Ion exchange resins

Ion exchange resin is a cross-linked porous polymer substance containing functional

(ionogenic) groups with mobile ions, which may be replaced with ions of the same charge
dissolved in the surrounding liquid media.
Structure of ion exchange resins
The polymer base of most of ion exchange resins is styrene-divinylbenzene copolymer.
The molecular structure of the copolymer presents a network of high-weight polystyrene
molecules cross-linked by the molecules of divinylbenzene (DVB).
Cross-linking provides toughness and insolubility of the resin.
The amount of the cross-linking agent (divinylbenzene) may vary within the range 2%-16%.

The functional groups are attached to the styrene rings.
The chemical formulas of some ion exchanging resins:
O 8SC
3
P
O 8SC
3
na
O 8CCCP
O 8nP
3
CP
Ion exchange resins may differ in their porous structure: microporous (gel) resins and
macroporous resins.
Gel resins are most widely used. Gel resins have higher ion capacity.
Macroporous resins are used for treating severely contaminated solutions due to their ability
to elute foulants.
Ion exchange equilibrium
The general chemical reaction of ion exchange:
ation exchange
nRA + B
n+
= R
n
B
n+
+ nA
+

or
Anion exchange
nRA + B
n-
= R
n
B
n-
+ nA
-


Where:
R - ionized resin molecule with an attached functional group;
A
+
/ A
-
- exchangeable ion;
B
n+
/ B
n-
- cation/anion dissolved in the liquid;
n+ /n- - electrical charge of the ion B.
The equilibrium constant of the reaction (selectivity coefficient):
K = [A]
n
[R
n
B]/[RA]
n
[B]

Where [A], [R
n
B], [RA], [B] - concentrations of A, R
n
B, RA and B.

Selectivity coefficient indicates the degree of the ions (A and B) exchanging. The higher the
selectivity coefficient the higher fraction of the ion B is replaced with the ion A.
Selectivity coefficient also determines a preference of an ion to another ion. The ions with
higher selectivity coefficient will replace the ions with lower selectivity coefficient in
the resin molecules.
The values of the selectivity coefficients for various cations in strong cation exchangers are
arranged as follows (decreasing order):
Fe
3+
, Al
3+
, Pb
2+
, Sr
2+
, Ca
2+
, Co
2+
, Ni
2+
, Cu
2+
, Zn
2+
, Mg
2+
, Mn
2+
, Ag
+
, Cs
+
, Cd
+
, K
+
, NH
4
+
, Na
+
,
H
+
, Li
+
, Hg
2+


The values of the selectivity coefficients for various anions in amino base anion exchangers
are arranged as follows (decreasing order):
SO
4
2-
, CrO
4
2-
, PO
4
3-
, HSO
4
-
, NO
3
-
, Br
-
, Cl
-
, HCO
3
-
, F
-
, OH
-


Properties of ion exchange resins
$elling. Ion exchange resins are hygroscopic. The amount of moisture hydrated by
a resin is determined by the cross-linkingand the type of functional group. Low cross-
linking gel resins with functional groups of sulfonic acid or quaternary ammonium
contain large amounts of water resulting in swelling. Frequent swelling and contraction
reduce the resin life.
apacity. Capacity is a number of chemical equivalents of ions that can be taken up by
a unit amount of the resin (dry weight/wet weight/wet volume). Cross-linking decreases
the capacity measured on the dry basis (fewer functional groups may be attached to
highly cross-linked polymer molecules). However cross-linking also decreases hydration
of the resin therefore the capacity measured on the wet basis increases with an increase
of the cross-linking level.
!article size. Ion exchange resins are available in different particle (bed) size. Common
ion exchange resins are manufactured in form of polydispersed spherical beds with the
size distributed within the range 0.01-0.05 (0.25-1.25mm) or in form of uniform
particle size (UPS). Smaller particles improve the kinetics of the ion exchanging reaction
but cause increase of the water pressure drop and decrease of the flow rate.
$tability. Mechanical (physical) stability of ion exchange resins is determined mainly by
the toughness of the polymer structure(cross-linking) and by the frequency of swelling-
contraction cycles. Chemical degradation of ion exchange resins may be caused by
fouling the resin pores by precipitates (e.g., iron hydroxide), breaking polymer structure,
loss of ion exchange capacity due to a modification of the functional groups.
Strong Acid Cation resins
Strong Acid Cation (SAC) resins behave similar to strong acids.
Strong Acid Cation resins are available in two forms: hydrogen (R-SO
3
H) or sodium (R-
SO
3
Na).

The typical strong acid cation exchange reaction:
2(R-$

a) + al
2
= (R-$

)
2
a + 2al

Cross-linking level of the Strong Acid Cation resins is 8-10%.
The ion exchange capacity of Strong Acid Cation resins does not depend on the solution PH.
Strong Acid Cation resins are used for water softening and demineralization.
The exhausted Strong Acid Cation resins may be regenerated.
Regeneration in hydrogen (acid) form is performed by a strong acid (e.g., HCL).
Regeneration in sodium (salt) form is performed by sodium chloride solution (NaCl).

Weak Acid Cation resins
Weak Acid Cation (WAC) resins behave similar to weak acids.
Weak Acid Cation resins are available in hydrogen form (R-COOH).
Weak Acid Cation resins have high affinity for hydrogen ions therefore they are easily
regenerated by stoichiometric amount of acid.
The ion exchange capacity of Weak Acid Cation resins increases with an increase of the
solution PH. WAC resins are not used for treatment acidic (PH<6) solutions.
Weak Acid Cation resins are used for demineralization and dealkalization of water.

Strong Base Anion resins
Strong Base Anion (SBA) resins behave similar to strong bases.
Strong Base Anion resins are available in hydroxide form: (R-NH
3
OH).

The typical strong base anion exchange reaction:
R-

= R-

+
2


Strong Base Anion resins are used for demineralization and dealkalization of water.
The exhausted Strong Base Anion resins may be regenerated by concentrated sodium
hydroxide (NaOH).

Weak Base Anion resins
Weak Base Anion (WBA)resins behave similar to weak bases.

The typical weak base anion exchange reaction:
R-
2
+

= R-

The ion exchange capacity of Weak Base Anion resins increases with a decrease of the
solution PH. WBA resins are not used for treatment basic (PH>6) solutions.
Weak Base Anion resins sorb only anions of strong acids (chlorides, nitrates, sulfates).
Weak Base Anion are easily regenerated by small amounts of weak bases (such as ammonia
or sodium carbonate), which neutralize the acid taken up by the resin.

Water treatment with ion exchange resins
Ion exchange resins are used for two types of water treatment:
ater softening. Hard water contains ions of calcium (Ca
2+
) and magnesium (Mg
2+
).
Sodium type Strong Acid Cation resins(e.g., R-SO
3
Na) are used for water softening. The
ions of calcium and magnesium dissolved in water are bound by the resinexchanging the
equivalent amount of sodium ions (Na
+
), which are released from the resin to water. PH
of water does not change in softening process. Anions are not removed in the process
therefore anion base resins are not used. The exhaustedresin is regularly regenerated.
The regeneration process includes the following stages:
Removing suspended hard particles by reverse flow of water.
Passing a solution containing high concentration of sodium ions (commonly a strong
solution of NaCl) for replacing the calcium and magnesium ions with fresh sodium
ions.
Rinsing the resin with water in order to remove the regenerating solution.
emineralization (deionization) of ater. Both types of ions cations and anions are
removed from the water in the demineralization process. Therefore two resin types are
used: Strong Acid Cation resins and Strong Base Anion resins. The cationresins are used
in hydrogen form (e.g., R-SO
3
H), the anion resins are used in hydroxide form (e.g., R-
NH
3
OH). The water first passes through the acid cation resin where the dissolved cations
are bound by the resin and replaced by the equivalent amount of ions of hydrogen (H
+
).
The water becomes slightly acidic. Then the water passes through the base
anion resin where the dissolved anions are replaced with the hydroxide ions, which are
released to the water. Hydroxide and hydrogen ions react and form neutral water. The
hydrogen type strong acid cation resin is regenerated by solutions of strong acids
(hydrochloric or sulfuric). The strong base anion resin is regenerated by solutions of
sodium hydroxide (NaOH).
http://www.substech.com/dokuwiki/doku.php?idionexchangeresins

lon exchange reslns are polymers LhaL are capable of exchanglng parLlcular lons wlLhln Lhe polymer wlLh
lons ln a soluLlon LhaL ls passed Lhrough Lhem 1hls ablllLy ls also seen ln varlous naLural sysLems such as
solls and llvlng cells 1he synLheLlc reslns are used prlmarlly for purlfylng waLer buL also for varlous
oLher appllcaLlons lncludlng separaLlng ouL some elemenLs
ln waLer purlflcaLlon Lhe alm ls usually elLher Lo sofLen Lhe waLer or Lo remove Lhe mlneral conLenL
alLogeLher 1he waLer ls sofLened by uslng a resln conLalnlng na+ caLlons buL whlch blnds Ca2+ and
Mg2+ more sLrongly Lhan na+ As Lhe waLer passes Lhrough Lhe resln Lhe resln Lakes up Ca2+ and Mg2+
and releases na+ maklng for a sofLer waLer lf Lhe waLer needs Lo have Lhe mlneral conLenL enLlrely
removed lL ls passed Lhrough a resln conLalnlng P+ (whlch replaces all Lhe caLlons) and Lhen Lhrough a
second resln conLalnlng CP (whlch replaces all Lhe anlons) 1he P+ and CP Lhen reacL LogeLher Lo glve
more waLer
1he process has some dlsadvanLages ln LhaL Lhere are subsLances occurlng ln some waLer (such as
organlc maLLer or le3+ lons) whlch can foul Lhe resln buL ln general Lhe advanLages of Lhe process (long
llfe of reslns cheap malnLalnance eLc) ouLwelgh Lhe dlsadvanLages ln addlLlon Lhe process ls very
envlronmenLally frlendly because lL deals only wlLh subsLances already occurlng ln waLer
Water soften|ng
ln waLer sofLenlng a caLlon resln ln Lhe sodlum form ls used Lo remove hard meLal lons (calclum and
magneslum) from Lhe waLer along wlLh Lroublesome Lraces of lron and manganese whlch are also ofLen
presenL 1hese lons are replaced by an equlvalenL quanLlLy of sodlum so LhaL Lhe LoLal dlssolved sollds
conLenL of Lhe waLer remalns unchanged as does Lhe pP and anlonlc conLenL AL regular Llme lnLervals
Lhe resln ls cleaned (llgure 3) 1hls lnvolves passlng lnfluenL waLer back up Lhrough Lhe resln Lo remove
suspended sollds passlng a regeneranL soluLlon down Lhrough Lhe resln Lo replace Lhe lons LhaL have
bound Lo Lhe resln and Lhen rlnslng agaln wlLh waLer Lo remove Lhe regeneranL soluLlon ln waLer
sofLenlng Lhe regeneranL ls a sLrong soluLlon of sodlum chlorlde
em|nera||sat|on
vlrLually all Lhe dlssolved maLLer ln naLural waLer supplles ls ln Lhe form of charged lons CompleLe
delonlzaLlon (le demlnerallsaLlon) can be achleved by uslng Lwo reslns 1he waLer ls flrsL passed
Lhrough a bed of caLlon exchange resln conLalned ln a vessel slmllar Lo LhaL descrlbed for sofLeners 1hls
ls ln Lhe hydrogen lon form broughL abouL by Lhe use of a sLrong acld regeneranL (elLher hydrochlorlc or
sulphurlc) uurlng servlce caLlons ln Lhe waLer are Laken up by Lhe resln whlle hydrogen lons are
released 1hus Lhe effluenL conslsLs of a very weak mlxLure of aclds 1he waLer now passes Lhrough a
second vessel conLalnlng anlon exchange resln ln Lhe hydroxlde form for whlch sodlum hydroxlde ls used
as Lhe regeneranL Pere Lhe anlons are exchanged for hydroxlde lons whlch reacL wlLh Lhe hydrogen
lons Lo form waLer Such Lwln bed unlLs wlll reduce Lhe LoLal sollds conLenL Lo approxlmaLely 12 mg L1
WlLh larger unlLs lL ls usual Lo pass waLer leavlng Lhe caLlon unlL Lhrough a degasslng Lower 1hls
removes mosL of Lhe carbonlc acld produced from carbon dloxlde and blcarbonaLe ln Lhe feed waLer and
reduces Lhe load on Lhe anlon unlL WlLhouL degasslng Lhe carbonlc acld would be Laken up by Lhe anlon
bed afLer converslon Lo carbonaLe lf compleLe demlnerallzaLlon ls requlred Lhls ls achleved by passlng
Lhe Lwln bed effluenL Lhrough a Lhlrd vessel conLalnlng elLher caLlon resln ln Lhe hydrogen form or a bed
of mlxed resln conslsLlng of boLh anlonlc and caLlonlc resln whlch has been lnLlmaLely comblned Mlxed
resln ls a very efflclenL demlnerallser and can produce waLer wlLh much lower levels of dlssolved
maLerlal Lhan can be achleved by dlsLlllaLlon lor small supplles such as ln laboraLorles mlxed resln ls
ofLen used ln dlsposable carLrldges 1hese are only used once buL larger mlxed resln unlLs can be
regeneraLed AfLer exhausLlon Lhe bed ls sub[ecLed Lo an up flow of waLer Anlonlc resln beads are less
dense Lhan Lhe caLlonlc ones and Lhey rlse Lo Lhe Lop so LhaL Lhe bed ls separaLed lnLo Lwo layers of
resln Lach ls regeneraLed ln slLu wlLh Lhe approprlaLe regeneranL Lhen rlnsed wlLh clean waLer 1he
lnLernal plpe work of Lhe vessel ls arranged so LhaL regeneranLs and washes enLer aL Lhe polnL
separaLlng Lhe Lwo reslns and flow elLher up or down as requlred An upflow of compressed alr Lhen
mlxes Lhe reslns up agaln

hLLp//nzlcorgnz/Chemrocesses/waLer/13updf
PesIn matrIx
About 90 of all Ion exchange resIns are based on a polystyrenIc matrIx. The buIldIng block used
to make thIs plastIc skeleton Is styrene monomer, an aromatIc compound also called vInylbenzene.
8elow are the chemIcal formulas:

Chemccl ]ormulc o] styrene

Smpl]ed representcton o] styrene
The vInyl double bond of thIs molecule enables polymerIsatIon. The next pIcture shows the
polymerIsed styrene, albeIt only wIth four vIsIble styrene groups. n realIty, mIllIons of groups are
attached together In very long chaIns.

A smcll ]rccton o] c polystyrene chcn
The resultIng lInear polymer chaIns are entangled together, but have lIttle physIcal strength: they
are relatIvely soft, and after actIvatIon they would probably dIssolve In water. To gIve the
polymer a more stable trIdImentIonal structure, the polystyrene chaIns are .ross-IInked wIth
another molecule at the tIme of polymerIsatIon. The crosslInkIng molecule must be able to
polymerIse at two or three ends. The most common crosslInker Is dIvInylbenzene (abbrevIated as
078).

0vnylbenzene (0\8)

Crosslnked polystyrene
The second bond of the 078 molecule Is shown In red and attaches to the next chaIn of lInear
polystyrene. The more 078 Is added to the InItIal reactIon mIxture, the more rIgId Is the polymer.
|ost Ion exchange resIns are polymerIsed In such a way that spherI.aI beads are obtaIned. ThIs
can occur eIther In a stIrred reactor or wIth a jettIng process. n the latter case, the bead sIze Is
very unIform.
CeI and ma.roporous resIn stru.ture
n the polymerIsatIon process descrIbed above, the crosslInker Is more or less evenly dIstrIbuted
throughout the matrIx. The voIds between the chaIns of polystyrene are called pores. They are
very small and theIr sIze Is only a few , but the sIze Is relatIvely constant: the matrIx has a
pseudocrystallIne structure, sImIlar to glass, and as a result the fInIshed Ion exchange resIIn
beads are transparent. n the pIcture below, the polystyrene chaIns are shown In blue wIthout the
aromatIc chemIcal detaIls, and the brIdges formed by 078 are shown In red.

6el structure
There Is a lImIt to the quantIty of 078 that can be used In gel type resIns: too much 078 creates a
stucture wIth very small pores, whIch In the fInal product may be a dIsadvantage, as larger Ions
cannot enter the resIn beads. AddItIonally, hIghly crosslInked polymers are more dIffIcult to
actIvate.
To overcome thIs problem, macroporous resIns have been Invented In the 1960's. The Idea Is to
create artIfIcal porosIty In the trIdImensIonal matrIx. To thIs effect, a thIrd component - called
porogen or phase extender - Is Incorporated In the reactIon mIxture, whIch does not react wIth
the monomers, but only takes room In the system. Dnce the polymerIsatIon reactIon Is fInIshed,
the porogen Is washed out and leaves voIds In the polymer structure. These are the ma.ropores.

Mccroporous structure
|acroporous resIns have a double porosIty: the small pores of the matrIx Itself and the large
macropores created by the phase extender. The fInal resIns are opaque. They are very stable, as
the matrIx Is usually hIghly crosslInked. They also very porous, thus can exchange large Ions.
Fun.tIonaIIsatIon of the poIymer
The polymer descrIbed above must be actIvated to convert the plastIc beads Into Ion exchange
resIns.
The actIvatIon Is chemIcally sImple: It Is a suIphonatIon reactIon. the polystyrene beads are
contacted at hIgh temperature wIth concentrated sulphurIc acId. The product Is a poloystyrene
sulphonate, whIch Is a strong acId.

Sulphoncton
ThIs reactIon produces the resIn In hydrogen form. f the product Is to be used as a softenIng resIn,
It must be converted In an addItIonal step to the sodIum form. ThIs can be done wIth sodIum
carbonate, for Instance.
The actIvatIon Is more complex, as It requIres two successIve steps. Also, the chemIcals used are
more expensIve, whIch explaIns that anIon exchange resIns are consIderably more expensIve than
SAC resIns. The fIrst step Is called .hIoromethyIatIon, and Is a reactIon between the polymer
beads and chloromethyl methylether:

Chloromethylcton
The product has chlorIde groups, but these are covalent, not IonIsed. At thIs stage, we don't have
an anIon exchange resIn yet. The second step of the actIvatIon Is an amInatIon, where the
covalent chlorIde Is replaced by an amIne.

Amncton
The pIcture shows an amInatIon made wIth trImethylamIne. The product Is a quaternary
ammonIum chlorIde salt. 8y conventIon, S8A resIns produced wIth trImethylamIne are called %ype
1. As produced, S8A resIns are In the chlorIde (Cl

) form and must be regenerated wIth caustIc

soda before use In a demIneralIsatIon system. Type 1 resIns are the most common strongly basIc
exchangers.
nstead of trImethylamIne, dImethylethanolamIne can be used to produce
the socalled%ype 2 S8A resIn. ThIs amIne Is shown on the left. Type 2 resIns have a lower basIcIty
than type 1. ThIs results In a better regenerabIlIty (conversIon to the DH

form) but type 2 resIns

are more sensItIve to temperature degradatIon, and have a lowerselectIvIty for Ions, so that the
leakage Is hIgher In servIce.
eakIy basI. anIon exchange resIns are produced In the same
way, but usIng a secondary Instead of a tertIary amIne. n most cases, dImethylamIne (shown on
the left) Is used. The product Is an Ion exchange resIn In the hydrochlorIc form, whIch Is
regenerated to the free base form for supply. ThIs W8A resIn Is shown on the rIght. n the
regenerated form, W8A resIns do not have exchangeable Ions. They can only remove strong acIds
from solutIon, whIch means they must be used after decatIonIsatIon. See Ion exchange reactIons.
StIll other amInes can be used to make specIal anIon exchange resIns, such as those selectIve for
nItrate, borate, or perchlorate.
These resIns are not produced by actIvatIon of polystyrene beads. nstead, they are made from
acrylIc polymers, eIther startIng from acrylonItrIle or from methyl acrylate.

Polymerscton o] ccrylontrle

Polymerscton o] methyl ccrylcte
The polymer obtaIned must be hydrolysed to form .arboxyII. a.Id groups. The polyacrylonItrIle
polymer Is hydrolysed wIth sulphurIc acId, whIlst the polyacrylate Is hydrolysed wIth caustIc sode.
n both cases, the same fInal compound Is obtaIned. Here only caustIc hydrolysIs Is shown:

Hydrolyss o] polyccrylcte wth ccustc sodc
The WAC resIn product obtaIned Is a weak acId, only partIally IonIsed In neutral envIronment. ts
acIdIty Is sImIlar to that of acetIc acId. 0ue to the alIphatIc (not aromatIc) lIghtweIght structure
of the matrIx, WAC resIns have a hIgher densIty of actIve groups than resIns based on polystyrene.
ThIs results In a hIgh total Ion exchange capacIty.

Dnce dIssocIated (wIth an alkalIne anIon, see reactIons), the resIn can exchange catIons. Here an
example wIth sodIum. A carboxylate salt Is formed.

WIth dIvalent metals, a stable .ompIex Is formed between two functIonal groups, as shown on the
left, whIch explaIns the hIgh selectIvIty of WAC resIns for these Ions.


W8A and S8A resIns can also be made startIng from an acrylIc Instead of an aromatIc copolymer.
The fIrst polymerIdsatIon step Is the same as that for a WAC resIn startIng from methyl acrylate,
as shown In the prevIous sectIon. The polyacrylate Is then reacted wIth a specIal dIamIne havIng a
prImary amIne at one end and a tertIary amIne at the other end:

Amdcton o] polyccrylcte wth 0MAPA
The product obtaIned Is a weakly basIc acrylIc anIon exchange resIn. From thIs, a strongly basIc
resIn can be obtaIned wIth an addItIonal quaternIsatIon step usIng methyl chlorIde or dImethyl
sulphate:

Qucternscton o] cn ccrylc W8A to S8A
AcrylIc anIon resIns are more hydrophIlIc than styrenIc resIns, and show a superIor resIstance to
organIc foulIng.
Several other resIn types have been developed, maInly to produce selectIve resIns. A few typIcal
actIve groups are shown below:

\crous other ]unctoncl yroups
heIatIng resIns
|ost of the above specIal resIns are of the chelatIng type. They are able to form complexes wIth
metals. TheIr name Is derIved from the Creek word meanIng claw, because the metallIc
Ions are captured lIke In a claw. The pIcture on the rIght shows a metal complexed by the
ImInodIacetIc functIonal group of a chelatIng resIn. The chelatIng resIns make complexes only wIth
multIvalent metals. These complexes are very stable. Therefore, these resIns have a hIgh
selectIvIty and are capable of removIng metals from solutIon selectIvely. See examples In the resIn
types page, wIth the correspondIng applIcatIons.



hLLp//dardellnfo/lx/resln_sLrucLurehLml

Mechanism of Ion Exchange Processes
most common ion exchange system includes a water-swollen ion exchange material and surrounding aqueous
solution. Ion exchange, like any heterogeneous process, is accomplished by transIer oI ions to and Irom the inter-
phase boundary, i.e. the chemical reaction itselI, diIIusion inside the material, and diIIusion in the surrounding
solution should be taken into account. Besides the two major phases, the thin Iilm oI solution at surIace oI the
exchanger should be accounted separately. The Iilm properties diIIer Irom properties oI the surrounding bulk
solution. Formation oI this Iilm is unavoidable.

Even a rigorous agitation (an intensive stirring in batch processes or turbulent hydrodynamic Ilow in column
systems) while being able to reduce the thickness oI the inter-phase Iilm can never take it oII completely.

Figure 10.1 shows the simplest illustration oI the mass transIer at ion exchange. Ions B diIIuse Irom the solution
through the Iilm into the beads and ions A diIIuse out oI the beads crossing the Iilm into the solution. This inter
phase diIIusion oI counterions is what is called ion exchange |5|. To complete the overall picture oI the interaction
mechanism, the stoichiometric character oI ion exchange must be emphasised. Any counterions which leave the ion
exchanger are replaced by an equivalent amount of other counterions |5|. This is a consequence oI the
electroneutrality requirement. When a counterion crosses the inter-phase boundary, an electric potential is created
between two phases. This potential must be compensated by the movement oI another counterion in opposite
direction (ion exchange) or by the movement oI a co-ion in the same direction (salt transIer).

In many systems, particularly in diluted solutions, Donnan exclusion restricts entering oI co-ions into the exchanger
during the whole process. In this case, co-ions do not participate in the reaction and thus have little direct eIIect on
the rate |5|. However, an indirect inIluence can be observed. For example, selectivity oI the ion exchange system
depends on the nature oI the co-ion, and the rate, in turn, may be aIIected by the selectivity. II the salt transIer is
negligible, the total content oI counterions in each phase (in equivalents) remains constant at any moment oI the
process irrespective oI the ionic composition.133

The consequence is equality oI the Iluxes Ior two exchanged ions. This phenomenon, so called coupling of fluxes, is
not limited by the inter-phase transIer oI ions. The same is valid Ior diIIusion oI ions inside each phase, i.e.
speciIicity oI the mass transIer in the ionic systems is that any transIer oI the ion is accomplished by corresponding
transIer oI charge-compensating ion(s) due to the electroneutrality principle.

s long as an ion exchanger can be considered as a 'quasi-liquid, the interIace between the material and
surrounding solution is no more than a limit beyond which the matrix (or crystalline structure in case oI inorganic
materials) does not extend |527|. No signiIicant resistance to mass transIer can be expected Irom such an interIace
unless some species are deposed on the surIace oI the material. Thus, the mechanism oI ion exchange can be
presented by Fig. 10.2. The Iollowing steps can be listed:
1. The Iirst step is diIIusion oI the Iirst ion Irom bulk oI the solution towards the interphase Iilm (process 2 in Fig.
10.2). This step can be easily manipulated because the diIIusion transport in the bulk solution can be assisted
with agitation. II a column process is considered, turbulence oI the local Ilows between the exchanger beads can
assist the mass transIer towards and Irom the inter-phase boundary.

2. The next step is diIIusion oI the ion through the Nernst Iilm (process 3). No convection can be established here.
The mass transIer is deIined solely by mobility oI the ion. gitation oI the external solution can somehow
reduce the thickness oI the Iilm but cannot remove it completely.

3. Iter the transIer oI the ion through the boundary between the Iilm and the solid, the ion diIIuses inside the
phase oI material (process 4). This process is deIined solely by properties oI the material and oI the ion. The
only driving Iorce is the concentration gradient.
In order to IulIil the electroneutrality principle, the above mentioned steps are compensated by the Iollowing:
$econd counterion diIIuses Irom bulk oI the ion exchange material towards the surIace (process 7).
Iter transIer oI the second ion, through the boundary, it diIIuses through the Iilm towards the bulk solution
(process 8).
Finally, the second ion diIIuses Irom the Iilm into bulk oI the solution (process 9).
There are also Iew steps which could accomplish the process:
Dissociation oI dissolved complexes which incorporate Iirst ion (process 1).
ssociation between Iirst ion and Iunctional group (process 5).
Dissociation oI associates between second ion and Iunctional group (process 6).
ssociation oI second ion in the solution phase (process 10).
These processes could take place only iI the system contains species which are able to
Iorm corresponding associates.

s described earlier, the stoichiometry oI ion exchange requires equivalency oI the Iluxes Ior two exchanging
counterions. This holds even though the counterion mobilities may diIIer signiIicantly. The simplest approach is
based on the assumption that the mass transport is limited by diIIusion oI the slowest ion (bottleneck principle).
However, the real ion exchange diIIusion is more complicated. The Iaster ion, oI course, tends to diIIuse at a higher
rate |5|. However, an initial disparity oI diIIusion Iluxes causes a deviation Irom electroneutrality. The electric
potential created aIIects diIIusion oI both ions, retarding the Iaster ion and accelerating the slower one. This eIIect is
illustrated in Fig. 10.3 as a sum oI vectors. The created electric potential created acts as a Iorce maintaining
electroneutrality or, rather, a state so close to electroneutrality that the deviation is negligible in almost all the cases
oI practical interest

Zagorodni, ndrei . 2007. on Exchange Materials Properties and Aplication, Elsevier, msterdam Hal 241

5ikasi daam Industri
Pengoahan ir Dengan Ion-Exchange Di Industri
ir untuk industri akhir-akhir ini menjadi isu besar dan menjadi salah satu kriteria dalam menentukan lokasi suatu
industri akan dibangun, pada era 80-an sumber-sumber air mudah didapat namun kondisi saat ini jauh berbeda,
sumber air semakin susah ditemukan ini ditengarai air permukaan yang kualitas dan kuantitasnya semakin terbatas
ditambah dengan proses ijin untuk menggunakan sumber dari sumur dalam (deep well) semakin susah didapat.
Belum lagi isu lingkungan turut menjadi pertimbangan dalam pemberian ijin eksploitasi sumber air untuk industri.

Tentunya bagi industri yang banyak melakukan kegiatan ekspor impor pasti akan memilih lokasi dekat dengan
pelabuhan guna memudahkan kegiatan operasi mereka, termasuk didalamnya industri berbasis minyak sawit
termasuk pabrik minyak dan lemak makanan, oleochemical dan biodiesel. Industri berbasis minyak sawit ini
menjadi eIisien apabila kriteria pokok pendirian pabrik dapat dipenuhi termasuk utilitas, process water, energi serta
jaringan transportasi yang memadai untuk menunjang kegiatan produksi serta ekspor produk.

da beberapa sumber air yang biasanya dipertimbangkan untuk menjadi sumber air utama seperti air permukaan,
sungai, waduk atau dari sumber air dalam, deep well sementara desalinasi air laut kurang Iavorit kerena selain
biayanya mahal juga dampak lingkungannya ynag cukup merepotkan. papun sumber yang akan digunakan sebagai
sumber air industri, maka air baku perlu dikondisikan dengan mengolah terlebih dahulu melalui water treatment
yang memadai, termasuk penggunaan kolom ion exchange.

Karakter air dan penggunaannya.

ir proses atau biasa kita kenal sebagai process water memiliki Iungsi yang berbeda satu sama lainnya, oleh karena
itu karakter serta spesiIikasi air yang diperlukan juga berbeda satu dengan yang lain, misalnya standar air untuk
boiler tentu berbeda dengan standar air untuk produksi hydrogen.

da beberapa peralatan proses yang membutuhkan air secara terus-menerus dan dengan siIat tertentu, seperti :

1. ir proses (process water) untuk hydrolysis, boiler dan destilasi. Kebutuhan process water untuk boiler,
hydrolysis serta produksi H2, dimana diperlukan air yang terlebih dahulu diperoleh melalui ion exchange untuk
meminimalisir timbulnya karat serta sumbatan pada pipa api dan jalur distribusi uap dan kondensatnya. Produk
air yang dihasilkan melalui ion exchange kemudian disebut sebagai soIt water bahkan untuk produksi hydrogen
diperlukan demineralized water (demin water) agar H2 yang diproduksi betul-betul 99,9 murni.

2. ir untu pendingin (Cooling Water) pada cooling tower, mesin, heat exchanger, condenser dll. Kebutuhan akan
air pendingin (cooling water) bisa di kategorikan kebutuhan umum dalam setiap mesin penggerak, pengolahan
air pendingin biasanya kurang diperhatikan oleh operator pabrik karena persepsi yang salah dimana setiap air
bersuhu rendah bisa digunakan. Tetapi mereka lupa bahwa air pendingin disalurkan melalui pipa-pipa yang
diameternya terkadang cukup kecil, panjang dan melingkar-lingkar sehingga rawan terhadap karat dan
sumbatan tentunya.

3. ir untuk kebutuhan domestik dan umum. ir yang akan digunakan sebagai air untuk keperluan domestik
seperti memasak, toilet dan cuci-cuci lain biasanya digunakan air dari sumber terdekat seperti Perusahaan air
Minum (PM) lokal maupun dari sumber sumur dalam. Pengolahan biasanya dilakukan secara terbatas seperti
penjernihan dan aerasi terutama untuk mengurangi kadar besi yang biasanya berasosiasi dengan air dari sumber
sumur dalam (deep well).

$umber air baku industri yang memerlukan pembahasan lebih lanjut adalah kebutuhan air dan siIat yang diperlukan
untuk keperluan proses dan sebagai pendingin pada cooling tower di pabrik.Ion Exchange untuk Process dan
Cooling.

Kebutuhan untuk air proses dan pendinginan sangat mendominasi kebutuhan air untuk pabrik karena lebih dari 80
kebutuhan akan air di pabrik dikonsumsi oleh kedua proses tersebut, sementara untuk kebutuhan domestik relatiI
kecil.

Penggunaan kolom atau tabung ion exchange untuk air baku untuk boiler (boiler Ieed water)dan sistim pendinginan
(cooling system) akan meningkatkan eIisiensi kedua sistim peralatan tersebut dengan cara membebaskan pipa-pipa
saluran air dan uap pada sistem tersebut dari karat dan endapan yang mengganggu yang dapat menimbulkan
kebocoran maupun tersumbatnya saluran pada kedua sistim tersebut.

Pabrik kelapa sawit (PK$), kernel crushing plant (KCP), pabrik minyak goreng dan oleochemical adalah pabrik-
pabrik yang banyak menggunakan prinsip thermodinamik pada proses produksinya terutama pada sistim Iraksinasi
dan destilasi dari bahan baku menjadi produk. Peralatan yang digunakan pada proses, hidrolisa, Iraksinasi, dan
destilasi pada dasarnya adalah ketel uap bertekanan yang semuanya menggunakan air sebagai media dan bahan baku
pada proses mereka.

Boiler untuk menghasilkan uap baik basah, kering maupun yang bertekanan menurut kebutuhan prosesnya, selain
digunakan sebagai media thermodinamik, uap yang dihasilkan juga dapat digunakan untuk menggerakkan turbin
pada generator listrik. Penggunaan boiler sebagai peralatan utama membawa konsekuensi pada pemilihan kualitas
air baku (Ieed water) untuk menjaga kontinyuitas operasi serta eIisiensi peralatan tersebut, secara umum untuk
menjaga agar boiler bisa bekerja dengan maksimum serta awet maka diperlukan air yang baik dalam arti air selalu
dijaga agar tidak menjadi penyebab sistem saluran pipa pada boiler menjadi berkarat ataupun tersumbat oleh
endapan-endapan organik yang biasanya dibawa oleh air baku.

ara kerja dan a5ikasi ion exchanger

Pada dasarnya cara kerja kolom ion exchange adalah penukaran ion muatan listrik yang dibawa oleh Iluida dengan
muatan ion pada resin yang tersedian didalam tabung ion exchanger. $ecara umum Iungsi kolom ion exchange
digunakan sebagai media puriIikasi dan Iiltrasi muatan ion mineral pada Iluida yang tidak dikehendaki seperti
Calcium dan Magnesium dan menukarnya dengan Potasium dan Hydrogen, sehingga Iluida yang keluar dari kolom
tersebut memenuhi kriteria yang kita kehendaki.

Ion Exchange sebagai water softening

plikasi ion exchanger sebagai water soItener merupakan Iungsi umum dan digunakan sangat luas di industri yang
memerlukan soIt water untuk proses dan bahan baku boiler . ir baku yang tingkat ke-sadahan-nya (hardness) tinggi
karena kandungan kalsium dan magnesium harus diturunkan dengan cara menggantikannya dengan muatan ion
sodium yang terdapat pada resin.

Proses pertukaran ion terus berjalan sampai tercapai equilibrium dan jenuh dan sesudah kondisi resin jenuh maka
segera dilakukan re-generasi dengan dicuci dengan air yang mengandung garam NaCl tinggi. $oIt water digunakan
untuk boiler Ieed water guna mencegah terjadinya endapan (scaling) pada pipa saluran air baik pada sistim boiler
maupun pada sistim pendingin.

Sebagai media 5urifikasi

Dalam hal penggunaan media ion exchange sebagai puriIier misalnya untuk mengangkat bahan- bahan beracun yang
dibawa oleh Iluida tertentu, maka ion exchanger dapat mengambil ion-ion logam berat seperti Cadmium, Lead dan
Copper dan menggantikannya dengan ion-ion garam sodium dan potassium. da jenis resin ion exchange lain yang
dapat menyaring kontaminan organik air baku dengan menambahkan karbon aktiI pada kolom ion exchange tersebut.

Pemilihan jenis resin akan menentukan Iungsi ion exchange pada pabrik yang menggunakannya sebagai water
soItening, sebagai media Iiltrasi logam berat Iluida tertentu maupun sebagai penyaring mineral pada air baku.
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