of supersaturation generation
Classified
Liquor recirculation is the mechanism of choice
Magma recirculation is the mechanism of choice for
Suspension
for control of supersaturation generation
control of supersaturation generation

Control of Supersaturation Generation

Magma
The goal is to bring growing crystals into
Attrition and crystal breakage in the recirculation flow
Recirculation
contact with liquid that becomes supersaturated
is to be avoided

It is not possible or desired to maintain a

classified suspension

Liquor
The goal is to have no crystals present when
Frequent changes and upsets in the operating
Recirculation
supersaturation is created, and then to bring
conditions are likely to upset the classified suspension

the stable supersaturated liquid into contact

with the growing crystals

A classified suspension can be and is maintained

in the active crystallization volume

Particle-Size Manipulation

Fines
Additional control over particle size distribution
These mechanisms are likely to interfere with the
Dissolution
is desired
active crystallization volume
and Classified
Crystals smaller than a certain size range and

Product
greater than a certain size range can be removed

Removal
without affecting the active crystallization volume

Asnotedearlier,itisverydifficulttoreliably
estimateorpredictthewidthofthemetastable

zoneforindustrialcrystallizers,although
laboratoryexperimentsdoofferuseful,but
limited,insights.Thus,inbothliquidand
magmarecirculation(seeFigures3and4),
streamsLandMaretypicallykeptascloseto
MLaspossiblebyusinghighrecirculation
rates.

Optional auxiliary mechanisms

Manipulationofparticlesizesisusefulfor
producinglargerandmoreuniformparticles.It
alsomakesitpossiblefortheprocesstoadaptto
changesinoperatingconditions.Fines
dissolutionandproductclassificationaretwo
auxiliarymechanismsthatareusedto
manipulateparticlesizes.

Finesdissolutioninvolvesremovalofparticles
smallerthanacertainsize(orsizerange)from
theactivecrystallizer

32 www.aiche.org/cep

October 2006

volume,dissolutionoftheseparticles,andthe
returnoftheresultingsolutionbacktothe
crystallizer.Thefinesareneitherallowedto
growintheactivecrystallizervolumenor
leavewiththeproductslurry.These
restrictionspromotetheformationoflarger,
moreuniformparticles,whichmakesthis
mechanismhighlydesirable.

Classifiedproductremovalinvolvestheselective
removalofonlyparticleslargerthanacertain
size(orsizerange)intheproductslurry,which
retainsthesmallerparticlesintheactive
crystallizervolumeandpromoteslargerparticle
sizes.Thismechanismisdesirable,butoptional.

Table1summarizestheconditionsunder
whicheachoperatingmechanismshouldand
shouldnotbeconsidered.Thefollowing
sectionsdescribetheimportantcrystallizer
configurationsinindustrialusetodayandthe
mechanismstheyemploy.

CEP

employmagmarecirculationtocontrol
supersaturationgeneration

Forced-circulation crystallizers

Forcedcirculation(FC)crystallizers:

useevaporationoradiabaticevaporative
coolingtogeneratesupersaturation

provideamixedsuspensionastheactive
volumeforrelievingthesupersaturation

donotprovideamechanismforfines
dissolution

can,insomecases,provideamechanismfor
classifiedproductremoval.

Figure5illustratesaforcedcirculation
crystallizer.Theequipmentconsistsofaclosed
vesselwithaconicalbottom.Recirculationis
providedbytherecirculationpipingandpump.
Therecirculatingmagmaisfedtothevessel
tangentially,belowthevaporliquidinterface.
Thefeedisaddedtotherecirculationpiping
aheadoftherecirculationpump.Theproduct

slurryiswithdrawnfromtherecirculationpiping
afterthecrystallizeroutletandbeforethefeed
inlet.

Whensupersaturationisgeneratedby
evaporation,asshownhere,therecirculating
magmaispassedthroughashellandtubeheat
exchanger.Thisheatsourceisomittedfrom
systemsusingadiabaticevaporativecooling.

Supersaturationisgeneratedatthevaporliquid
interface.Inbothmechanisms(evaporationand
adiabaticevaporativecooling),therecirculating
magmacreateslocaltemperatureand
compositionchangesattheinterfaceupon
enteringthevessel.Thesechangesleadtosolvent
evaporationattheinterfaceandsubsequent
generationofsupersaturation.Therestofthe
vessel,containingtheswirlingmassofmixed
suspension,providestheactivevolumefor
relievingthissupersaturationandalsoprovides
thematerialformagmarecirculation.

Forcedcirculationcrystallizersgenerallydonot
haveamechanismforfinesdissolution.Insome
cases,classifiedproductremovalisachievedby
employinganelutriationleg,whichislocatedatthe
bottomoftheconicalpartofthevessel.The
elutriationfluid,whichisessentiallyasmallamount
ofthemotherliquor,flowsupwardthroughtheleg.
Thisflowpreventscrystalsbelowacertainsize,
whosefreesettlingrateintheelutriationlegisless
thantheupwardflow,frombeingwithdrawnwith
theproductslurry.Theproductslurryisdrawnfrom
theelutriationleginsteadoftherecirculationpiping.

provideamixedsuspensionastheactive
volumeforrelievingthesupersaturation

employinternalmagmarecirculationtocontrol
supersaturationgeneration

usuallyprovideamechanismforclassified
productremoval

provideamechanismforfinesdissolution
whenabaffleispresent(DTBconfigurations;
DTconfigurationsdonotprovideamechanism
forfinesdissolution).

ThebasicDTBcrystallizerisshowninFigure6.
Aclosedvesselcontainsaninternalskirtbaffle
positionedsothatitprovidesapartitioned
settlingzone.Insidethebaffleisaverticaldraft
tube,centeredbysupportvanes.Aslowly
rotatingagitatorislocatedconcentricallyatthe
bottomofthedrafttube.Anelutriationlegis
usuallyfittedtothebottomoftheconetoprovide
classifiedproductremoval.Thefeedinletis
locatedatthebaseofthebottomconeandis
directedintothedrafttube.Thesettlingzone
providesanoutletforthemotherliquor.The
elutriationleghasaninletfortheelutriation
liquidandanoutletfortheproductslurry.

Draft-tube crystallizers

Drafttube(DT)anddrafttubebaffle(DTB)
crystallizersaresimilar,exceptthatDTunits
havenobaffle.DTBandDTcrystallizers:

usedirectcontactcooling,evaporationor
adiabaticevaporativecoolingtogenerate
supersaturation

Anyofthethreesupersaturationgeneration
mechanismsmaybeemployedinaDTB
crystallizer.However,withcooling,onlydirect
contactcoolingwitharefrigerantmaybeused.In
allcases,supersaturationisgeneratedatthevapor
liquidinterfaceasaresultoflocaltemperatureand
compositionchangesthatleadtosolvent(or
refrigerant)evaporation.

Vapor to

Exchanger

Condenser

(omitted

Tangential
from

Conden-

Feed Entry
systems

Steam

using

sate

Inlet

Active

Product

Adiabatic

Outlet
Discharge

Evaporative

Volume

Heat
Cooling)

Recirculation
Recirculation
Fresh

Pump

Feed

Figure 5. A forced-circulation crystallizer can

employ evaporation (as shown here) or adiabatic
evaporative cooling (without the heat exchanger) to
generate supersaturation.

Loop

CEP

October 2006 www.aiche.org/cep

33

Solid/Liquid Separations

Vapor

Vapor to
Vapor to

Condenser/

Condenser

Agitator

Vacuum System

Assembly

Mother Liquor
Mother Liquor

Mother Liquor
with Fines

Skirt

with Fines

with Fines

Baffle

Settling

Dissolution

Draft

Zone
Steam

Fresh
Liquid

Tube

Inlet

Fresh

Active

Feed

Feed

Volume

Feed

Inlet

Dissolution

Product

Condensate
Tank

Discharge

Outlet

Fines Dissolution

Elutriation
and Recirculation Loop

Refrigerant Vapor

Vapor to

Liquid

Condenser/
to Condenser

Vacuum System

Figure 6. Draft-tube-baffle crystallizers (above) can

employ various options(right): (a) evaporation, (b) adia-

batic evaporative cooling with feed addition for fines

Mother Liquor

Mother Liquor

dissolution, (c) adiabatic evaporative cooling with a

with Fines

with Fines

fines dissolution tank, or (d) direct-contact cooling.

Refrigerant

IneithertheDTBorDTconfiguration,

thedrafttubeservesasthemagmarecircula

Fresh

Fresh

tionleg,andtheareaoutsidethedrafttube

Feed

Feed

asthemixedsuspensionactivecrystalliza

tionarea.Thefeedisintroducedintothe

baseofthecrystallizerandisdirected

upwardintothedrafttubeflow.Theagitator

inducestheflow,circulatingtheliquorandcrystalsfrom

Whenevaporationisthemechanismforsupersaturation

thebottomoftheunittothetopliquidsurface.Thedraft

generation,thefeedandthedrawoffarepassedthrougha

tubeandtheagitatorarrangementthusactasaninternal

shellandtubeheatexchanger(Figure6a).Theheatexchang

magmarecirculationloop(asshownbythearrowsin

eractsasbothaheatsourceandafinesdissolver.Whenadia

Figure6).Itmaintainslargerecirculationratesatextreme

baticevaporativecoolingisused,finesdissolutionisaccom

lylowheads(comparedwithexternalrecirculation)and

plishedeitherbymixingwithdilutefeed(Figure6b)orby

continuallybringsgrowingcrystalsfromtheactivecrys

mixingwithmotherliquororsolventinaseparatedissolution

tallizationvolumetothevaporliquidinterface,wherethe

tank(Figure6c).Thesetwooptionsarealsousedwhen

supersaturationisgenerated.Thisinternalrecirculation

supersaturationisgeneratedbydirectcontactcooling,in

significantlyreducesattritionandcrystalbreakagecom

whichcasetherefrigerantisaddedseparatelytothebaseof

paredtoexternalmagmarecirculationviarecirculation

thecrystallizer(Figure6d).Notethatthefinesdissolution

loopsandpumps.

loopdoesnotconstitutetherecirculationmechanismrecir

Thesettlingzoneprovidedbytheskirtbaffleiskeyin

culationisprovidedinternallyasdiscussedabove.

bringingaboutfinesremoval.Astreamiscontinuouslydrawn

BecauseDTcrystallizersdonothavetheskirtbaffle,they

offfromthetopofthesettlingzone.Thisinducesanupward

cannotprovideforfinesdissolution.Intheseunits,freshfeed

flowintothesettlingzone.Finesbelowacertainsize,whose

isaddeddirectlytothecrystallizer.

freesettlingrateislowerthantheupwardflow,stayinthis

Surface-cooled crystallizers

zoneandareremovedinthedrawoff.Thedrawoffthen

consistsmostlyofmotherliquorwithasmallamountof

Surfacecooled(SC)andsurfacecooledbaffle(SCB)

fines.Itismixedwiththefreshfeedandsentbacktothe

crystallizersarethesameexceptfortheabsenceofabafflein

crystallizerafterthefinesarecompletelydissolved.

theSCunits.SCBandSCcrystallizers:

34 www.aiche.org/cep

October 2006

CEP

useonlysurfacecoolingtogenerate

Dissolved Fines Recirculation

supersaturation

provideamixedsuspensionastheactive

Mother Liquor

volumeforrelievingthesupersaturation

with Fines

employmagmarecirculationtocontrol
Skirt

supersaturationgeneration
Baffle
Settling

donotprovideamechanismforclassi

Central

Zone

fiedproductremoval

Feed

provideamechanismforfinesdissolu
Tube
Active

tionwhenabaffleispresent(SCBconfigu

Fresh Feed
Volume

rations;SCconfigurationsdonotprovidea

mechanismforfinesdissolution).
Coolant

Figure7illustratesacommonSCBcon
Outlet
Product
Dissolution

figuration.Itconsistsofashellandtube

Liquid

Discharge

heatexchanger,avesselwithaninternal

skirtbaffle,andarecirculationpump.The

Cooler

baffleispositionedsothatitactsasaparti

Coolant

tionbetweenasettlingzoneandtheactive

Inlet
Dissolution Tank

crystallizationvolume.Thefeedinletis

Recirculation

locatedontherecirculationpipejustprior
Recirculation
Loop

Pump

totherecirculationpump.Thesettlingzone

outsidethebaffleprovidesanoutletforthe
Figure 7. A surface-cooled baffle crystallizer uses an external heat-exchange surface to

motherliquor.Therecirculatingmagmais
generate supersaturation by cooling.

returnedtothecrystallizervesselthrougha

Classified-suspension crystallizers

centraltubeextendingintotheactivecrystallizationvolume.

Theoperationofthiscrystallizercorrespondstothe
AlsoknownasOslocrystallizers,classifiedsuspension

schematicinFigure4.Thedesiredsupersaturationisgenerat
crystallizers:

edbycoolingthemixedstreamformedbythefreshfeedand
usesurfacecooling,evaporationoradiabaticevaporative

therecirculatingslurryinthetubesoftheshellandtubeheat
coolingtogeneratesupersaturation

exchanger.Theheatexchangesurfaceisthecoldestpartof
provideaclassifiedsuspensionastheactivevolumefor

theprocessandispronetosolidsbuildup.Theheatexchang
relievingthesupersaturation

eristhereforeoperatedsuchthatthetemperaturedifference
employliquorrecirculationtocontrolsupersaturation

betweenthetubesideandtheshellsidetypicallydoesnot
generation

exceed510C.

provideabuiltinmechanismforfinesdissolution

Therecirculationpumpandtheexternalrecirculationloop
provideabuiltinmechanismforclassifiedproduct

providethemagmarecirculation.Therecirculationratesaresuf
removal.

ficientlyhightoensurethatthesupersaturationgeneratedinthe
Figure8adepictstheOsloconfigurationthatusesevapo

heatexchangerislow.Returningtherecirculatingslurry
rationtogeneratesupersaturation.Itconsistsofasuspension

throughacentraltubeextendingintothebaffledvolumeensures
tankandavaporizer.Recirculationisprovidedbyrecircula

thoroughmixinginsidetheactivecrystallizationvolume.
tionpipingandapump.Therecirculatingliquorisfedtothe

FinesdissolutioninanSCBcrystallizerworksinmuch
vaporizer.Freshfeedisaddedtotherecirculationlegahead

thesamewayasinaDTBcrystallizer.Astreamiscontinu
oftherecirculationpump,andtheproductslurryistakenoff

ouslydrawnofffromthetopofthesettlingzonecreatedby
nearthebottomofthesuspensiontank.

thebaffle.Thisdrawoffinducesanupwardflowintotheset
Whenevaporationisusedtogeneratesupersaturation,the

tlingzone.Finesbelowacertainsize(whosefreesettlingrate

recirculatingliquorispassedthroughashellandtubeheat

islessthantheupwardflow)stayinthiszoneandare
exchanger(asillustrated).Whenadiabaticevaporativecooling

removedinthedrawoff.Thefinesareusuallydissolvedina
isused,theheatexchangerisomitted(thisversionisnot

separatedissolutiontankandsentbacktothecrystallizer.
shown).Inbothmechanisms,evaporationofsolventfromthe

BecausetheSCconfigurationdoesnothaveaskirtbaffle,
recirculatingliquorenteringthevaporizergeneratesthesuper

itlacksafinesdissolutionmechanism.Itissimilartothe
saturation.Theliquorrecirculationrateishighenoughtoensure

SCBconfigurationinallotherrespects.

thatthesupersaturatedliquidinthevaporizerstaysinthe

CEP

October 2006 www.aiche.org/cep

35

Solid/Liquid Separations

Vapor to

Condenser

Suspension

Vaporizer

Tank

Recirculation

Loop

Heat
Steam
Suspension

Classified Bed

Tank

Active Volume

Inlet

Exchanger

Fresh

(omitted

Product

Weir
Feed

from

systems

Baffles

Discharge

using

Coolant

Adiabatic

Classified Bed

Evaporative

Inlet

Active Volume

Cooling)

Cooler

Steam

Product

Recirculation

Outlet

Discharge

Loop

Recirculation

Fresh

Coolant

Feed
Pump
Outlet

Recirculation Pump

Figure 8. A classified-suspension, or Oslo, crystallizer can employ (a) evaporation, adiabatic evaporative cooling (not shown), or (b) surface cooling.

metastablezoneandremainsstableandnearthesolubilitylimit.
Theliquidfromthevaporizerflowsdownintothesuspen

siontankthroughadowncomerthatextendstonearthebot
tomofthetank.Thesuspensiontankprovidestheactive
crystallizationvolumeintheformoffluidizedclassification
ofgrowingcrystals.Theclassificationensuresthatthesuper
saturatedliquidcomingfromthedowncomercomesinto

contactwiththelargercrystalsfirst.Italsoensuresthatnear
thetopoftheactivevolume,theliquidissufficientlyclear
andcanbewithdrawnforliquorrecirculation.Insomecases,
weirbafflesareincludedtopromoteliquorrecirculation.

Theseconfigurationshavebuiltinmechanismsforfines
dissolutionandclassifiedproductremoval.Iftheliquor
drawnfromthetopofthesuspensiontankcontainsfines,the
additionofheat(incaseofevaporation)orfeed(incaseof
adiabaticevaporativecooling)dissolvesthefines.Theprod
uctslurryistakenoffnearthebottomofthesuspensiontank.
Classificationinsidethetankensuresclassifiedproduct
removal.Asaresult,additionalprovisionsforfinesdissolu
tionandclassifiedproductremovalareusuallynotneeded.

Figure8bshowstheOsloconfigurationthatusessurface
coolingforsupersaturationgeneration.Thissystemalsohasa
classifiedsuspensiontank.However,itusesashellandtube
heatexchangerinsteadofavaporizertogeneratesupersatura
tion.ThisissimilartotheSCB/SCconfigurations.However,
unliketheSCB/SCdesign,itusesliquorrecirculation.

InallOsloconfigurations,liquorrecirculationensuresthat
therewillbeno(orminimal)attritionandcrystalbreakage.
However,asnotedearlier,theabilitytomaintainaclassified
suspensionissensitivetochangesintherecirculationrate.

Summing up

Table2summarizestheoperatingmechanismsemployed
inthevariouscrystallizerconfigurations.Thissummary,
alongwiththeguidanceregardingoperatingmechanisms

providedinTable1,providesinsightsforselectingthe
appropriatecrystallizerdesign.

Theseconfigurationsarethemostcommonlyusedin
industrialpractice.Severalothermodificationsand
combinationsemployingthebasicoperatingmechanisms
discussedhereareusedforspecificapplications.
Regardlessoftheconfiguration,engineersdesigningand
operatingacontinuouscrystallizerforaspecific
applicationshouldpayattentiontothefollowing:

Theresidencetimeprovidedfortheliquidphaseshould
beenoughtoensurelowsupersaturationintheactive
crystallizationvolume.

Theimpactofpossiblechangestotheresidencetimedue
tofuturechangesinoperatingconditionsshouldbetaken
intoaccount.

Changesinoperatingconditionsthatmaybringabout
significantchangesintheresidencetimeshouldbeavoided.

Therecirculationrateshouldbehighenoughtocontrolthe
generationofsupersaturation.Asaruleofthumb:when
surfacecoolingisused,thetemperaturedropintheheat
exchangershouldbelimitedtoabout12C;whenevapora
tionisused,thetemperatureincreaseintheheatexchanger
shouldbelimitedtoabout15C;andwhendirectcontact
coolingoradiabaticevaporativecoolingisused,the
temperaturedropatthevaporliquidinterfaceshouldbe
about15C.

Therecirculationrateshouldalsobecompatible

36 www.aiche.org/cep

October 2006

CEP

Table 2. Commonly used crystallizer configurations.

ForcedDraft-Tube

Surface-Cooled

Mechanism
Circulation
Baffle

Draft Tube
Baffle
Surface-Cooled
Oslo

Supersaturation Generation

Cooling

Direct-contact
Direct-contact
Surface
Surface
Surface

Evaporation

Adiabatic Evaporative Cooling

Relieving the Supersaturation

Mixed Suspension

Classified Suspension

Control of Supersaturation Generation

Magma Recirculation

Internal

Internal

Liquor Recirculation

Particle-Size Manipulation

Fines

Type based on

Type based on

Internal

Dissolution
supersaturation generation
supersaturation generation

Classified Product
With
With

With

Internal

Removal
elutriation leg
elutriation leg
elutriation leg

withthedegreeofmixednessrequiredtosustainthe
recirculationtype.

Whenmagmarecirculationisused,therecirculationrates
andequipmentshouldnotcausesevereattritionandcrystal
breakage.

Whenliquorrecirculationisused,futurechangesin
operatingconditionsthatmayimpacttheabilitytomain
tainaclassifiedsuspensionshouldbeevaluated.

Whenliquorrecirculationisused,changesinoperating
conditionsthatmayleadtomixedsuspensionandchangeto
magmarecirculationshouldbeavoided.

eral,theoperatingcostsforindustrialcrystallizers
dominatetheprocesseconomics.

Thetotalcostforthecrystallizerthatgiveshigherqual
ityproductandtroublefreeoperationoveralong
periodoftimeismuchlowerthanforacrystallizerthat
requireslesscapitalbutproducespoorerquality
productandrequiresfrequentmaintenanceand
cleaning.

Itisourhopethatthedescriptionsandinsightsprovidedin
thisarticlewillbeusefulforchemicalengineersdealing
withcontinuouscrystallizationbasedprocesses.The
discussionhereisbynomeanscomprehensive.
Additionaldetailsrelatedtocrystallizationmechanisms,
crystallizerdesign,operationalissuesandauxiliary
equipmentarefound

insourcessuchasRefs.16.
CEP

Bothcapitalandoperatingcostsmustbeconsideredwhen
designingacrystallizerforaparticularapplication.In
general,rankingsbasedoncapitalcosts,fromhighestto
lowest,areDTB/DT,Oslo,FC,SCB/SC.Thisisonlya
roughruleofthumb,however,ascapitalcostsdependon
theactualdesignspecificationsfortheapplication.Ingen

Literature Cited

Bennett,R.C.,CrystallizerSelectionandDesign,inHandbookof
IndustrialCrystallization,2ndedition,Myerson,A.S.,ed.,Butterworth
Heinemann,Boston,MA,pp.115140(2002).

Wibowo,C.,L.OYoung,andK.M.Ng,Streamlining
CrystallizationProcessDesign,Chem.Eng.Progress,100(1),pp.
3039(Jan.2004).

Mullin,J.W.,Crystallization,4thedition,ElsevierButterworth
Heinemann,Boston,MA(2001).

Kwok,K.S.,etal.,ExperimentalDeterminationofSolidLiquid
EquilibriumPhaseDiagramsforCrystallizationBasedProcessSynhesis,
Ind.Eng.Chem.Res.,44,pp.37883798(2005).

Bamforth,A.W.,IndustrialCrystallization,TheMacmillanCo.,New
York,NY(1966).

Jancic,S.J.,andP.A.M.Grootscholten,IndustrialCrystallization,
UniversityPress,Delft,TheNetherlands(1984).

KETAN D. SAMANT is a senior engineer and founding member at

ClearWaterBay Technology, Inc. (CWB Tech, 20311 Valley Blvd., Suite C,
Walnut, CA 91789; Phone: (909) 595-8928; Fax: (909) 595-8928; E-mail:
ketan@cwbtech.com). He also acts as product manager for SLEEK, CWB
Techs process-development tool for crystallization. In this role, he is involved
in various technology initiatives and consulting projects dealing with the
synthesis, design and operation of crystallizers and crystallization-based
processes. He received a BTech (Honors) from the Indian Institute of
Technology, Kharagpur, and a PhD from the Univ. of Massachusetts Amherst,
both in chemical engineering.

LIONEL OYOUNG is president and co-founder of CWB Tech (E-mail:

lionel@cwbtech.com). He has more than 15 years of experience in process
synthesis and development in the petrochemical, fine chemicals and
pharmaceuticals industries, and he holds patents for various petrochemical
processes. He earned both BS and PhD degrees in chemical engineering
from the Univ. of Manchester Institute of Science and Technology (UMIST;
Manchester, U.K.) and is a member of AIChE.

CEP

October 2006 www.aiche.org/cep

37