Chapter 4: Removal of specific

ions
Decrease of salt concentration (brackish
water or seawater)
Complete ion removal
Heavy metals: Pb, Cd,…
Ba, Ra, U,…
Calcium: later
Sulfates, fluoride, arsenic, chromate,…
(Nitrate)
Removal of ions by RO
Also (small) organic compounds!
Ions:
Divalent > 99%
Monovalent ~ 98%
Viruses,… « 100% »
Osmotic pressure determines energy
consumption
Typical pressures ~ 20-50 bar
 Nanofiltration Reverse
(NF) osmosis (RO)
Permeability 1.5-15 0.05-1.5
(l / h.m².bar)
Pressure difference 5 – 20 20-100
(bar)
Pore size (nm) 0.1 - 5 0.05-1
Retention
Monovalent ions - +
Divalent ions + +
Small organic -/+ +
compounds
macromolecules + +
Particles + +
Separation principle Sieving, charge diffusion
interactions,
diffusion
Spiral wound modules
Full scale RO
Configurations
Limitation of RO: salinity
Limitation of RO: salinity
Ion exchange
Ions in solution  ions on resin
An old process…
Moses sweetened the waters of Mariah (Exodus
15:23-25)
320 BC: Aristotle used 20 earthen containers with a
material that has ion exchange properties: seawater
desalination
1854: first systematic report describing ion exchange
phenomena (ammonium ions adsorbed on soil,
releasing Ca in the same quantities)
Natural materials: clays, peat, charred bone, soils,
silicates, zeolites
Synthetic ion exchangers: polymeric functionalized
resins (since 1935)
Ion exchange
Types:
Strong acid cation exchanger
• Low pKa (<0), releases a proton over a wide pH range
(1-14)
Weak acid cation exchanger
• pKa = 4-5 → strong pH dependence!
Strong alkaline anion exchanger
• pKb = 0-1 → anion exchange when pH < 13
Weak alkaline anion exchanger
• pKb = 5.7-7.3 → pH below 8.3 to 6.7
Ion exchange properties
Polymer properties:
• Structure
• Degree of crosslinking
• Functional groups
• Ionic form
• Water content – (reversible) swelling
• Ion exchange capacity
• Chemical and thermal stability
Particle size – uniformity – density – total weight –
% resin – sphericity
Ion exchange
Strong acid cation exchangers, strong alkaline
basic anion exchangers
RH + NaOH  RNa + H2O (R ~ sulfonyl)
ROH + HCl  RCl + H2O (R ~ quaternair
ammoniumhydroxide)
Excess!
Weak acid cation exchangers, weak alkaline
anion exchangers
Less dissociation
Simple regeneration
Fixed bed operation
Ion exchange
SAC:
Ag > Cs > K > NH4 > Na > H > Li
Ba > Pb > Sr > Ca > Ni > Cd > Cu > Co > Zn >
Mg
WAC:
H >> Cu > Pb > Ni > Co > Fe > Ca > Mg > Na >
K > Cs
SBA:
SO4 > HSO4 > I > NO3 > Br > Cl > HCO3 > HSiO3
> ClO4 > F > OH
WBA:
OH >> SO4 > HSO4 > I > NO3 > Br > Cl > F
Ion exchange
Favourable / non-favourable
Used for…
Removal of ions
Recovery of ions
Metathesis
Separation, e.g. chromatography
Breakthrough curve: regeneration
Backwashing: suspended solids, fouling
components, released resin particles; avoid canal
formation by expansion
Regeneration of ion exchange
resins
Weak acid/alkaline easier to regenerate
Strong acid/base with excess regenerant
Co-flow
• Optimization: amount of regenerans
• leakage (slip / elution leak)
• Kinetic leaks (fouling)
Counter-flow
• No leaks
• Better regeneration
Regeneration of ion exchange
resins
Regeneration - technically
Ion exchange
Applications in water treatment:
Softening: SAC, Ca/Mg  Na
• Municipal
• Industrial
Dealkalisation: WAC, Na  H
Removal of NOM: SBA, 50-70%
Nitrate removal: nitrate selective resins
Oxygen removal: R2SO3  R2SO4
Demineralization: SAC + SBA
Pilot ion exchanger
Electrodialysis
Membrane stack: cation exchange and anion
exchange membranes
Electrodes: graphite, stainless steel, nickel
alloys, platina
Membrane material: ion exchange resin
Heterogeneous: crushing of resin + binding
polymer
Homogeous: polymer film (crosslinks!) + ionizable
groups (optimum: avoid swelling)
Electrodialysis

Diluate Concentrate

- - - - - -
Anode
Cathode (+)
(-) + + + + + +

Electrode
rinse
Electrodialysis
Operation: ED – EDR
Scaling: turbulence - antiscalants
Description of performance: Transport
number
z  D F c
Electrical resistance i  ilim  A    T
b

  t  t 
lim m bl

Limiting current density

Back diffusion: CF ~ 150-250
Applications: desalination of brackish water –
nitrate removal
Implementation
Determine objectives
Which ions?
Separation?
Concentration level?
Lab scale experiments
Membrane choice
Transport number and power consumption per
unit of volume
Scale-up:
Cost (energy consumption, investment)
Number of modules, residence time per module
Specific technologies (to be
continued...)
Seawater desalination
Water softening