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Basic Ion Exchange and Applications
Bill Koebel North East Technical RepResinTech, Inc.
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ResinTech, Inc.
Bill Koebel Northeast Regional Sales Manager Ion Exchange Resins and Activated Carbon Experts in water and wastewater ion
exchange applications
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ResinTech History
Founded in 1986 Located in West Berlin, NJ
– Processing plant– Laboratories– Sales & Marketing– Warehousing
Other Warehouses– Florida– Texas– California
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ResinTech Services
Technical– Resin Rating
Projections– Laboratory analysis– Resin selection– Troubleshooting– Comprehensive
website
People– All sales staff technical
experts– Available by phone,
fax, or email for immediate assistance
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Applications
Pharmaceutical Semiconductor Textile Automotive Electroplating Beverage Hemodialysis Pulp & Paper
Nuclear Power Aquaculture Laboratory Portable exchange Residential EDM Remediation Municipal
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Topics of Discussion
History How resins are made Basic Terminology Ion Exchange Process Resin Types Basic Applications Q & A
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Early Ion Exchange History
Desalting of brackish waters mentioned in:– The Bible & Ancient Greeks– Sir Francis Bacon
1850 - Thompson & Way report to Royal Agriculture Society– Exchange of ions in soil– Attributed to aluminum silicates
1858 - Eichorn proves reaction is reversible
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Synthetic Exchangers
1905 - Gans develops synthetic exchanger– Called Zeolites, from Greek words Zein and
Lithos 1913 - First synthetic zeolites marketed in
America 1944 - D’Alelio develops cation exchanger
based on styrene/DVB copolymer 1948 - Anion exchanger developed
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Ion Exchange Today
Tiny plastic beads that have been chemically activated
They are manufactured products that are made from petrochemical based monomers
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Make the Beads
Styrene DiVinyl Benzene (Crosslinkage) Suspension Polymerization No Water Content Neither Cation or Anion resin Beads are called co-polymer Functionalized to an Ion Exchange resin
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Material Properties
Size between 16 to 50 U.S. Mesh Resistance to fracture Insoluble Permanently attached sites High capacity for ions Temperature effects negligible
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What is Ion Exchange?
Exchange of undesirable ions for desirable ones
Selectivity drives the reaction The process is reversible via regeneration
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Definition of Ions
Cations – Positively charged ions dissolved in solution
Anions – Negatively charged ions dissolved in solution
Law of Electroneutrality – In any solution the number of cations equals the number of anions
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Basic Products
Cation Resins Anion Resins Mixed Bed Resins Selective Resins & Zeolites
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Cation Resins
Used to remove cations from water– Hardness, Heavy Metals or all cations
Strong Acid Cation– Typically use Na+ or H+ forms
Weak Acid Cation– Typically use Na+ or H+ forms
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Common Cations
Iron Fe2+
Calcium Ca2+
Magnesium Mg2+
Sodium Na+
Potassium K +
Hydrogen H +
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Anion Resins
Used to remove anions from water– Complexes, oxy anions (Cromate, Sulfate, etc.)
Strong Base Anion– Typically use Cl- or OH- forms
Weak Base Anion– Typically use Cl- or free base forms
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Common Anions
Phosphate PO4-3
Sulfate SO4-2
Nitrate NO3-
Chloride Cl -
Bicarbonate HCO3-
Hydroxide OH-
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Selective Resins & Media
Used to remove various ions from water– Heavy metals most common
Chelating Resins – Typically use Na+ or H+ forms– Many types
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Ion Exchange Processes
Softening Dealkalization Deionization Nitrate removal Condensate polishing Pollution control
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Selectivity The attraction, of one ion over
another, to an ion exchange resin Function of ion charge, size and
concentration For SACs and SBAs:
– Bigger the ion, higher the charge, the more selective the ion becomes
– I.e. -3>-2>-1 and +3>+2>+1
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Inside the Resin Bead
PS-DVB Resin bead
Crosslinks betweenpolymer chains (DVB)
Polymer chains(polystyrene- PS)
-
-
-
-
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-
- -
-
Functional siteson polymer
Inside the Resin Bead
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+-
++
+
- -
-
Functional sitesshown occupied
by regenerant ions (i.e. H+)
Inside the Resin Bead
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+-
++
+
- -
-
Water contactsresin beads. Beadsare ~50% water.
The Resin Bead in Action
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+-
++
+
- -
-
Water containing unwanted ions, in contact with water inside beads, allows ions todiffuse in/out of beads.
The Resin Bead in Action
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-
- -
-
Calcium ions enter
Ca+2
+++
+
Ca+2
Hydrogen ions are exchanged and exit producingimproved water
The Resin Bead in Action
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Ion Exchange - High Purity Water
A-
-
-- -
-
--
--
+
++
+
+
++
+
H +
H +
H +
H +
OH_
OH_
OH_
OH_
OH_
OH_
SO42-
HCO3-Cl
-Ca 2+
Na +
Mg 2+
H +
C
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Ion Exchange - High Purity Water
A-
-
-- -
-
--
--
+
++
+
+
++
+
H +
H +H +
H +
OH_
OH_
OH_
OH_
OH_
OH_ SO4
2-
HCO3-
Cl-
Ca 2+
Na +
Mg 2+
H +
C
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Ion Exchange - High Purity Water
A-
-
-- -
-
--
--
+
++
+
+
++
+
H +
H +H +
OH_
OH_
OH_
SO42-
HCO3-
Cl-
Ca 2+
Na +
Mg 2+
C
HO
H(-)(+)
HO
H(-)(+)
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Definition Chelating ResinChela: Gr. The pincer like claw(s) of a crab, lobster,
or scorpion.
Ligand: The chemical term for an electron pair donor (Lewis base) when it forms a bond with a metal ca
Chelating Resin: Ion exchange resins that have ligands that can bon with metal cations. The ligands may be in additio to or in place of conventional ion exchange sites.
Selectivity: The preference of an ion exchange material fora particular ion. Selectivity is always relative toa particular operating condition.
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Chelating Lobster
Chela
Fish
Lobster
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Chelating & Selective Resins True Chelating Resins
– Iminodiacetate (SIR-300)– Aminophosphonic (SIR-500)– Picolyamine (SIR-1000)
Selective Resins– Thiol (SIR-200)– Thiouronium (SIR-400)– Exhausted Weak Base (WBMP & SIR-700)– Natural Zeolites (SIR-600, greensand, & others)– Weak Acid Cation Resins (WACG & WACMP)– Nitrate & Perchlorate Selective (SIR-100 & SIR-110)
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What Makes a Chelating Resin Selective?
Ionic Charge (Valence)– Most chelating resins prefer di-valent ions to mono-valent or tri-
valent ions, because the chelant group has two “Chela” (claws). Hydrated Ionic Radius
– When the size of the hydrated radius of the ion closely fits the space between the “Chela” the resin is very selective for that particular ion.
Ligand Bonding– Nitrogen (and oxygen) can possess an exposed electron pair,
making them Lewis bases (electron pair donors). Metals that are Lewis acids form ligands with Lewis bases.
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Iminodiacetate Chelant“SIR-300”
CH CH2
CH2 NCOOCH2
CH2 COOCu+
+
Sodium Form (unstable charge balanc
Copper Form (very stable charge balan
CH CH2
CH2 NCOOCH2
CH2 COO Na
+
+
Na
Ligand bonding
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Iminodiacetate Chelant (SIR-300)Operating Limits
Dissolved Solids– Unaffected by Sodium and other Group 1A metals (except
hydrogen)– Practically unaffected by Calcium and other Group 2A metals– Selectivity is affected by other complexing agents
EDTA blocks exchange entirely for many metals Ammonia affects exchange significantly Chloride has a minor effect on selectivity
pH– Optimum pH is usually slightly acidic– Selectivity is lower at high pH– Loses selectivity below pH of approx.. 2.0
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Iminodiacetate Chelant (SIR-300)Criteria for Selection
Removal of divalent Group IV (transition) metals High TDS background (greater than 1000 ppm) Significant calcium concentration present (equal to
or greater than the metal concentration) pH is slightly acidic (optimum pH is approx. 4)
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Capacity of SIR-300Various Metals (at saturation)
0
1
2
3
4
5
0 1 2 3 4 5
inlet pH
Cap
acit
y (l
bs
met
al/ c
uft
)
CopperNickelIron
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TDS Limits of various ResinsUsed for Metals Removal
Strong Cation Resin (Hydrogen form) 500 ppm Strong Cation Resin (Sodium form) 1,000 ppm Weak Cation Resin (Sodium form) 10,000 ppm Chelating Cation Resin (Sodium form) no limit Mixed Bed Resin 500
ppm
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What do we need to Know? Viability of ion exchange
– TDS (or conductivity) with min and max if variable– pH and Temperature with min and max if variable– basic inorganic analysis of ions (Ca, Mg, Na, Cl, SO4)– presence or absence of oxidants– presence or absence of complexing agents– level and type of organic molecules– level of suspended solids
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Definitions
PPM (mg/l) – Parts per Million (milligrams per liter) a measure of the concentration of ions as defined by their weight
“as CaCO3” – A measure of the concentrations of ions based on the number of ionic charges.
Grains – a very small unit of weight, originally equal to a grain of wheat.
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Conversion Factors
7000 grains = 1 pound 17.1 PPM (as CaCO3) = 1 grain per gallon 7.48 gallons = 1 cubic foot 40% = resin void volume
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Resin Selection
Feedwater analysis Desired effluent quality Operating conditions Economics Type of equipment Regeneration chemicals available
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Typical Resin Life
Operating Life– Cation – 8 to 10 years– Anion – 4 to 6 years
Factors– Oxidants– Temperature– Regeneration frequency
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Factors Affecting Resin Performance
Oxidation– Chlorine– Temperature
Loss of capacity Fouling
– Organic– Oil
Loss of resin– Backwash loss
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Equipment Troubleshooting
Equipment Failure Distribution Problems Control malfunctions Operator error Changing Water analysis
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Types of Waste Treated
Rinse Waters– Acid and neutral Rinses– Alkaline cyanide Rinses– EDM Machines– PCB washers
Plating Baths– Tri chrome
Wastewater– End of pipe polishing
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Typical Plating Rinse Tank Set-up
PlatingBath
DeadRinse
FirstRinse
SecondRinse
FinalRinse
IX Columns
Pre-filter
Sump
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Misc Ion Exchange Possibilities
Silver (and other precious metals) Lead (and other heavy metals) pH control (by ion exchange buffering) Fluoborate (and other exotic ions) Carbonate Removal (from cyanide baths)
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Bulk Regeneration for base transition metals
pH Adjustment Carbamate precipitation Filter Press Final Filtration Ion Exchange Polishing
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Bulk Waste Treatment Schematic
Ion ExchangeColumns
Pre-filter
Filter Press
MixTank
Waste Inlet
FinalwasteTank
AcidCausticPolymerCarbamate
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Regeneration Sequence
Backwash Chemical Injection Displacement / Slow rinse Fast Rinse
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Backwash
A flow of water is passed upward through the resin bed
The resin bed expands and fluidizes Suspended solids are removed The resin bed is classified, increasing the
void space Mixed bed backwash also serves to separate
the cation and anion beads
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Chemical Injection
A dilute solution of acid or caustic flows through the bed
The relatively high concentration of hydrogen or hydroxide ions causes a reverse exchange
The resin is restored to the hydrogen or hydroxide form
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Displacement Rinse
Increases contact time between regenerant and the bottom of the bed
Helps push remaining regenerant through the bed without significant mixing
Begins the rinse process
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Fast Rinse
Removes the last traces of regenerant chemical from the resin
Prepares the resin for the next service cycle
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Effluent Water Quality
Selectivity and Leakage – least strongly held ion first to come off
Regeneration Dose – the higher the dose, the lower the leakage
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Questions & Answer
Bill Koebel North East Technical RepResinTech, Inc.