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Ion Exchange (IEX) Process
Mohammad Mahdi BazriChemical and Biological Engineering Department
University of British ColumbiaVancouver, BC, CANADA
December 2011-Tehran-Iran
Water analysis
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Introduction3
Initially developed around 5o’s A powerful technology to soften and demineralise water Industrial and domestic applications Industrial and drinking water treatment applications Chemistry and chromatography
Applications Water Treatment Food Industry
• Sugar industry• Dairy products
Chemical Industry• Metal recovery• Selective removal of various elements
Pharmaceutical Industry• Extract and purification of drug
Other Applications• Mining • Enzyme immobilization• Analytical chromatography
Fundamentals5
Exchange of the ions on the resin structure with the ones present in the solution
Schematic cation and anion exchange resin beads
Fundamentals6
Exchange of the ions on the resin structure with the ones present in the solution
Schematic cation and anion exchange resin beads
Resin Structure7
Polystyrene
Polyacrylic Weakly anionic
Strongly anionic
DVB
Resin Types8
Remove hardness/alkalinity and other cations:
• Weakly Acidic Cation Exchange Resins (-COOH)• Strongly Acidic Cation Exchange Resins (-HSO3
- )
Remove anions (NO3, SO4, HCO3) and NOM:
• Weakly Basic Anion Exchange Resins (-N(CH3)2)• Strongly Basic Anion Exchange resins (-N(CH3)3 OH)
o Type I (trimethyl amine)o Type II (dimethyl ethanol amine, lower basicity, better
regenerability)
Terminologies: capacity
Exchange capacity (eq/L)
The number of ion exchange sites
Operating Capacity (useful capacity)
The number of ion exchange sites where exchange has really taken place during the loading run.
Operating capacity < Total capacity
The typical operating capacity of a weak base anion exchange resin is 70 to 90 % of the total capacity.
For weak acid cation resin, operating capacity depends on several parameters, so there is no such simple estimate.
The typical operating capacity of SAC and SBA resins is about 40 to 60 % of their total capacity.
Operating capacity depends on:
Concentration and type of ions to be adsorbed
Service flow rate
Temperature
Type, concentration and quantity of regenerant
Type of regeneration process (co-flow, reverse flow)
Bed depth (reverse flow regeneration only)
Particle size of the ion exchange resins
Performance data and computer programs
Terminologies: exchange zoneThe area between fully regenerated and fully exhausted resin is called exchange zone or reaction zone.
Ion leakage endpoint of run
Weak acid and weak base resins are sensitive to flow rate, higher flow rate longer reaction zones.
SAC and SBA resins are less sensitive to flow rate.
Shorter reaction zone, higher utilization of total capacity , higher achievable operating capacity.
Fine resins have generally higher kinetics: shorter path for the ions to travel inside the resin beads
Water SofteningRemove hardness mainly Ca+2 and Mg+2
Strongly acidic cation exchange resin in Na+ form
Applications• Domestic and industrial water boilers• Laundries, Dish washer• Soft drink plants
Resins used• Amberlite IR120 Na; SR1L Na , AmberjetTM 1000 Na
Treated water quality• Residual hardness < 0.02 meq/L (1 mg/L as CaCO3)
with reverse flow regeneration Regeneration: brine (NaCl as a 10 % solution)
Water Softening
SAC (Na+)
Water Softening
The water salinity is unchanged, only the hardness is replaced by sodium.
Sodium salts have much higher solubility, so they don't form scale or deposits.
A small residual hardness is still there, its value depends on regeneration conditions.
Water De-alkalizationRemove bicarbonate and temporary associated hardnessWeakly acidic cation exchange resin in H+ form
Applications• Beverages, Soft drink plants, municipal water
Resins used• Amberlite IRC86 (industrial), Amberlite PWC13
(municipal), ImacTM HP333 and HP335 (household filter cartridges)
Treated water quality• Endpoint at 10 % of the raw water alkalinity• Contains CO2 which requires degasifier
Regeneration: Acid (preferably HCl at 5 % concentration)
Degasification2 R-H + Ca (HCO3)2 R2-Ca+2 H+ + 2 HCO3
-
H+ + HCO3CO2 + H2O (CO2 solubility @ 25 : 1.5 g/L)
• Reduce the ionic load thus regenerant• CO2 residual 10 mg/L
Degasifier
Degasifier• Atmospheric degasser (bicarbonate + CO2 < 0.6
meq/L)
• Forced draft degasser
• Thermal degasser, (O2-CO2)
• Vacuum degasser, (1-5 kPa, O2-CO2)
• Membrane degasser
Small size, for RO permeates with low pH and high
free CO2, small demineralization systems
Water DemineralizationRemove all the ions from water CIX (H+) - AIX (OH-)Treated water contains only traces of sodium and silica
Applications• Beverages, soft drink plants, municipal water
Resins used• Amberlite IRC86 (WAC), Amberlite IR120 or Amberjet
1000 or 1200 (SBA), Amberlite IRA96 or IRA67 (WBA), Amberlite IRA402 or Amberjet 4200 or 4600 (SBA)
Treated water quality (lower than RO or Distillation)• Conductivity: 0.2 to 1 µS/cm • Residual silica 5 to 50 µg/L
Regeneration: strong acid and caustic soda
Operational aspect Column Operation
• Co-flow regeneration• Counter flow regeneration
Batch (well-mixed)• MIEX, other IEX resins
Fluidized or Suspended • MIEX or any other IEX resin
Column Operation
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Column operationFreeboard columns
• Air or water hold down vessels (requires inert resin)• Stratified (weak/strong mix) vessels• Split flow regeneration unit (avoid disturb, hard to adjust)
Packed bed columns• Very little extra space, Smaller and cheaper• Usually higher depth• Floating bed with almost not fluidization • WAC/SAC and WBA/SBA are separated via a plate with
nozzlesMix beds
• Hard to regenerate • Not very efficient due to shallow depth
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Practical limitations
Affinity difference
Effective for low concentrations (brackish or sea water )
Only ionized targets can be eliminated
Regeneration (cost, environmental burden)
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Practical limitations
Affinity difference
Effective for low concentrations (brackish or sea water )
Only ionized targets can be eliminated
Regeneration (cost, environmental burden)
Regenerant
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• NaCl or KCl (10% ) for SAC and SBA• HCl for nitrate removal• Demineralization (SAC)
o HCl (5%), efficient no precipitationo H2SO4 (0.7-6%), cheaper and easier to store , less
efficient, potential for precipitationo HNO3, exothermic reaction, dangerous, not
recommended
• De-alkalization WAC , HCl, H2SO4 (0.7%)• SBA , NaOH (4%)• WBA, NaOH, NH3, bicarbonate
Regeneration
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Co-flow regenerationReverse exchange (displacement of low affinity with high affinity ions)Requires large excess of solution to fully regenerateLeakage in the next run
Counter-flow regenerationHigher reg. Efficiency, lower reg. quantityLower elution leakageLower resin inventoryImproved water qualityHard to keep the resin bed consolidatedResin mixingPurity of the regenerant
Regeneration steps
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• Backwash the bed to remove the suspended solids (co-flow)• Regenerant injection at low flow-rate (20-40 minutes)• Rinsing • Washing with service water
Regeneration ratioAmberjet 1200 regenerated with 55 g HCl per litreoperating capacity : 1.20 eq/L 55 g/L HCl = 55/36.5 = 1.507 eq/L Regenerant ratio = 1.507/1.20 = 1.26 = 126 %
Regeneration ratio
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• WAC resins: A safe number is 105 to 110 %.
• WBA resins: 115 to 140 %, due to presence of some strongly basic functional groups.
• SAC resins: Regenerated with sulphuric acid, larger excess (at least 40%) than those regenerated with HCl.
• SBA resins: Depends on the type of SBA resin (styrenictype I, type II or acrylic resins). Not economical to regenerate the resin totally.
• SAC and SBA resins: Larger excess than their weak counterparts.
Thoroughfare regeneration
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Throughput32
Volume produced until the cartridge has to be replaced
• Salinity of the feed water • Volume of resin in the cartridge (throughput is
approximately proportional to resin volume) • Type of resin used • Quality and efficiency of the off-site regeneration process • Endpoint (conductivity at which the unit is considered
exhausted)
With good resins and good regeneration, the throughput can be approximately calculated as:
Throughput [L] = 500 × (Resin volume [L]) / (Salinity [meq/L])
Kinetics33
Kinetics34
In normal practice, solution is withdrawn at the outlet of the column so the equilibrium is permanently shifted to the right.
R-A+ + B+ R-B+ + A+
Na+-form SAC resins initially remove divalent cations fromwater, but not other monovalent cations (selectivity)
2 R-Na + Ca+2 (HCO3–)2 R2-Ca + 2 Na+ HCO3
–
Selectivity35
WAC (H-form) resin removes only hardness, and only when alkalinity is present.
For softening WAC resin must first be converted to the Na-form with an alkali.
OH– form resins are not used to remove bicarbonate or carbonate from neutral water when it contains hardness (precipitation risk)
Selectivity36
OH-form resin reacts with very weak acids, such as silica (SiO2) or boric acid (H3BO3).
Special SBA resins with different functional groups are used with an increased nitrate, sulphate, perchlorateselectivity.
R-OH + H+HSiO3– R-HSiO3 + H+OH–
Selectivity37
Selectivity38
Selectivity39
Selectivity40
Selectivity41
Selectivity42
Selectivity43
Nitrate removal
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RSBA-Cl + NO3- RSBA-NO3 + Cl-
SAB (Cl-)
Amberlite PWA5 –PWA15Purolite A520E
SIR-100-HP
Methemoglobinemia, also known as “blue baby syndrome
Nitrate removal
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Anion resins are less dense and require a backwash flow rate about 1/3 that of softening resin.
salt concentrations are typically applied at 4 percent to 8 percent.
Regenerant levels must be high enough in nitrate removal to ensure that nitrate leakages are kept to acceptably low levels.
Natural Organic Matter
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Removal Mechanisms by IEX resins :• Adsorption (blocking exchange sites)• Size Exclusion (blocking exchange sites)• Ion exchange (favourable)
Easier regeneration (lower conc., lower flow rate/contact time)
Hydrophobic Hydrophilic
Neutral
Very Complex Mixture
IEX for NOM removal47
• A relatively recent concept
• Polystyrene resins are more hydrophobic /selective thanPolyacrylic resins.
• Polystyrene resins have shown stronger affinity witharomatic moieties.
• Competition kinetics exist between NOM and inorganicIons
SO4 > NO3 > NOM > Cl > HCO3 > OH > F
Important characteristics of resin48
• Functional group (strong or weak basic)
• Backbone structure (acrylic or styrene)
• Resin water content
• Physical form (gel or macroporous)
• Bead size
• Treatment process
IEX for NOM removal49
• Efficient reactor design
• Enforce IEX as the dominant removal mechanism• Shorter contact time
• Combined different IEX resins
• Enhance the NOM removal• Combination of weakly-strongly basic IEX resin• Combination of Polystyrene-Polyacrylic IEX resins
• Microbial growth on IEX resins
• Disinfection• set-up configuration
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