Ion exchange process

Dr. Akepati S. Reddy Associate Professor, Thapar University Adjunct Scientist, TCIRD Patiala (PUNJAB) ± 147 001

Ion exchange process
Ion exchange process: displacement of ionic species from ion-exchange resin by different ionic species in solution Used for the removal of undesirable anions and cations from water and wastewater Used in water softening ± Na+ ions from cation exchange resin are replaced by Ca2+ and Mg2+ ions of the water Used in demineralized water production
± H+ ions from cation exchange resin are replaced by different cations of water ± OH- ions from anion exchange resin are replaced by different anions of water

Used for the removal of nitrogen, heavy metals and total dissolved solids from wastewater By adequate selection of ion exchangers most wastewater problem of an inorganic nature can be handled

Ion exchange process
The process can be a batch process or a continuous process Batch process:
± ion exchange resin is stirred with water until the ion exchange reaction is complete ± spent resin is removed, regenerated and reused again

Continuous process
± Ion exchange resin is placed in a bed or packed column ± Water is passed through it usually down-flow ± when ion exchange capacity of the resin is exhausted the column is backwashed (to remove trapped solids), regenerated and reused again

Ion exchange resin
Naturally occurring ion exchange material
± Zeolites (alumino-silicates with sodium as the mobile ion)

Synthetic ion exchange materials
± Resins are porous phenolic polymer particles of 0.5 mm diameter with functional groups that reversibly exchange ions in solution introduced by reacting the polymeric matrix with a chemical compound containing the desired functional groups ± Number of functional groups determine the exchange capacity ± Functional groups determine the ion selectivity and position of ion exchange equilibrium ± Manufactured by copolymerization of styrene and divinylbenzene ± Styrene serves as a basic matrix and divinylbenzene is used to cross link the polymer and produce soluble tough resin ± Functional groups are added by chemical reaction procedures

Ion exchange resin
Important properties of the ion exchange resins are
± Exchange capacity of the resin Expressed as eq/l or eq/kg ± also often expressed in terms of grams of CaCO3 per cubic meter resin Capacity of synthetic resins is 2 ± 10 eq/kg Capacity of zeolite cation exchanger is 0.05 to 0.1 eq/kg Construct breakthrough curve for estimating the capacity Break through point and exhaustion point (corresponds to 5% and 95% of influent concentration!) For use to exhaustion point operate columns in series and organize regeneration schedules ± Resin particle size - Rate of exchange is proportional to the inverse of the square of the particle diameter ± Stability of the resin - important from the long term performance point of view

Breakthrough curve for ion-exchange resin

Ion exchange resin
Synthetic resins are five types ‡ Strong acid cationic
± behave similar to a strong acid ± Functional group could be RSO3H or RSO3Na ± Ion exchange process involved

RSO3 H  Na  m RSO3 Na  H 
RS Na  Ca 2  m RS 3

2 Ca  2 Na  3

‡ Weak acid cationic
± have weak acid functional groups (RCOOH/RCOONa) ± behave like weak organic acid ± Ion exchange process involved is

RCOONa  Ca 2  m ( RCOO ) 2 Ca  2 Na 

Ion exchange resin
‡ Strong base anionic
± Have strong base functional groups (RR3NOH) ± Used in hydroxide for water deionization ± Ion exchange process involved is
' ' RR3 NOH  Cl  m RR3 NCl  OH  ‡ Weak base anionic

± Have weak base functional groups (RNH3OH/RNH3Cl) ± Degree of ionization is pH dependent ± Ion exchange process involved is

RNH 3OH  Cl  m RNH 3Cl  OH 
2 RNH 3Cl  SO4  m ( RNH 3 ) 2 SO4  2Cl  ‡ Heavy metal selective chelating resins

± Functional group is usually EDTA (R-EDTA-Na) ± Behaves like weak acid cationic resin ± Exhibits high degree of selectivity for heavy metal cations

Ion exchange chemistry & selectivity coefficient 
nR  A   B  n m Rn B  n  nA

?A A ?R B A! K ?R A A?B A 
n   n  n n n

A p B  n

KA+pB+ is selectivity coefficient R-A+ is concentration of A on the resin A+ is concentration of A in solution Rn-B+n is concentration of B+n on resin B+n is concentration of B in solution

Selectivity coefficient depends on
± Nature and valence of the ion ± Type of resin and its saturation ± Ion concentration in the wastewater

‡ The selectivity coefficient is valid over a narrow pH range ‡ At low concentrations selectivity coefficient for exchange of monovalent ions by divalent ions is larger than that for exchange of monovalent ions by monovalent ions

Regeneration of ion exchange resin beds
‡ Backwash removal of solid deposits ‡ Passing of regenerating chemical solution
± 2-5% solution (by weight) of NaCl or H2SO4 or HCl for cation exchange resin beds (5-10% in case of NaCl) ± 5-10% solution (by weight) of sodium or ammonium hydroxides for anion exchange resin beds

‡ Rinsing of the beds to remove residual regenerant ‡ Generates regenerant waste consisting of
± cationic salts in case of cation exchange resin beds ± Anionic salts in case of anion exchange resin beds

‡ Volume of wastewater generated may be 10-15% to volume of water treated

Run a complete cation-anion analysis of the water/ wastewater to be treated
± Express concentration of individual ions in meq/liter or as concentration as CaCO3

Obtain information on TDS, dissolved CO2 and SiO2 and pH Find exchange capacity of the resin by laboratory tests Estimate regenerant requirements of the resin (weight per unit volume of the resin)
± Degree of attaining theoretical ion exchange capacity depends on the amount of regenerant employed ± Performance curves in this regard may be supplied by the supplier of the resin

Find out rinse water requirements (liters/unit volume of resin)
± Can be determined in laboratory or may also be available from the resin manufacturers

Decide on column dimensions: decide bed depth (free space over the bed is about 50% of bed depth)
± Wastewater application rates may range from 0.2 to 0.4 m3/m2.min ± Typical bed depths are 0.75 to 2.0 m

Decide on number of columns based on
± reliability of operation needed ± need for use of the bed till exhaustion point

Ion-exchange process: Nitrogen control
Ammonical (NH4+) and nitrate (NO3-) ionic forms are typically removed Clinoptilolite (a natural zeolite) is best for NH4+ removal (has greater affinity for NH4+ ions) ‡ On exhaustion, the zeolite is left for regeneration with lime ± over time (at high pH) NH4+ ion is converted to NH3 and removed through stripping ‡ Formation of CaCO3 precipitate within the bed and in the stripping tower and piping appurtenances is a problem
± Backwashing can take care of the precipitates in the zeolite bed

Synthetic resins are used for nitrate removal ‡ The removal by conventional synthetic resins suffers from
± Nitrate having lesser affinity than sulfate (but has greater affinity over chloride and bicarbonate) ± higher sulfate levels (>25% of nitrate plus sulfate), NO3- selective resins are used ± Since the performance of NO3- selective resins vary with the composition of the wastewater pilot testing is usually needed

Ion-exchange process: Heavy metals
ion-exchange processes for metal removal is economically feasibility if recovery of valuable metals is involved
± Use of resins that have high selectivity for the desired metals also improves the economics

Materials used include zeolites, weak & strong anion & cation resins, chelating resins and microbial and plant biomass
± Clinoptilolite and chabazite have been used to treat wastewater with mixed metal backgrounds ± Chelating resins, aminophosphonic and iminodiacetic resins, have high selectivity for metals such as Cu, Ni, Cd and Zn

Selectivity of resin, pH, temperature, other ionic species and chemical background all influence the exchange process
± Ion exchange process is highly pH dependent - most metals bind better at higher pH (less competition from protons) ± Presence of oxidants, particles, solvents, and polymers may affect the performance of the ion exchange resin

Ion-exchange process: Operational considerations
Problems associated with the ion exchange process
± Need for extensive pre-treatment of the wastewater ± Requirement of complex regeneration system ± Limited life of the ion exchange resin ± Fouling of the resin ± Residual organics can cause resin binding ± High influent TSS can clog or plug the ion-exchange beds

‡ Pre-filtration or use of scavenger exchange resin can take care of many wastewater treatment related problems ‡ Regenerants & restorants should be capable to remove both inorganic and organic materials from spent resin ‡ The restorants found successful in removing the organic materials include NaOH, HCl, methanol and bentonite

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