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CHAPTER 7
CHAPTER7

TreatmentTechnology IonExchange

INTRODUCTION
HYSTORY
CLASSIFICATIONSOFIONEXCHANGERESINS
SODIUM ZEOLITE SOFTENING
SODIUMZEOLITESOFTENING
PriciplesofZeoliteSoftening
Equipment
SoftenerOperation
Softener Regeneration
SoftenerRegeneration
DEMINERALIZATION
PriciplesofDemineralization
EquipmentandOperation
Advantages and Limitations
AdvantagesandLimitations
COUNTERFLOWANDMIXEDBEDDEIONIZATION
CounterflowCationExchangers
MixedBedExchangers
OTHERDEMINERALIZATIONPROCESSES
DecarbonatorsandDegassers
WeakAcidandWeakBaseResins
RegenerantReuse

*
*

COMMONIONEXCHANGESYSTEMPROBLEMS
Operational problems
Mechanical problems
RESINFOULINGANDDEGRADATION
Causeof Resin Fouling
Causeof irreversible Resin degradation
RESINTESTINGANDANALYSIS
THERATIONALEOFCONDENSATETREATMENT
TYPESOFCONDENSATETREATMENTSYSTEMS
THEDECOREXPROCESS
DECOREXELEMENTS
DECOREXSYSTEMSFLEXIBLEANDVERSATILE
HIGHRATEMIXEDBEDPROCESS
COMRECMIXEDBEDREGENERATIONPROCESS

Allnaturalwaterscontain,invariousconcentrations,dissolvedsaltswhich
dissociate in water to form charged ions Positively charged ions are called
dissociateinwatertoformchargedions.Positivelychargedionsarecalled
cations;negativelychargedionsarecalledanions.Ionicimpuritiescan
seriouslyaffectthereliabilityandoperatingefficiencyofaboilerorprocess
system Overheating caused by the buildup of scale or deposits formed by
system.Overheatingcausedbythebuildupofscaleordepositsformedby
theseimpuritiescanleadtocatastrophictubefailures,costlyproduction
losses,andunscheduleddowntime.Hardnessions,suchascalciumand
magnesium,mustberemovedfromthewatersupplybeforeitcanbeused
b
df
h
l b f
b
d
asboilerfeedwater.Forhighpressureboilerfeedwatersystemsandmany
processsystems,nearlycompleteremovalofallions,includingcarbon
dioxideandsilica,isrequired.Ionexchangesystemsareusedforefficient
removalofdissolvedionsfromwater.
Ion exchangers exchange one ion for another hold it temporarily and then
Ionexchangersexchangeoneionforanother,holdittemporarily,andthen
releaseittoaregenerantsolution.Inanionexchangesystem,undesirable
ionsinthewatersupplyarereplacedwithmoreacceptableions.For
example,inasodiumzeolitesoftener,scaleformingcalciumand
l i
di
lit
ft
l f
i
l i
d
magnesiumionsarereplacedwithsodiumions.

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HISTORY
In1905,Gans,aGermanchemist,usedsyntheticaluminosilicate
materialsknownaszeolitesinthefirstionexchangewatersofteners.
Althoughaluminosilicatematerialsarerarelyusedtoday,theterm
"zeolitesoftener"iscommonlyusedtodescribeanycationexchange
process.
Thesyntheticzeoliteexchangematerialwassoonreplacedbyanaturally
occurringmaterialcalledGreensand.
Greensand had a lower exchange capacity than the synthetic material,
Greensandhadalowerexchangecapacitythanthesyntheticmaterial,
butitsgreaterphysicalstabilitymadeitmoresuitableforindustrial
applications.Capacityisdefinedastheamountofexchangeableionsa
q
y f
f
unitquantityofresinwillremovefromasolution.
Itisusuallyexpressedinkilograinspercubicfootascalciumcarbonate.
Microscopicviewofcellularresinbeads(2050mesh)ofasulfonated
Mi
i i
f ll l
i b d (20 50
h) f
lf
t d
styrenedivinylbenzenestrongacidcationexhcanger.(CourtesyofRohm
andHaasCompany.)
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Microscopicviewofcellularresinbeads(2050mesh)ofasulfonated
styrenedivinylbenzene
styrene
divinylbenzenestrongacidcationexhcanger.
strong acid cation exhcanger

Thedevelopmentofasulfonatedcoalcationexchangemedium,referredto
ascarbonaceouszeolite,extendedtheapplicationofionexchangeto
hydrogencycleoperation,allowingforthereductionofalkalinityaswellas
hardness.Soon,ananionexchangeresin(acondensationproductof
polyamines and formaldehyde) was developed. The new anion resin was
polyaminesandformaldehyde)wasdeveloped.Thenewanionresinwas
usedwiththehydrogencyclecationresininanattempttodemineralize
(removealldissolvedsaltsfrom)water.
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However,earlyanionexchangerswereunstableandcouldnotremovesuch
weakly ionized acids as silicic and carbonic acid
weaklyionizedacidsassilicicandcarbonicacid.
Inthemiddle1940's,ionexchangeresinsweredevelopedbasedonthe
copolymerizationofstyrenecrosslinkedwithdivinylbenzene.
Theseresinswereverystableandhadmuchgreaterexchangecapacities
thantheirpredecessors.
The polystyrenedivinylbenzenebased
Thepolystyrene
divinylbenzene basedanionexchan
anion exchanger
gercouldremoveall
could remove all
anions,includingsilicicandcarbonicacids.Thisinnovationmadethe
completedemineralizationofwaterpossible.
Polystyrenedivinylbenzeneresinsarestillusedinthemajorityofion
exchangeapplications.Althoughthebasicresincomponentsarethesame,
theresinshavebeenmodifiedinmanywaystomeettherequirementsof
specificapplicationsandprovidealongerresinlife.
Oneofthemostsignificantchangeshasbeenthedevelopmentofthe
macroreticular or macroporous resin structure
macroreticular,ormacroporous,resinstructure.
Standardgelularresins,suchasthoseshowninFigure71,havea
permeablemembranestructure.Thisstructuremeetsthechemicaland
physicalrequirementsofmostapplications.
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However,insomeapplicationsthephysicalstrengthandchemical
resistance required of the resin structure is beyond the capabilities of the
resistancerequiredoftheresinstructureisbeyondthecapabilitiesofthe
typicalgelstructure.Macroreticularresinsfeaturediscreteporeswithina
highlycrosslinkedpolystyrenedivinylbenzenematrix.Theseresinspossess
a higher physical strength than gels as well as a greater resistance to
ahigherphysicalstrengththangels,aswellasagreaterresistanceto
thermaldegradationandoxidizingagents. Macroreticularanionresins
(Figure72)arealsomoreresistanttoorganicfoulingduetotheirmore
porousstructure.

Figure72.Microscopicviewofamacroporousstrongbaseanionresin.

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Inadditionto polystyrenedivinylbenzeneresins(Figure73),thereare
newer resins with an acrylic structure which increases their resistance to
newerresinswithanacrylicstructure,whichincreasestheirresistanceto
organicfouling.

Figure73.Chemicalstructuralformulaofsulfonicstrongacidcationresin,(XL):crosslink;(PC):polymerchain;
(ES):exchangesite;(EI):exchangeableion..

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Inadditiontoaplasticmatrix,ion
exchange resin contains ionizable
exchangeresincontainsionizable
functionalgroups.Thesefunctional
groupsconsistofbothpositively
charged cation elements and
chargedcationelementsand
negativelychargedanionelements.
However,onlyoneoftheionicspecies
ismobile.Theotherionicgroupis
bl h
h
attachedtothebeadstructure.
g
f
Figure74isaschematicillustrationof
astrongacidcationexchangeresin
bead,whichhasionicsitesconsisting
of immobile anionic (SO3))radicals
ofimmobileanionic(SO3
radicals
andmobilesodiumcations(Na+).Ion
exchangeoccurswhenrawwaterions
diff
diffuseintothebeadstructureand
i t th b d t t
d
exchangeforthemobileportionofthe
functionalgroup.Ionsdisplacedfrom
thebeaddiffusebackintothewater
solution.

Figure74.Schematicofhydratedstrongacidcation
exchanger.

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CLASSIFICATIONSOFION
EXCHANGE
EXCHANGERESINS
RESINS
Ionizablegroupsattachedtotheresinbeaddeterminethefunctional
capabilityoftheresin.Industrialwatertreatmentresinsareclassified
capability
of the resin. Industrial water treatment resins are classified
intofourbasiccategories:
StrongAcidCation(SAC)
WeakAcidCation(WAC)
StrongBaseAnion(SBA)
Strong Base Anion (SBA)
WeakBaseAnion(WBA)
SACresinscanneutralizestrongbasesandconvertneutralsaltsintotheir
correspondingacids.SBAresinscanneutralizestrongacidsandconvert
p
g
neutralsaltsintotheircorrespondingbases.Theseresinsareutilizedin
mostsofteningandfulldemineralizationapplications.WACandWBA
resinsareabletoneutralizestrongbasesandacids,respectively.These
resinsareusedfordealkalization,partialdemineralization,or(in
combinationwithstrongresins)fulldemineralization.
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SACresinsderivetheirfunctionalityfromsulfonicacidgroups(HSO3).
When used in demineralization SAC resins remove nearly all raw water
Whenusedindemineralization,SACresinsremovenearlyallrawwater
cations,replacingthemwithhydrogenions,asshownbelow:

Theexchangereactionisreversible.Whenitscapacityisexhausted,the
The
exchange reaction is reversible When its capacity is exhausted the
resincanberegeneratedwithanexcessofmineralacid.
StrongacidcationexchangersfunctionwellatallpHranges.Theseresins
havefoundawiderangeofapplications.Forexample,theyareusedinthe
sodiumcycle(sodiumasthemobileion)forsofteningandinthehydrogen
cycle for decationi ation.
cyclefordecationization.
Weakacidcationexchangeresinsderivetheirexchangeactivityfroma
carboxylicgroup(COOH).Whenoperatedinthehydrogenform,WAC
resinsremovecationsthatareassociatedwithalkalinity,producing
i
ti
th t
i t d ith lk li it
d i
carbonicacidasshown:

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Thesereactionsarealsoreversibleandpermitthereturnoftheexhausted
WAC resin to the regenerated form WAC resins are not able to remove all
WACresintotheregeneratedform.WACresinsarenotabletoremoveall
ofthecationsinmostwatersupplies.Theirprimaryassetistheirhigh
regenerationefficiencyincomparisonwithSACresins.Thishighefficiency
reduces the amount of acid required to regenerate the resin thereby
reducestheamountofacidrequiredtoregeneratetheresin,thereby
reducingthewasteacidandminimizingdisposalproblems.
Weakacidcationresinsareusedprimarilyforsofteninganddealkalization
ofhighhardness,highalkalinitywaters,frequentlyinconjunctionwithSAC
sodiumcyclepolishingsystems.Infulldemineralizationsystems,theuseof
p
y f
WACandSACresinsincombinationprovidestheeconomyofthemore
efficientWACresinalongwiththefullexchangecapabilitiesoftheSAC
resin.
SBA i d i th i f ti
SBAresinsderivetheirfunctionalityfromquaternaryammoniumfunctional
lit f
t
i
f ti
l
groups.Twotypesofquaternaryammoniumgroups,referredtoasTypeI
andTypeII,areused.TypeIsiteshavethreemethylgroups:

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InaTypeIIresinoneofthemethylgroupsisreplacedwithanethanol
group The Type I resin has a greater stability than the Type II resin and is
group.TheTypeIresinhasagreaterstabilitythantheTypeIIresinandis
abletoremovemoreoftheweaklyionizedacids.TypeIIresinsprovidea
greaterregenerationefficiencyandagreatercapacityforthesame
amount of regenerant chemical used
amountofregenerantchemicalused.
Wheninthehydroxideform,SBAresinsremoveallcommonlyencountered
anionsasshownbelow:

Aswiththecationresins,thesereactionsarereversible,allowingforthe
regeneration of the resin with a strong alkali, such as caustic soda, to
regenerationoftheresinwithastrongalkali,suchascausticsoda,to
returntheresintothehydroxideform.
Weakbaseresinfunctionalityoriginatesinprimary(RNH2),secondary(R
NHR')
NHR'),ortertiary(RNR'2)aminegroups.WBAresinsreadilyremove
t ti
(R NR'2)
i
WBA i
dil
sulfuric,nitric,andhydrochloricacids,asrepresentedbythefollowing
reaction:
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SODIUMZEOLITESOFTENING
Sodiumzeolitesofteningisthemostwidelyapplieduseofionexchange.
In zeolite softening water containing scaleforming ions such as calcium
Inzeolitesoftening,watercontainingscaleformingions,suchascalcium
andmagnesium,passesthrougharesinbedcontainingSACresininthe
sodiumform.Intheresin,thehardnessionsareexchangedwiththe
sodium,andthesodiumdiffusesintothebulkwatersolution.The
di
d th
di
diff
i t th b lk t
l ti Th
hardnessfreewater,termedsoftwater,canthenbeusedforlowto
mediumpressureboilerfeedwater,reverseosmosissystemmakeup,
somechemicalprocesses,andcommercialapplications,suchas
laundries.

Pi i l
PrinciplesofZeoliteSoftening
f Z lit S ft i
Theremovalofhardnessfromwaterbyazeolitesofteningprocessis
described by the following reaction:
describedbythefollowingreaction:

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Waterfromaproperlyoperatedzeolitesoftenerisnearlyfreefrom
detectable hardness However
detectablehardness.How
ever,somesmallamountsofhardness,knownas
some small amounts of hardness known as
leakage,arepresentinthetreatedwater.Thelevelofhardnessleakageis
dependentonthehardnessandsodiumlevelintheinfluentwaterandthe
amount of salt used for regeneration
amountofsaltusedforregeneration.

Figure75.Typicalsodiumzeolitesoftenereffluentprofile.

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Figure75isatypicalprofileofeffluenthardnessfromazeolitesoftener
during a service cycle After final rinse the softener produces a low nearly
duringaservicecycle.Afterfinalrinse,thesoftenerproducesalow,nearly
constantlevelofhardnessuntiltheionexchangeresinnearsexhaustion.At
exhaustion,theeffluenthardnessincreasessharply,andregenerationis
required.
required
Asillustratedbythesofteningreactions,SACresinreadilyacceptscalcium
andmagnesiumionsinexchangeforsodiumions.Whenexhaustedresinis
regenerated,ahighconcentrationofsodiumionsisappliedtotheresinto
replacecalciumandmagnesium.Theresinistreatedwitha10%sodium
,
g
p
g
f
g
chloridesolution,andregenerationproceedsaccordingtothefollowing
equation:

Duringregeneration,alargeexcessofregenerant(approximately3times
theamountofcalciumandmagnesiumintheresin)isused.Theeluted
hardnessisremovedfromthesofteningunitinthewastebrineandby
rinsing.

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Afterregeneration,smallresidualamountsofhardnessremainintheresin.
If resin is allowed to sit in a stagnant vessel of water some hardness will
Ifresinisallowedtositinastagnantvesselofwater,somehardnesswill
diffuseintothebulkwater.
Therefore,attheinitiationofflow,thewatereffluentfromazeolite
softenercancontainhardnessevenifithasbeenregeneratedrecently.
f
i h d
if i h b
d
l
Afterafewminutesofflow,thehardnessisrinsedfromthesoftener,and
thetreatedwaterissoft.
Thedurationofaservicecycledependsontherateofsoftenerflow,the
hardnesslevelinthewater,andtheamountofsaltusedforregeneration.
Table 71
Table7
1showstheeffectofregenerantlevelonthesofteningcapacityof
shows the effect of regenerant level on the softening capacity of
agelularstrongcationresin.
Notethatthecapacityoftheresinincreasesastheregenerantdosage
increases,buttheincreaseisnotproportional.Theregenerationisless
efficientatthehigherregenerantlevels.
Therefore, softener operating costs increase as the regenerant level
Therefore,softeneroperatingcostsincreaseastheregenerantlevel
increases.
AsshownbythedatainTable71,a150%increaseinregenerantsalt
providesonlya67%increaseinoperatingcapacity.
id
l 67% i
i
ti
it
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Table71.Effectofregenerantsaltlevelonstrongacidcationresin
softening capacity
softeningcapacity.

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Equipment
Theequipmentusedfor
sodiumzeolitesoftening
consists of a softener
consistsofasoftener
exchangevessel,control
valvesandpiping,anda
systemforbrining,or
t f bi i
regenerating,the
resin. Usually,thesoftener
tankisaverticalsteelpressure
vesselwithdishedheadsas
g
showninFigure76.
Majorfeaturesofthe
softeningvesselincludean
inlet distribution system free
inletdistributionsystem,free
boardspace,aregenerant
distributionsystem,ion
exchangeresin,andaresin
h
i
d
i
retainingunderdrain
collectionsystem.

Figure76.Sodiumzeolitesoftener.

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Theinletdistributionsystemisusuallylocatedatthetopofthetank.The
inlet system provides even distribution of influent water This prevents the
inletsystemprovidesevendistributionofinfluentwater.Thispreventsthe
waterfromhollowingoutflowchannelsintheresinbed,whichwould
reducesystemcapacityandeffluentquality.Theinletsystemalsoactsasa
collector for backwash water
collectorforbackwashwater.
Theinletdistributorconsistsofacentralheader/hubwithdistributing
laterals/radialsorsimplebaffleplates,whichdirecttheflowofwater
evenlyovertheresinbed.Ifwaterisnotpreventedfromflowingdirectly
ontothebedortankwalls,channelingwillresult.
The volume between the inlet distributor and the top of the resin bed is
Thevolumebetweentheinletdistributorandthetopoftheresinbedis
calledthefreeboardspace.Thefreeboardallowsfortheexpansionofthe
resinduringthebackwashportionoftheregenerationwithoutlossofresin.
It h ld b
Itshouldbeaminimumof50%oftheresinvolume(80%preferred).
i i
f 50% f th
i
l
(80%
f
d)
Theregenerantdistributorisusuallyaheaderlateralsystemthatevenly
distributestheregenerantbrineduringregeneration.Thelocationofthe
distributor,6in.abovethetopoftheresinbed,preventsthedilutionof
regenerantbywaterinthefreeboardspace.Italsoreduceswaterand
time requirements for displacement and fast rinse. The regenerant
timerequirementsfordisplacementandfastrinse.Theregenerant
distributorshouldbesecuredtothetankstructuretopreventbreakageand
subsequentchannelingoftheregenerant.
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Waterissoftenedbythebedofstrongacidcationexchangeresininthe
sodium form The quantity of resin required depends on the water flow
sodiumform.Thequantityofresinrequireddependsonthewaterflow,
totalhardness,andtimedesiredbetweenregenerationcycles.Aminimum
beddepthof24in.isrecommendedforallsystems.
Th
Theunderdrainsystem,locatedatthebottomofthevessel,retainsion
d d i
l
d
h b
f h
l
i i
exchangeresininthetank,evenlycollectstheserviceflow,andevenly
distributesthebackwashflow.Unevencollectionofwaterinserviceor
unevendistributionofthebackwashwatercanresultinchanneling,resin
fouling,orresinloss.
Although several underdrain designs are used there are two primary
Althoughseveralunderdraindesignsareused,therearetwoprimary
typessubfillandresinretaining.Asubfillsystemconsistsofmultiplelayers
ofsupportmedia(suchasgradedgraveloranthracite)whichsupportthe
resin,andacollectionsystemincorporatingdrilledpipesorsubfillstrainers.
i
d
ll ti
t i
ti d ill d i
bfill t i
Aslongasthesupportlayersremainintact,theresinwillremaininplace.If
thesupportingmediabecomesdisturbed,usuallyduetoimproper
backwash,theresincanmovethroughthedisruptedlayersandexitthe
vessel.Aresinretainingcollector,suchasascreenedlateralorprofilewire
strainer,ismoreexpensivethanasubfillsystembutprotectsagainstresin
loss.
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Themainvalveandpipingsystemdirectstheflowofwaterandregenerant
to the proper locations The valve system consists of a valve nest or a single
totheproperlocations.Thevalvesystemconsistsofavalvenestorasingle
multiportvalve.Avalvenestincludessixmainvalves:serviceinletand
outlet,backwashinletandoutlet,regenerantinlet,andregenerant/rinse
drain The valves may be operated manually or automatically controlled by
drain.Thevalvesmaybeoperatedmanually,orautomaticallycontrolledby
air,electricalimpulse,orwaterpressure.Insomesystems,asingle
multiportvalveisusedinplaceofthevalvenest.Asthevalverotates
throughaseriesoffixedpositions,portsinthevalvedirectflowinthesame
h
h
ff d
h
l d
fl
h
mannerasavalvenest.Multiportvalvescaneliminateoperationalerrors
causedbyopeningoftheincorrectvalvebutmustbeproperlymaintained
toavoidleaksthroughtheportseals.
Thebriningsystemconsistsofsaltdissolving/brinemeasuringequipment,
and dilution control equipment to provide the desired regenerant strength
anddilutioncontrolequipmenttoprovidethedesiredregenerantstrength.
Thedissolving/measuringequipmentisdesignedtoprovidethecorrect
amountofconcentratedbrine(approximately26%NaCl)foreach
regeneration,withoutallowinganyundissolvedsaltintotheresin.Most
ti
ith t ll i
di l d lt i t th
i M t
systemsuseafloatoperatedvalvetocontrolthefillanddrawdownofthe
supplytank,therebycontrollingtheamountofsaltusedinthe
regeneration.
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Usually,theconcentratedbrineisremovedfromthetankbymeansofan
eductor system which also dilutes the brine to the optimum regenerant
eductorsystem,whichalsodilutesthebrinetotheoptimumregenerant
strength(810%NaCl).Thebrinecanalsobepumpedfromthe
concentratedsalttankandmixedwithdilutionwatertoprovidethedesired
regenerant strength
regenerantstrength.

SoftenerOperation
Asodiumzeolitesofteneroperatesthroughtwobasiccycles:theservice
cycle,whichproducessoftwaterforuse,andtheregenerationcycle,which
p y
restoresresincapacityatexhaustion.
Intheservicecycle,waterentersthesoftenerthroughtheinletdistribution
systemandflowsthroughthebed.Thehardnessionsdiffuseintotheresin
andexchangewithsodiumions,whichreturntothebulkwater.Softwater
d
h
ith di
i
hi h t
t th b lk t S ft t
iscollectedintheunderdrainsystemanddischarged.Servicewaterflowto
thesoftenershouldbeasconstantaspossibletopreventsuddensurges
andfrequentonoffoperation.
Duetoresinrequirementsandvesseldesigns,thesofteningoperationis
most efficient when a service flow rate between 6 and 12 gpm per square
mostefficientwhenaserviceflowratebetween6and12gpmpersquare
footofresinsurfaceareaismaintained.
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Mostequipmentisdesignedtooperateinthisrange,butsomespecial
designs utilize a deep resin bed to permit operation at 1520
designsutilizeadeepresinbedtopermitoperationat15
20gpm/ft
gpm/ft.
Continuousoperationabovethemanufacturer'ssuggestedlimitscanlead
tobedcompaction,channeling,prematurehardnessbreakthrough,and
h d
hardnessleakage.Operatingwellbelowthemanufacturer'srecommended
l k
O
i
ll b l
h
f
'
d d
flowratescanalsonegativelyaffectsoftenerperformance.Atlowflow
rates,thewaterisnotsufficientlydistributed,andtheoptimumresinwater
contactcannottakeplace.
Whenasoftenerisexhausted,theresinmustberegenerated.Monitoring
of the effluent hardness reveals resin exhaustion When hardness
oftheeffluenthardnessrevealsresinexhaustion.Whenhardness
increases,theunitisexhausted.Automaticmonitorsprovideamore
constantindicationoftheconditionofthesoftenerthanperiodicoperator
samplingandtesting,butrequirefrequentmaintenancetoensure
li
d t ti
b t
i f
t
i t
t
accuracy.Manyfacilitiesregeneratesoftenersbeforeexhaustion,basedon
apredeterminedtimeperiodornumberofgallonsprocessed.
Mostsofteningsystemsconsistofmorethanonesoftener.Theyareoften
operatedsothatonesoftenerisinregenerationorstandbywhiletheother
units are in service. This ensures an uninterrupted flow of soft water. Prior
unitsareinservice.Thisensuresanuninterruptedflowofsoftwater.Prior
toplacingastandbysoftenerintoservice,theunitshouldberinsedto
removeanyhardnessthathasenteredthewaterduringtheMain Menu
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standingtime.
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SoftenerRegeneration
Theregenerationcycleofasodiumzeolitesoftenerconsistsoffoursteps:
backwash,regeneration(brining),displacement(slowrinse),andfastrinse.
Back ash D ring the ser ice c cle the do n ard flo of ater ca ses
Backwash.Duringtheservicecycle,thedownwardflowofwatercauses
suspendedmaterialtoaccumulateontheresinbed.Resinisanexcellent
filterandcantrapparticulatematterthathaspassedthroughupstream
filtrationequipment.Thebackwashstepremovesaccumulatedmaterial
andreclassifiestheresinbed.Inthebackwashstep,waterflowsfromthe
underdraindistributorupthroughtheresinbedandouttheservice
distributortowaste.Theupwardflowliftsandexpandstheresin,allowing
forremovalofparticulatematerialandresinfinesandtheclassificationof
the resin. Resin classification brings the smaller beads to the top of the unit
theresin.Resinclassificationbringsthesmallerbeadstothetopoftheunit
whilethelargerbeadssettletothebottom.Thisenhancesthedistribution
oftheregenerantchemicalandservicewater.
B k
Backwashingshouldcontinueforaminimumof10minoruntileffluent
hi
h ld
i
f
i i
f 10 i
il ffl
fromthebackwashoutletisclear.Thebackwashflowshouldbesufficient
toexpandtheresinbedvolumeby50%ormore,dependingonthe
availablefreeboard.
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Insufficientbackwashcanleadtobedfoulingandchanneling.Excessive
backwash flow rates result in the loss of resin Backwash flow rates usually
backwashflowratesresultinthelossofresin.Backwashflowratesusually
varybetween48(ambienttemperature)and1215(hotservice)gpmper
squarefootofbedarea,buteachmanufacturer'srecommendationshould
be followed The ability of water to expand the resin is greatly affected by
befollowed.Theabilityofwatertoexpandtheresinisgreatlyaffectedby
temperature.Lessflowisrequiredtoexpandthebedwithcoldwaterthan
withwarmwater.Resinbedexpansionshouldbecheckedregularlyandthe
fl
flowrateadjustedasneededtomaintainproperbedexpansion.
d
d
d d
b d
Usually,thebackwashwaterisfilteredrawwater.Waterleavingthe
g
y
p
backwashoutletisunchangedinchemistrybutcancontainsuspended
solids.Inordertoconservewater,thebackwasheffluentcanbereturnedto
theclarifierorfilterinfluentfortreatment.
R
Regeneration(Brining).Afterbackwash,regenerantbrineisapplied.The
ti (B i i ) Aft b k
h
tb i i
li d Th
brinestreamenterstheunitthroughtheregenerantdistributorandflows
downthroughtheresinbedataslowrate(usuallybetween0.5and1gpm
persquarefootofresin).Brineflowiscollectedthroughtheunderdrainand
senttowaste.Theslowflowrateincreasescontactbetweenthebrineand
resin.Toachieveoptimumefficiencyfromthebrine,thesolutionstrength
shouldbe10%duringbrineintroduction.
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Displacement(SlowRinse).Followingtheintroductionofregenerantbrine,
a slow flow of water continues through the regenerant distribution system
aslowflowofwatercontinuesthroughtheregenerantdistributionsystem.
Thiswaterflowdisplacestheregenerantthroughthebedatthedesired
flowrate.
Th di l
Thedisplacementstepcompletestheregenerationoftheresinbyensuring
l
h
i
f h
i b
i
propercontactoftheregenerantwiththebottomoftheresinbed.The
flowrateforthedisplacementwaterisusuallythesamerateusedforthe
dilutionoftheconcentratedbrine.
Thedurationofthedisplacementstepshouldbesufficienttoallowfor
approximately one resin bed volume of water to pass through the unit This
approximatelyoneresinbedvolumeofwatertopassthroughtheunit.This
providesa"plug"ofdisplacementwaterwhichgraduallymovesthebrine
completelythroughthebed.
FastRinse.Aftercompletionofthedisplacementrinse,waterisintroduced
throughtheinletdistributoratahighflowrate.
This rinse water removes the remaining brine as well as any residual
Thisrinsewaterremovestheremainingbrineaswellasanyresidual
hardnessfromtheresinbed.Thefastrinseflowrateisnormallybetween
1.5and2gpmpersquarefootofresin.Sometimesitisdeterminedbythe
service rate for the softener
servicerateforthesoftener.
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Initially,therinseeffluentcontainslargeamountsofhardnessandsodium
chloride Usually hardness is rinsed from the softener before excess sodium
chloride.Usually,hardnessisrinsedfromthesoftenerbeforeexcesssodium
chloride.Inmanyoperations,thesoftenercanbereturnedtoserviceas
soonasthehardnessreachesapredeterminedlevel,butsomeusesrequire
rinsing until the effluent chlorides or conductivity are near influent levels
rinsinguntiltheeffluentchloridesorconductivityarenearinfluentlevels.
Aneffectivefastrinseisimportanttoensurehigheffluentqualityduring
theservicerun.Ifthesoftenerhasbeeninstandbyfollowinga
regeneration,asecondfastrinse,knownasaservicerinse,canbeusedto
df
k
b
d
removeanyhardnessthathasenteredthewaterduringstandby.

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DEMINERALIZATION
Softeningaloneisinsufficientformosthighpressureboilerfeedwaters
and for many process streams especially those used in the manufacture
andformanyprocessstreams,especiallythoseusedinthemanufacture
ofelectronicsequipment.Inadditiontotheremovalofhardness,these
processesrequireremovalofalldissolvedsolids,suchassodium,silica,
alkalinity,andthemineralanions(Cl,SO4,NO3).
lk li it
d th i
l i
(Cl SO4 NO3)
Demineralizationofwateristheremovalofessentiallyallinorganicsalts
y
g
p
g
y g
byionexchange.Inthisprocess,strongacidcationresininthehydrogen
formconvertsdissolvedsaltsintotheircorrespondingacids,andstrong
baseanionresininthehydroxideformremovestheseacids.
Demineralization produces water similar in quality to distillation at a
Demineralizationproduceswatersimilarinqualitytodistillationata
lowercostformostfreshwaters.

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PrincipleofDemineralization
Ademineralizersystemconsistsofoneormoreionexchangeresincolumns,
whichincludeastrongacidcationunitandastrongbaseanionunit.The
cation resin exchanges hydrogen for the raw water cations as shown by the
cationresinexchangeshydrogenfortherawwatercationsasshownbythe
followingreactions:

Ameasureofthetotalconcentrationofthestrongacidsinthecation
f
f
g
effluentisthefreemineralacidity(FMA). Inatypicalservicerun,theFMA
contentisstablemostofthetime,asshowninFigure78.

Figure78.Typicaleffluentprofileforstrongacidcationexchanger.

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Ifcationexchangewere100%efficient,theFMAfromtheexchangerwould
be equal to the theoretical mineral acidity (TMA) of the water The FMA is
beequaltothetheoreticalmineralacidity(TMA)ofthewater.TheFMAis
usuallyslightlylowerthantheTMAbecauseasmallamountofsodium
leaksthroughthecationexchanger.Theamountofsodiumleakage
depends on the regenerant level the flow rate and the proportion of
dependsontheregenerantlevel,theflowrate,andtheproportionof
sodiumtotheothercationsintherawwater.Ingeneral,sodiumleakage
increasesastheratioofsodiumtototalcationsincreases.
Asacationexchangeunitnearsexhaustion,FMAintheeffluentdrops
sharply,indicatingthattheexchangershouldberemovedfromservice.At
g
,
thistimetheresinshouldberegeneratedwithanacidsolution,which
returnstheexchangesitestothehydrogenform.Sulfuricacidisnormally
usedduetoitsaffordablecostanditsavailability.However,improperuse
of sulfuric acid can cause irreversible fouling of the resin with calcium
ofsulfuricacidcancauseirreversiblefoulingoftheresinwithcalcium
sulfate.
Topreventthisoccurrence,thesulfuricacidisusuallyappliedatahighflow
rate(1gpmpersquarefootofresin)andaninitialconcentrationof2%or
less.Theacidconcentrationisgraduallyincreasedto68%tocomplete
regeneration.
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Someinstallationsusehydrochloricacidforregeneration.Thisnecessitates
the use of special materials of construction in the regenerant system As
theuseofspecialmaterialsofconstructionintheregenerantsystem.As
withasodiumzeoliteunit,anexcessofregenerant(sulfuricorhydrochloric
acid)isrequireduptothreetimesthetheoreticaldose.
T
Tocompletethedemineralizationprocess,waterfromthecationunitis
l
h d i
li i
f
h
i
i i
passedthroughastrongbaseanionexchangeresininthehydroxideform.
Theresinexchangeshydrogenionsforbothhighlyionizedmineralionsand
themoreweaklyionizedcarbonicandsilicicacids,asshownbelow:

Theabovereactionsindicatethatdemineralizationcompletelyremovesthe
cationsandanionsfromthewater.Inreality,becauseionexchange
reactionsareequilibriumreactions,someleakageoccurs.Mostleakage
ti
ilib i
ti
l k
M tl k
fromcationunitsissodium.Thissodiumleakageisconvertedtosodium
hydroxideintheanionunits.Therefore,theeffluentpHofatwobed
cationaniondemineralizersystemisslightlyalkaline.Thecausticproduced
intheanionscausesasmallamountofsilicaleakage.
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Theextentofleakagefromtheanionsdependsonthechemistryofthe
water being processed and the regenerant dosage being used
waterbeingprocessedandtheregenerantdosagebeingused.
Demineralizationusingstronganionresinsremovessilicaaswellasother
dissolvedsolids.Effluentsilicaandconductivityareimportantparameters
tomonitorduringademineralizerservicerun.
i d i
d i
li
i
B h ili
Bothsilicaandconductivity
d
d i i
arelowattheendofthefastrinse,asshowninFigure79

Figure79.Conductivity/silicaprofileforstrongbaseanionnexchanger

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Whensilicabreakthroughoccursattheendofaservicerun,thetreated
water silica level increases sharply Often the conductivity of the water
watersilicalevelincreasessharply.Often,theconductivityofthewater
decreasesmomentarily,thenrisesrapidly.
Thistemporarydropinconductivityiseasilyexplained.Duringthenormal
servicerun,mostoftheeffluentconductivityisattributedtothesmalllevel
i
f h ffl
d i i i
ib d
h
ll l l
ofsodiumhydroxideproducedintheanionexchanger.
g
,
y
g
,
Whensilicabreakthroughoccurs,thehydroxideisnolongeravailable,and
thesodiumfromthecationexchangerisconvertedtosodiumsilicate,
whichismuchlessconductivethansodiumhydroxide.
As anion resin exhaustion progresses the more conductive mineral ions
Asanionresinexhaustionprogresses,themoreconductivemineralions
breakthrough,causingasubsequentincreaseinconductivity.
Whentheendofademineralizerrunisdetected,theunitmustberemoved
fromserviceimmediately.
Ifthedemineralizerisallowedtoremaininservicepastthebreakpoint,the
level of silica in the treated water can rise above that of the influent water
levelofsilicainthetreatedwatercanriseabovethatoftheinfluentwater,
duetotheconcentratingofsilicathattakesplaceintheanionresinduring
theservicerun.
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Strongbaseanionexchangersareregeneratedwitha4%sodiumhydroxide
solution As with cation regeneration the relatively high concentration of
solution.Aswithcationregeneration,therelativelyhighconcentrationof
hydroxidedrivestheregenerationreaction.
Toimprovetheremovalofsilicafromtheresinbed,theregenerantcaustic
i
isusuallyheatedto120Fortothetemperaturespecifiedbytheresin
ll h
d 120F
h
ifi d b h
i
manufacturer.Silicaremovalisalsoenhancedbyaresinbedpreheatstep
beforetheintroductionofwarmcaustic.

EquipmentandOperation
Theequipmentusedforcation
The
equipment used for cationanion
aniondemineralizationissimilartothat
demineralization is similar to that
usedinzeolitesoftening.Theprimarydifferenceisthatthevessels,valves,
andpipingmustbemadeof(orlinedwith)corrosionresistantmaterials.
R bb
Rubberandpolyvinylchloride(PVC)arecommonlyusedforionexchange
d l i l hl id (PVC)
l
df i
h
vessellinings.Thecontrolsandregenerantsystemsfordemineralizersare
morecomplex,toallowforsuchenhancementsasstepwiseacidandwarm
causticregenerations.
Demineralizersaresimilarinoperationtozeolitesofteners.Theservice
flow rate guidelines for a demineralizer range from 6 to 10 gpm per square
flowrateguidelinesforademineralizerrangefrom6to10gpmpersquare
footofresin.
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Flowratesofover10gpmpersquarefootofresincauseincreasedsodium
and silica leakage with certain waters Anion resin is much lighter than
andsilicaleakagewithcertainwaters.Anionresinismuchlighterthan
cationresin.
Therefore,thebackwashflowratesforanionexchangeresinsaremuch
l
lowerthanthoseforcationresins,andanionresinexpansionisaffectedby
h
h
f
i
i
d i
i
i i ff
db
thetemperatureofthewatermorethancationresinexpansion.
f
p f
g
f
Thewaterusedforeachstepofanionresinregenerationshouldbefree
fromhardness,topreventprecipitationofhardnesssaltsinthealkaline
anionresinbed.
Continuous conductivity instruments and silica analyzers are commonly
Continuousconductivityinstrumentsandsilicaanalyzersarecommonly
usedtomonitoranioneffluentwaterqualityanddetecttheneedfor
regeneration.
Insomeinstances,conductivityprobesareplacedintheresinbedabove
theunderdraincollectorstodetectresinexhaustionbeforesilica
breakthrough into the treated water occurs..
breakthroughintothetreatedwateroccurs..

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AdvantagesandLimitations
Demineralizerscanproducehighpuritywaterfornearlyeveryuse.
Demineralizedwateriswidelyusedforhighpressureboilerfeedwaterand
for many process waters The quality of water produced is comparable to
formanyprocesswaters.Thequalityofwaterproducediscomparableto
distilledwater,usuallyatafractionofthecost.Demineralizerscomeina
widevarietyofsizes.Systemsrangefromlaboratorycolumnsthatproduce
onlyafewgallonsperhourtosystemsthatproducethousandsofgallons
l f
ll
h
t
t
th t
d
th
d f ll
perminute.
Likeotherionexchangesystems,demineralizersrequirefilteredwaterin
ordertofunctionefficiently.Resinfoulantsanddegradingagents,suchas
ironandchlorine,shouldbeavoidedorremovedpriortodemineralization.
Anion resins are very susceptible to fouling and attack from the organic
Anionresinsareverysusceptibletofoulingandattackfromtheorganic
materialspresentinmanysurfacewatersupplies.Someformsofsilica,
knownascolloidal,ornonreactive,arenotremovedbyademineralizer.
Hot alkaline boiler water dissolves the colloidal material forming simple
Hot,alkalineboilerwaterdissolvesthecolloidalmaterial,formingsimple
silicatesthataresimilartothosethatentertheboilerinasolubleform.As
such,theycanformdepositsontubesurfacesandvolatilizeintothesteam.
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COUNTERFLOWANDMIXED
BED DEIONIZATION
BEDDEIONIZATION
Duetoincreasingboileroperatingpressuresandthemanufactureof
productsrequiringcontaminantfreewater,thereisagrowingneedfor
higherwaterqualitythancationaniondemineralizerscanproduce.
f ,
y
fy
Therefore,ithasbecomenecessarytomodifythestandard
demineralizationprocesstoincreasethepurityofthetreatedwater.The
mostsignificantimprovementsindemineralizedwaterpurityhavebeen
produced by counterflow cation exchangers and mixed bed exchangers
producedbycounterflowcationexchangersandmixedbedexchangers.

CounterflowCationExchangers
Inaconventionaldemineralizersystem,regenerantflowisinthesame
directionastheserviceflow,downthroughtheresinbed.Thisschemeis
knownascocurrentoperationandisthebasisformostionexchange
systemdesigns.Duringtheregenerationofacocurrentunit,the
contaminantsaredisplacedthroughtheresinbedduringthe
regeneration. At the end of the regeneration, some ions, predominately
regeneration.Attheendoftheregeneration,someions,predominately
sodiumions,remaininthebottomoftheresinbed.
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Becausetheupperportionofthebedhasbeenexposedtofresh
regenerant it is highly regenerated As the water flows through the resin
regenerant,itishighlyregenerated.Asthewaterflowsthroughtheresin
duringservice,cationsareexchangedintheupperportionofthebedfirst,
andthenmovedownthroughtheresinasthebedbecomesexhausted.
Sodium ions that remained in the bed during regeneration diffuse into the
Sodiumionsthatremainedinthebedduringregenerationdiffuseintothe
decationizedwaterbeforeitleavesthevessel.Thissodiumleakageenters
theanionunitwhereanionexchangeproducescaustic,raisingthepHand
conductivityofthedemineralizedwater.
d
f h d
l d
Inacounterflowregeneratedcationexchanger,theregenerantflowsinthe
pp
f
f
p , f
f
oppositedirectionoftheserviceflow.Forexample,iftheserviceflowis
downwardthroughthebed,theregenerantacidflowisupthroughthe
bed.Asaresult,themosthighlyregeneratedresinislocatedwherethe
service water leaves the vessel The highly regenerated resin removes the
servicewaterleavesthevessel.Thehighlyregeneratedresinremovesthe
lowlevelofcontaminantsthathaveescapedremovalinthetopofthebed.
Thisresultsinhigherwaterpuritythancocurrentdesignscanproduce.To
maximizecontactbetweentheacidandresinandtokeepthemosthighly
i i
t tb t
th
id d i
dt k
th
t hi hl
regeneratedresinfrommixingwiththerestofthebed,theresinbedmust
staycompressedduringtheregenerantintroduction.
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Thiscompressionisusuallyachievedinoneoftwoways:
ablockingflowofwaterorairisused
a blocking flow of water or air is used
theacidflowissplit,andacidisintroducedatboththetopandthe
bottomoftheresinbed

Figure711.Counterflowcationprofileshowingdualacidflowblockingmethod Main Menu

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MixedBedExchanger
Amixedbedexchangerhasbothcationandanionresinmixedtogetherina
singlevessel.Aswaterflowsthroughtheresinbed,theionexchange
processisrepeatedmanytimes,"polishing"thewatertoaveryhigh
purity. Duringregeneration,theresinisseparatedintodistinctcationand
f
g
anionfractionsasshowninFigure712.

Figure712.Significantstepsintheregenerationsequenceforamixedbedexchanger. Main Menu

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Theresinisseparatedbybackwashing,withthelighteranionresinsettling
on top of the cation resin Regenerant acid is introduced through the
ontopofthecationresin.Regenerantacidisintroducedthroughthe
bottomdistributor,andcausticisintroducedthroughdistributorsabovethe
resinbed.Theregenerantstreamsmeetattheboundarybetweenthe
cation and anion resin and discharge through a collector located at the
cationandanionresinanddischargethroughacollectorlocatedatthe
resininterface.Followingregenerantintroductionanddisplacementrinse,
airandwaterareusedtomixtheresins.Thentheresinsarerinsed,andthe
unitisreadyforservice.
d f
Counterflowandmixedbedsystemsproduceapurerwaterthan
,
q
p
conventionalcationaniondemineralizers,butrequiremoresophisticated
equipmentandhaveahigherinitialcost.Themorecomplicated
regenerationsequencesrequirecloseroperatorattentionthanstandard
systems This is especially true for a mixed bed unit
systems.Thisisespeciallytrueforamixedbedunit.

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OTHERDEMINERALIZATION
PROCESS
Thestandardcationanionprocesshasbeenmodifiedinmanysystemsto
reducetheuseofcostlyregenerantsandtheproductionofwaste.
Modificationsincludetheuseofdecarbonatorsanddegassers,weak
,
g
(
acidandweakbaseresins,strongbaseanioncausticwaste(to
regenerateweakbaseanionexchangers),andreclamationofaportion
ofspentcausticforsubsequentregenerationcycles.

DecarbonatorsandDegassers
Decarbonatorsanddegassersareeconomicallybeneficialtomany
demineralizationsystems,becausetheyreducetheamountofcaustic
requiredforregeneration.Waterfromacationexchangerisbrokeninto
smalldropletsbyspraysandtraysorpackinginadecarbonator.The
waterthenflowsthroughastreamofairflowingintheopposite
direction.Carbonicacidpresentinthecationeffluentdissociatesinto
carbon dioxide and water.
carbondioxideandwater.
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Thecarbondioxideisstrippedfromthewaterbytheair,reducingtheload
to the anion exchangers Typical forced draft decarbonators are capable of
totheanionexchangers.Typicalforceddraftdecarbonatorsarecapableof
removingcarbondioxidedownto1015ppm.However,watereffluent
fromadecarbonatorissaturatedwithoxygen.
I
Inavacuumdegasser,waterdropletsareintroducedintoapackedcolumn
d
d l
i
d di
k d l
thatisoperatedunderavacuum.Carbondioxideisremovedfromthe
waterduetoitsdecreasedpartialpressureinavacuum.Avacuum
degasserusuallyreducescarbondioxidetolessthan2ppmandalso
removesmostoftheoxygenfromthewater.However,vacuumdegassers
p
p
p
f
f
aremoreexpensivetopurchaseandoperatethanforceddraft
decarbonators.

Weak Acid and Weak Base Resins

WeakAcidandWeakBaseResins
Weakfunctionalityresinshaveamuchhigherregenerationefficiencythan
theirstrongfunctionalitycounterparts.Weakacidcationresins,as
describedinthedealkalizationsection,exchangewithcationsassociated
withalkalinity.Weakbaseresinsexchangewiththemineralacidanions
(SO4,Cl,NO3)inastrongacidsolution.
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Theregenerationefficiencyofweakresinsisvirtuallystoichiometric,the
removal of 1 kgr of ions (as CaCO3) requires only slightly more than 1 kgr of
removalof1kgrofions(asCaCO3)requiresonlyslightlymorethan1kgrof
theregenerantion(asCaCO3).Strongresinsrequirethreetofourtimesthe
regenerantforthesamecontaminantremoval.
W kb
Weakbaseresinsaresoefficientthatitiscommonpracticetoregeneratea
i
ffi i
h i i
i
weakbaseexchangerwithaportionofthe"spent"causticfrom
regenerationofthestrongbaseanionresin.Thefirstfractionofthecaustic
fromthestrongbaseunitissenttowastetopreventsilicafoulingofthe
weakbaseresin.Theremainingcausticisusedtoregeneratetheweak
f
f
y
baseresin.Anadditionalfeatureofweakbaseresinsistheirabilitytohold
naturalorganicmaterialsthatfoulstrongbaseresinsandreleasethem
duringtheregenerationcycle.Duetothisability,weakbaseresinsare
commonly used to protect strong base resins from harmful organic fouling
commonlyusedtoprotectstrongbaseresinsfromharmfulorganicfouling.

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RegenerantReuse
Duetothehighcost ofcausticsodaandtheincreasingproblemsofwaste
disposal,manydemineralizationsystemsarenowequippedwithacaustic
reclaimfeature.Thereclaimsystemusesaportionofthespentcaustic
fromthepreviousregenerationatthebeginningofthenextregeneration
cyc e e eused caust c s fo o ed by f es caust c to co p ete t e
cycle.Thereusedcausticisfollowedbyfreshcaustictocompletethe
regeneration.Thenewcausticisthenreclaimedforuseinthenext
regeneration.Typically,sulfuricacidisnotreclaimed,becauseitislowerin
cost and calcium sulfate precipitation is a potential problem
costandcalciumsulfateprecipitationisapotentialproblem.

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COMMONIONEXCHANGE
SYSTEM PROBLEMS
SYSTEMPROBLEMS
Asinanydynamicoperatingsystemincorporatingelectricaland
mechanicalequipmentandchemicaloperations,problemsdooccurin
ionexchangesystems.
The problems usually result in poor effluent quality decreased service
Theproblemsusuallyresultinpooreffluentquality,decreasedservice
runlengths,orincreasedconsumptionofregenerant.
Tokeeptheionexchangesystemoperatingefficientlyandreliably,
changesinwaterquality,runlengths,orregenerantconsumptionshould
beconsideredwheneverproblemsaredetected.

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Thecauseeffectdiagramsforshortruns(Figure714) and poorquality

effluent (Figure 715)
effluent(Figure7
15) showthattherearemanypossiblecausesfor
show that there are many possible causes for
reducedperformanceofademineralizationsystem.Someofthemore
commonproblemsarediscussedbelow.

Figure714.Causeeffectdiagramforshortrunsinatwobeddemineralizersystem.

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Figure714.Causeeffectdiagramforshortrunsinatwobeddemineralizersystem.

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OperationalProblems
Changes inrawwaterqualityhaveasignificantimpactonboththerun
lengthandtheeffluentqualityproducedbyanionexchangeunit.Although
mostwellwatershaveaconsistentquality,mostsurfacewater
compositionsvarywidelyovertime.A10%increaseinthehardnessofthe
ate to a sod u eo te softe e causes a 0% dec ease t e se ce u
watertoasodiumzeolitesoftenercausesa10%decreaseintheservicerun
length.Anincreaseintheratioofsodiumtototalcationscausesincreased
sodiumleakagefromademineralizersystem.Regularchemicalanalysisof
the influent water to ion exchangers should be performed to reveal such
theinfluentwatertoionexchangersshouldbeperformedtorevealsuch
variations.
Othercausesofionexchangeoperationalproblemsinclude:

Improperregenerations,causedbyincorrectregenerantflows,times,or
concentrations.Manufacturer'srecommendationsshouldbefollowed
when regenerating ion exchange resins
whenregeneratingionexchangeresins.

Channeling,resultingfromeitherhighorlowflowrates,increased
suspended solids loading or poor backwashing This causes premature
suspendedsolidsloadingorpoorbackwashing.Thiscausespremature
exhaustionevenwhenmuchofthebedisinaregeneratedstate.
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Resinfoulingordegradation,causedbypoorqualityregenerant.

Failuretoremovesilicafromtheresin,whichcanresultfromlow
regenerantcaustictemperature.Thiscanleadtoincreasedsilica
leakage and short service runs
leakageandshortserviceruns.

Excesscontaminantsintheresin,duetopreviousoperationpast
exhaustion loads Because the resin becomes loaded with more
exhaustionloads.Becausetheresinbecomesloadedwithmore
contaminantsthananormalregenerationisdesignedtoremove,a
doubleregenerationisrequiredfollowinganextendedservicerun.

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MechanicalProblems
Typicalmechanicalproblemsassociatedwithionexchangesystemsinclude:

ea g a es,
c cause poo qua ty eff ue t a d p o o ged ses
Leakingvalves,whichcausepoorqualityeffluentandprolongedrinses.

Brokenorcloggeddistributor,whichleadstochanneling.

Resinloss,duetoexcessivebackwashingorfailureintheunderdrain
screeningorsupportmedia.

Cationresinintheanionunit,causingextendedrinsetimesandsodium
leakageintothedemineralizedwater.

Instrumentationproblems,suchasfaultytotalizersorconductivity
meters,whichmayindicateaproblemwhennoneexists,ormay
introduce poor quality water to service. Instrumentation in the
introducepoorqualitywatertoservice.Instrumentationinthe
demineralizerareashouldbecheckedregularly.

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RESINFOULINGAND
DEGRADATION
Resincanbecomefouledwithcontaminantsthathindertheexchange
process.
Figure716showsaresinfouledwithiron.

Fi
Figure716.Ironfouledresin.
7 16 I
f l d i

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Theresincanalsobeattackedbychemicalsthatcauseirreversible
destruction Somematerials,suchasnaturalorganics(Figure7
destruction.
Some materials such as natural organics (Figure 717)
17),foul
foul
resinsatfirstandthendegradetheresinastimepasses.

Figure717.Anionresinfouledwithorganicmaterial.

Thisisthemostcommoncauseoffoulinganddegradationinionexchange
This
is the most common cause of fouling and degradation in ion exchange
systems,andisdiscussedunder"OrganicFouling,"laterinthischapter
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CausesofResinFouling
IronandManganese.
Ironmayexistinwaterasaferrousorferricinorganicsaltorasa
seq estered organic comple Ferro s iron e changes in resin b t ferric
sequesteredorganiccomplex.Ferrousironexchangesinresin,butferric
ironisinsolubleanddoesnot.Ferricironcoatscationresin,preventing
exchange.Anacidorastrongreducingagentmustbeusedtoremovethis
iron.Organicallyboundironpassesthroughacationunitandfoulsthe
anionresin.Itmustberemovedalongwiththeorganicmaterial.
Manganese,presentinsomewellwaters,foulsaresininthesamemanner
asiron.
Aluminium.
Al i
Aluminumisusuallypresentasaluminumhydroxide,resultingfromalum
i
ll
t
l i
h d id
lti f
l
orsodiumaluminateuseinclarificationorprecipitationsoftening.
Aluminumfloc,ifcarriedthroughfilters,coatstheresininasodiumzeolite
softener.Itisremovedbycleaningwitheitheracidorcaustic.Usually,
aluminumisnotafoulantinademineralizersystem,becauseitisremoved
f
fromtheresinduringanormalregeneration.
g
g
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HardnessPrecipitates.
Hardness precipitates carry through a filter from a precipitation softener
Hardnessprecipitatescarrythroughafilterfromaprecipitationsoftener
orformafterfiltrationbypostprecipitation.Theseprecipitatesfoulresins
usedforsodiumzeolitesoftening.
Th
Theyareremovedwithacid.SulfatePrecipitation.Calciumsulfate
d i h id S lf
P i i i
C l i
lf
precipitationcanoccurinastrongacidcationunitoperatedinthe
hydrogencycle.
Attheendofaservicecycle,thetopoftheresinbedisrichincalcium.If
sulfuricacidisusedastheregenerant,anditisintroducedattoohigha
f
,p p
f
f
concentrationortoolowaflowrate,precipitationofcalciumsulfate
occurs,foulingtheresin.
Aftercalciumsulfatehasformed,itisverydifficulttoredissolve;therefore,
resin fouled by calcium sulfate is usually discarded Mild cases of calcium
resinfouledbycalciumsulfateisusuallydiscarded.Mildcasesofcalcium
sulpfatefoulingmaybereversedwithaprolongedsoakinhydrochloric
acid.
B i
Bariumsulfateisevenlesssolublethancalciumsulfate.Ifawatersource
lf t i
l
l bl th
l i
lf t If
t
containsmeasurableamountsofbarium,hydrochloricacidregeneration
shouldbeconsidered.
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OilFouling.
Oil coats resin blocking the passage of ions to and from exchange sites A
Oilcoatsresin,blockingthepassageofionstoandfromexchangesites.A
surfactantcanbeusedtoremoveoil.Caremustbeexercisedtoselecta
surfactantthatdoesnotfoulresin.Oilfouledanionresinsshouldbe
cleanedwithnonionicsurfactantsonly.
l
d ih
i i
f
l
MicrobiologicalFouling.Microbiologicalfoulingcanoccurinresinbeds,
p
y
f
especiallybedsthatareallowedtositwithoutserviceflow.
Microbiologicalfoulingcanleadtoseverepluggingoftheresinbed,and
evenmechanicaldamageduetoanexcessivepressuredropacrossthe
fouled resin If microbiological fouling in standby units is a problem a
fouledresin.Ifmicrobiologicalfoulinginstandbyunitsisaproblem,a
constantflowofrecirculatingwatershouldbeusedtominimizethe
problem.Severeconditionsmayrequiretheapplicationofsuitable
sterilizationagentsandsurfactants.
t ili ti
t
d f t t
SilicaFouling.
Silica fouling can occur in strong base anion resins if the regenerant
Silicafoulingcanoccurinstrongbaseanionresinsiftheregenerant
temperatureistoolow,orinweakbaseresinsiftheeffluentcausticfrom
theSBAunitusedtoregeneratetheweakbaseunitcontainstoomuch
silica At low pH levels polymerization of the silica can occur in a weak
silica.AtlowpHlevels,polymerizationofthesilicacanoccurinaweak
baseresin.Itcanalsobeaprobleminanexhaustedstrongbaseanion
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resin.Silicafoulingisremovedbyaprolongedsoakinwarm
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CausesofIrreversibleResinDegradation
Oxidation.
Oxidizingagents,suchaschlorine,degradebothcationandanionresins.
O idants attack the di in lben ene cross links in a cation resin red cing
Oxidantsattackthedivinylbenzenecrosslinksinacationresin,reducing
theoverallstrengthoftheresinbead.Astheattackcontinues,thecation
resinbeginstoloseitssphericalshapeandrigidity,causingittocompact
duringservice.Thiscompactionincreasesthepressuredropacrossthe
resinbedandleadstochanneling,whichreducestheeffectivecapacityof
theunit.
Inthecaseofrawwaterchlorine,theanionresinisnotdirectlyaffected,
becausethechlorineisconsumedbythecationresin.However,
downstream strong base anion resins are fouled by certain degradation
downstreamstrongbaseanionresinsarefouledbycertaindegradation
productsfromoxidizedcationresin.
Ifchlorineispresentinrawwater,itshouldberemovedpriortoion
exchangewithactivatedcarbonfiltrationorsodiumsulfite.Approximately
1.8ppmofsodiumsulfiteisrequiredtoconsume1ppmofchlorine.
Oxygensaturated
Oxygen
saturatedwater,suchasthatfoundfollowingforceddraft
water such as that found following forced draft
decarbonation,acceleratesthedestructionofstrongbaseexchangesites
thatoccursnaturallyovertime.Italsoacceleratesdegradation Main Menu
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d
duetoorganicfouling.
i f li
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ThermalDegradation.
Thermal degradation occurs if the anion resin becomes overheated during
Thermaldegradationoccursiftheanionresinbecomesoverheatedduring
theserviceorregenerationcycle.Thisisespeciallytrueforacrylicresins,
whichhavetemperaturelimitationsaslowas100F,andTypeIIstrong
b
baseanionresins,whichhaveatemperaturelimitof105Fwheninthe
i
i
hi h h
li i f 105F h i h
hydroxideform.
g
g
OrganicFouling.
Organicfoulingisthemostcommonandexpensiveformofresinfouling
anddegradation.Usually,onlylowlevelsoforganicmaterialsarefoundin
well waters However surface waters can contain hundreds of parts per
wellwaters.However,surfacewaterscancontainhundredsofpartsper
millionofnaturalandmanmadeorganicmatter.Naturalorganicsare
derivedfromdecayingvegetation.Theyarearomaticandacidicinnature,
andcancomplexheavymetals,suchasiron.Thesecontaminantsinclude
tannins,tannicacid,humicacid,andfulvicacid.
Initially, organics block the strong base sites on a resin. This blockage
Initially,organicsblockthestrongbasesitesonaresin.Thisblockage
causeslongfinalrinsesandreducessaltsplittingcapacity.Asthefoulant
continuestoremainontheresin,itbeginstodegradethestrongbase
sites reducing the salt splitting capacity of the resin
sites,reducingthesaltsplittingcapacityoftheresin.
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Thefunctionalityofthesitechangesfromstrongbasetoweakbase,
and finally to a nonactive site Thus a resin in the early stages of
andfinallytoanonactivesite.Thus,aresinintheearlystagesof
degradationexhibitshightotalcapacity,butreducedsaltsplitting
capacity.Atthisstage,cleaningoftheresincanstillreturnsome,butnot
all of the lost operating capacity A loss in salt splitting capacity reduces
all,ofthelostoperatingcapacity.Alossinsaltsplittingcapacityreduces
theabilityoftheresintoremovesilicaandcarbonicacid.
Organicfoulingofanionresinisevidencedbythecoloroftheeffluent
fromtheanionunitduringregeneration,whichrangesfromteacolored
todarkbrown.Duringoperation,thetreatedwaterhashigherconductivity
p
andalowerpH.
Prevention.
Thefollowingmethodsareused,eitheraloneorincombination,toreduce
organicfouling:

Prechlorinationandclarification.Waterisprechlorinatedatthesource,
andthenclarifiedwithanorganicremovalaid.
d h
l ifi d i h
i
l id

Filtrationthroughactivatedcarbon.Itshouldbenotedthatacarbon
fl h
filterhasafinitecapacityforremovaloforganicmaterialandthatthe
f
f
l f
l d h h
removalperformanceofthecarbonshouldbemonitored
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frequently.

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Macroporousandweakbaseresinaheadofstrongbaseresin.The
weak base or macroporous resin absorbs the organic material and is
weakbaseormacroporousresinabsorbstheorganicmaterialandis
elutedduringregeneration.
Specialtyresins.Acrylicandotherspecialtyresinsthatareless
susceptibletoorganicfoulinghavebeendeveloped.
ibl
i f li h
b
d l
d
InspectionandCleaning.
In addition to these preventive procedures a program of regular inspection
Inadditiontothesepreventiveprocedures,aprogramofregularinspection
andcleaningoftheionexchangesystemhelpstopreservethelifeofanion
resin.Mostcleaningproceduresuseoneofthefollowing:

Warm(120F)brineandcaustic.Mildoxidantsorsolubilizingagents
canbeaddedtoimprovethecleaning.

Hydrochloricacid.Whenresinsarealsofouledwithsignificantamounts
ofiron,hydrochloricacidsareused.

Solutionsof0.250.5%sodiumhypochlorite.Thisproceduredestroys
theorganicmaterialbutalsosignificantlydegradestheresin.
H
Hypochloritecleaningisconsideredalastresort.
hl it l
i i
id d l t
t
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Itisimportanttocleananorganicallyfouledresinbeforeexcessive
permanent degradation of the strong base sites occurs Cleaning after
permanentdegradationofthestrongbasesitesoccurs.Cleaningafter
permanentdegradationhasoccurredremovessignificantamountsof
organicmaterialbutdoesnotimproveunitperformance.Theconditionof
the resin should be closely monitored to identify the optimum schedule for
theresinshouldbecloselymonitoredtoidentifytheoptimumschedulefor
cleaning.

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RESINTESTINGANDANALYSIS
Totracktheconditionofionexchangeresinanddeterminethebesttime
forcleaningit,theresinshouldbeperiodicallysampledandanalyzedfor
physicalstability,foulantlevels,andtheabilitytoperformtherequired
g
ionexchange.
Samplesshouldberepresentativeoftheentireresinbed.
Therefore,samplesshouldbecollectedatdifferentlevelswithinthebed,
oragrainthieforhollowpipeshouldbeusedtoobtaina"core"sample.
Duringsampling,theinletandregenerantdistributorshouldbe
examined, and the condition of the top of the resin bed should be noted.
examined,andtheconditionofthetopoftheresinbedshouldbenoted.
Excessivehillsorvalleysintheresinbedareanindicationofflow
distributionproblems.

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Theresinsampleshouldbeexaminedmicroscopicallyforsignsoffouling
and cracked or broken beads It should also be tested for physical
andcrackedorbrokenbeads.Itshouldalsobetestedforphysical
properties,suchasdensityandmoisturecontent(Figure718).

Figure718.Periodicsamplingandevaluationoftheresinisrequiredtokeepperformanceandefficiencyat
optimumlevels.

Theleveloforganicandinorganicfoulantsintheresinshouldbe
determinedandcomparedtoknownstandardsandthepreviouscondition
of the resin. Finally, the salt splitting and total capacity should be measured
oftheresin.Finally,thesaltsplittingandtotalcapacityshouldbemeasured
onanionresinsamplestoevaluatetherateofdegradationororganic
fouling.
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