IonExchangeResins

Generalresininformation
FunctionalGroups
Synthesis
Types
Structure
ResinData
Kinetics
Thermodynamics
Distribution
Radiationeffects
IonSpecificResins

71

IonExchangeResins
Resins
Organicorinorganicpolymerusedto
exchangecationsoranionsfromasolution
phase
GeneralStructure
Polymerbackbonenotinvolvedinbonding
Functionalgroupforcomplexinganionor
cation
72

Resins
Properties
Capacity
Amountofexchangeableionsperunitquantityof
material
* Protonexchangecapacity(PEC)
Selectivity
Cationoranionexchange
* Cationsarepositiveions
* Anionsarenegativeions
Someselectivitieswithingroup
* Distributionofmetalioncanvarywithsolution

73

Resins
Exchangeproceedsonanequivalentbasis
Chargeoftheexchangeionmustbeneutralized
Z=3mustbindwith3protonexchanginggroups
OrganicExchangeResins
Backbone
Crosslinkedpolymerchain
* Divinylbenzene,polystyrene
* Crosslinkinglimitsswelling,restrictscavity
size

74

OrganicResins
Functionalgroup
Functionalizebenzene
* Sulfonatedtoproducecation
exchanger
* Chlorinatedtoproduceanion
exchanger

75

76

77

ResinSynthesis
HO

OH

HO

OH

NaOH,H 2 O
resorcinol

HCOH

OH

n
OH

OH

OH
NaOH,H 2 O

catechol

HCOH

n
78

Resins
Structure
Randomnessincrosslinkingproducesdisordered
structure
Rangeofdistancesbetweensites
Environments
* Nearorganicbackboneormainlyinteracting
withsolution
Sorptionbasedresins
Organicwithlongcarbonchains(XADresins)
Sorbsorganicsfromaqueoussolutions
Canbeusedtomakefunctionalizedexchangers

79

OrganicResingroups

SO3 H

Linkagegroup

CH2 Cl

Chloride

Cationexchange

CH 2 N(CH3 )3 Cl

Anionexchange

710

Resin
Structure

711

InorganicResins
Moreformalizedstructures
Silicates(SiO4)
Alumina(AlO4)
Bothtetrahedral
Canbecombined
* (Ca,Na)(Si4Al2O12).6H2O
Aluminosilicates
* zeolite,montmorillonites
* Cationexchangers
* Canbesynthesized
Zirconium,Tinphosphate

712

Zeolite

713

InorganicIonExchanger
OPO(OH)2 OH

OH
Zr

Zr

Zr

OPO(OH)2
O

Zr

OPO(OH)2 OPO(OH)2 OPO(OH)2 OPO(OH)2

Easytosynthesis
Metalsaltwithphosphate
Precipitateforms
Grindandsieve
Zrcanbereplacedbyothertetravalentmetals
Sn,Th,U
714

Kinetics
Diffusioncontrolled
Filmdiffusion
Onsurfaceofresin
Particlediffusion
Movementintoresin
Rateisgenerallyfast
Increaseincrosslinkingdecreaserate
Theoreticalplatesusedtoestimatereactions
Swelling
Solvationincreasesexchange
Greaterswellingdecreasesselectivity

715

Selectivity
DistributionCoefficient
D=Ionpermassdryresin/Ionpervolume
Thestabilityconstantsformetalionscanbefound
Basedonmolality(equivalents/kgsolute)
Ratio(neutralizedequivalents)
Equilibriumconstantsrelatedtoselectivity
constants
Thermodynamicconcentrationbaseduponamountofsites
available
Constantscanbeevaluatedforresins
Needtodeterminesiteconcentration

716

717

718

719

720

721

722

723

724

725

726

727

728

Radioactiveconsiderations

Highselectivity
CsfromNa
Radiationeffects
Notsensitivetoradiation
Inorganicstendtobebetterthanorganics
Highloading
Needtolimitresinchange
Limitedbreakthrough
Easeofchange
Flushingwithsolution
Goodwasteform
Radioactivewaste

729

730

HanfordTanks
177Tanks
EachTank3,800,000Liters
Threesections
Saltcake
Sludge
Supernatant
InterestedinextractingCs,Sr,Tc,andActinideswith
Silicatitanates
Resorcinolformaldehyde
CS100(syntheticzeolite)

731

IonSelectiveResins
Selectedextractionofradionuclides
Csforwastereduction
AmandCmfromlanthanides
Reprocessing
Transmutation
Separationbasedondifferencesinradiiandligand
interaction
sizeandligand
Prefersolidliquidextraction
Metalionusedastemplate

732

CharacteristicsofResins
Abilitytoconstructspecificmetalionselectivity
Usemetalionastemplate
EaseofSynthesis
Highdegreeofmetalioncomplexation
Flexibilityofapplications
Differentfunctionalgroups
Phenol
Catechol
Resorcinol
8Hydroxyquinoline
733

ResinSynthesis
Catecholformaldehyderesin(CF)
Resorcinolformaldehyderesin(RF)
Phenol8hydroxyquinolineformaldehyderesin
(PQF)
Catechol8hydroxyquinolineformaldehyderesin
(CQF)
Resorcinol8hydroxyquinolineformaldehyderesin
(RQF)
ResinsanalyzedbyIRspectroscopy,moistureregain,
andionexchangecapacity
734

OH

HO

OH

OH

Resorcinol Formaldehyde Resin

OH

Catechol Formaldehyde Resin

OH

OH

x = 0, Phenol-8-Hydroxyquinoline Formaldehyde Resin

x = 1, Catechol-8-Hydroxyquinoline Formaldehyde Resin
735
x = 1, Resorcinol-8-Hydroxyquinoline Formaldehyde Resin

Experimental
IRspectroscopy
Resincharacterization
OH,C=CAromatic,CH2,CO
Moistureregain
24hourheatingof0.1gat100C
Ionexchangecapacity
Titrationof0.25gwith0.1MNaOH

736

MoistureRegainandIEC
Resin
CF
RF
PQF
CQF
RQF

Moisture
%
20
40
10
20
19

IEC
meq/g
8.6
11.5
5.9
9.6
9.9

TheoryIEC
%
55
74
80
70
70

Phenolic resins have lower IEC

8-hydroxyquinoline increase IEC

737

Experimental
Distributionstudies
WithH+andNa+forms
0.05gresin
10mLof0.005.1Mmetalion
MetalconcentrationdeterminedbyICP
AESorradiochemically
Ci Cf V
Distributioncoefficient
D
Ci=initialconcentration
Cf
m
Cf=finalsolutionconcentration
V=solutionvolume(mL)
m=resinmass(g)

738

CesiumExtraction
1.8
catechol resorcinol

1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
Li

Na

Rb

Cs

Alkali Metals
739

DistributionCoefficientsforGroup1
elements.
Allmetalionsashydroxidesat0.02M,5mLsolution,25mg
resin,mixingtime5hours
D(mL/g(dry)
Na
K
Rb

Resin

Li

PF
RF
CF

10.5 0.01
93.9 59.4
128.2 66.7

8.0
71.9
68.5

13.0
85.2
77.5

Cs

Selectivity
Cs/Na
Cs/K

79.8
229.5
112.8

7980
3.9
1.7

10
3.2
1.6

740

CesiumColumnStudieswithRF
pH14,Na,Cs,K,Al,V,As
40

0.1 M HCl

1.0 M HCl

Eluant Concentration (g/mL)

35
30
25
20

Cs
Na
K
Al

15
10
5
0
0

6
8
10
Volume Eluant (mL)

12

14

16

741

Eu/LaCompetitiveExtraction
Distribution Coefficients, 2.5 mM Eu,La, pH 4
Resin
CF
RF
PQF
CQF
RQF

La
2.38x106
2.59x106
64.4
98.1
78.4

Eu
2.03x106
2.18x106
400
672
817

Eu/La
0.85
0.84
6.21
6.85
9.91

742

10
9
8
7
6
5
4
3
2
1
0

CF

RF

PQF

CQF

RQF

Resin
[Eu]=[La]=0.0025molL1,T(shaking)=20h,m=0.05g

743

EuLaSeparation
12
10

D Eu/D

La

8
6
4

CQF
PQF
RQF

2
0
0

20

40

60
80
100
Mixing Time (Hours)

120

140
744

Studieswith243Am
ConditionssimilartoEustudies
10mLsolution
0.05gresin
RF,CF,PQF,RQF,CQF
millimolarAmconcentration
Analysisbyalphascintillation
>99%ofAmremovedbyCF,RF,PQF
95%ofAmremovedbyCQF,RQF
243AmremovedfromresinbyHNO3

745

IonSpecificResins
Effectivecolumnseparationpossible
Phenolexhibitsselectivity
Incorporationof8hydroxyquinolineleadsto
selectivity,butlowerextraction
Eu/Laseparationpossible
Possibletoprepareionspecificresinsforthe
actinides

746