RESIN FOULING AND

DEGRADATION AND METHODS OF

REMEDIATION

Presented by David Naden,

Purolite International
 RESIN FOULING

Fouling is non regenerated uptake of fouling

agents such as:

Cation resins
- iron, manganese and aluminium
- calcium sulphate
- polyelectrolytes
Anion resins
- organics
- silica
- iron
All resins
- oil
- bacteria/algae etc
- suspended solids and mud
 RESIN FOULING

• Fouling results in poor plant performance

– reduced resin capacity
– poor regeneration
– leakage of cations and anions into
product
– long rinse times
 CATION RESIN FOULING
IRON, MANGANESE AND ALUMINIUM FOULING

Caused by
- Higher valent ions not being efficiently removed
by acid on regeneration

Removed by
- Treatment with 6% HCl wash

Iron Fouling Treatment

- reduction of ferric iron to ferrous iron by
4% solution of sodium dithionite

Iron Fouling can be prevented by

- reduction of ferric to ferrous iron in the feed
by sodium bisulphite addition
- removal of iron in feed to less than 0.1 ppm
e.g. by manganese green sand (Purolite MZ10)
 CATION RESIN FOULING

 Cation Resin Fouling

 Calcium Sulphate Fouling
 CATION RESIN FOULING
BY CALCIUM SULPHATE

– Caused by calcium sulphate precipitations

in the resin

– Difficult to remove (hydrochloric acid

sometimes partially effective)

– Prevented by controlling sulphuric acid

concentration (stepwise regeneration)

– If severe fouling change resin

 ANION RESINS FOULING BY ORGANICS

• Where do organics come from?

• What are they?
• How do we measure them?
• How does resin fouling effect plant
operation?
• What resins are used?
• How is organic fouling prevented?
• How is organic fouling removed?
 RESIN FOULING

 Anion Resin Fouling

 Organic fouling
 ANION RESINS FOULING BY ORGANICS:
SOURCES OF ORGANICS
Insoluble Matter

• Particulates of vegetable and animal origin

• Certain humic compounds
• Micro organisms
• Vegetable and mineral oils
 ANION RESINS FOULING BY ORGANICS
SOURCES OF ORGANICS

Soluble Matter

• Humic and fulvic acid, tannins (mainly

from surface waters)
• (Industrial) synthetic organics
• Saccharides
• Certain amino acids and proteins
 ANION RESINS FOULING BY ORGANICS:
THE FOULING MECHANISM

• Soluble organics are held by ion exchange

and adsorption and ionic forces
• Large organic molecules diffuse into beads
• Diffusion out of the beads is slow and is not
complete on regeneration with caustic
• Fraction of the organics not removed on
regeneration causes Fouling”
 ANION RESINS FOULING BY ORGANICS:
SYMPTOMS OF ORGANIC FOULING

• Rinse is longer because Na is adsorbed by

the organics during regeneration and
hydrolyzes off slowly (alkaline rinse)
• Leakage increases
• Operating capacity decreases
• Pressure drop can increase
 ANION RESINS FOULING BY ORGANICS:
REMOVAL OF ORGANICS FROM WATER

Insoluble and Colloidal Matter

• Coagulation and Filtration
• Ultrafiltration

Soluble Matter
• Adsorption on activated carbon filter
• Use organic scavenger Purolite A860 or
A500P, regenerated by brine or caustic
brine, ahead of demineralisation units.
 ANION RESINS FOULING BY ORGANICS:
RESIN CLEANING BY CAUSTIC BRINE TREATMENT

• Backwash resin to remove suspended solids

• Prepare 3 BV 10% NaCl + 2% Caustic Solution
• Pass 1st BV at a flow of maximum 2 BV/h
• Pass 2nd BV at same flow and leave to soak for
at least 4 hours (better overnight)
• Periodically apply some agitation of air
scouring where possible
• Pass 3rd BV of brine at flow of 1 BV/h
• Rinse with softened or demineralised water
• Double regenerate the anion before going back
on line
• Brine should be applied at minimum 35C
(better at 60C), but observe temperature limits
for resins
 ORGANIC FOULING OF ANION RESIN:
SELECTION OF RESINS AND OPERATING CONDITIONS

High Organics:
- Use Acrylic WBA (A845/A847) or Styrenic WBA
(A100) to protect SBA in demin unit
Medium Organics
- Use Acrylic Type 1 (A850), Acrylic Dual Base
(A870) or Styrenic Macroporous Type 2 (A510) in
demineraliser unit
Low Organics
- Use Styrenic Type 1 SBA Gel (A400), Macroporous
(A500) or Type 2 (A200) in demineraliser unit
Use Puredesign to:
- Predict maximum recommended organics loading
- Optimise regeneration
 ANION RESIN ORGANIC FOULING:
SUMMARY

- Caused by:
- large organic molecules blocking resin pores

-Removed by:
-soak in alkaline brine (10% NaCl, 2% NaOH)
at up to 60C

- Can be prevented by:

- pre-treatment of feed water using
active carbon or organic scavenger resins
Purolite A500P or A860
- correct selection of anion exchange resin
 ANION RESIN FOULING BY SILICA

• Silica can accumulate on anion resins when

regeneration is not adequate (low
regenerant levels, low temperatures)
• Soluble silica can unpredictably polymerise
and form precipitations on the resin
• Weak base resins can be fouled during
regeneration when regenerated in series
with strong base resin (especially at high
silica level on SBA, high NaOH concentration
and high regeneration temperature)
• Silica is less soluble at lower pH values as
we find it on exhausted weak base resin
 SILICA FOULING OF ANION RESINS:
PREVENTION

Where silica fouling has been detected or where

silica levels in the feed water is high.
• Increase SBA volume to reduce silica load
• For strong base anion (SBA)
– Increase regeneration temperature
– Increase regeneration level
• For weak base anion (WBA) regeneration
– Avoid high silica concentration to WBA
– Reduce regeneration temperature on SBA
– Reduce regenerant concentration on SBA
– Dilute regenerant after passing through
SBA
– Discard first part of regenerant (high in
silica) after SBA
 SILICA FOULING OF ANION RESINS:
RESIN CLEANING
• Backwash resin extensively
• Prepare 3 BV 4% NaOH Solution
• Pass 1st BV at a flow of maximum 2 BV/h
• Pass 2nd BV at same flow and leave to soak for at
2-4 hours
• Periodically apply some agitation of air scouring
where possible
• Pass 3rd BV of NaOH at flow of 1 BV/h
• Rinse with softened or de-mineralised water to
remove cleaning solution
• Double regenerate the anion before going back on
line
• The treatment should be applied at hot (maximum
50C for weak base and type 1 resins and at 35C for
type 2 resins)
 SILICA FOULING OF ANION RESINS:
SUMMARY

- Caused by:
- silica polymerising in the resin bead
- insufficient regeneration
- Removed by:
- soak in sodium hydroxide at up to 60C
- Can be prevented by:
- efficient regeneration
- optimising strong and weak anion
regeneration
 ANION RESIN FOULING BY IRON

- Caused by iron organic complexes entering

the resin and precipitating as iron hydroxide
during regeneration

- Removed by 6% HCl treatment followed by

alkaline brine treatment for organic removal

-Can be prevented by
- use of organic scavenger Purolite A500P or
A860 ahead of cation resin
- use of Purolite MZ10 ahead of cation resin
 ANION EXCHANGE RESIN FOULING BY IRON:
ACID CLEANING
Where the presence of iron is detected on the
resin , iron/organic complexes are likely to be
present
• Prepare 6% hydrochloric acid Check that
materials of construction are suitable for HCl
• Pass 1st BV at a flow of maximum 2 BV/h
• Pass 2nd BV at same flow and leave to soak for
at least 4 hours (better overnight)
• Periodically apply some agitation of air
scouring where possible
• Pass 3rd BV of acid at flow of 1 BV/h
• Rinse with softened or demineralised water to
remove cleaning solution
• Carry out alkaline brine treatment
 RESIN FOULING BY OIL
• Oil fouling coating resin beads
– Caused by:
• Present in feed water
• Oil leaks from pumps etc
– Results in
• Coating of resin beads and blinding of resin
pores
• Poor mixed bed resin separation
• Increased bed pressure drop
• Channelling in the bed
– Prevented by:
• Improved plant maintenance
• Improved pre-treatment
– Remediation:
• Surfactant wash of resin bed
 RESIN FOULING:
BIO FOULING

- Caused by
• growth of algae and/or bacteria in pipes,
vessels and on resin bead surface
- Results in
• high pressure drop across bed and resin
breakage
• all the problems of organic fouling

- Removed by
• air scouring of resin bed and backwash
• algaecides and bactericides treatment
 peracetic acid (low H2O2 grade)
 formaldehyde
 sodium hypochlorite
 RESIN FOULING:
FOULING BY SUSPENDED SOLIDS AND MUD

- Caused by
– Suspended solids present in feed water collect
in the bed
- Results in
– High pressure drop across the resin bed and
resin breakage
– Flow channelling in the resin bed
- Removed by
– Extended resin bed backwashing
– Air scouring and backwashing of the resin bed
- Prevented by
– Efficient pre-treatment of feed water
 RESIN BREAKDOWN
Resin breakdown is an irreversible process!
 RESIN BREAKDOWN DUE TO
CHEMICAL ATTACK

- Caused by
• oxidising agents such as chlorine, peroxide,
ozone catalysed by iron or manganese on
the resin

- Results in
• bead weakening and eventual resin breakage
• loss of resin active groups/loss of capacity

- Prevented by
• chlorine removal by active carbon
• chlorine reduction by sodium bisulphite
addition
 RESIN BREAKDOWN:
PHYSICAL BREAKDOWN

Caused by:
- Chemical attack (as above)
- High pressure drop across the bed due to
 fines accumulation
 high flow rates
- Feed flow pulsing e.g. due to water hammer
- Poor backwash and bed compaction

Prevented by
- Remediation of causes
 RESIN BREAKDOWN:
THERMAL DEGRADATION

- Caused by
• too high service or regeneration
temperature

-Results in
- loss of active groups/ loss of operating
capacity
- lower throughputs
- higher leakages of weaker ions

- Prevented by
- reducing temperatures
- selecting correct anion resins
HOFFMAN DEGRADATION OF SBA RESINS
 RESIN BREAKDOWN
OSMOTIC SHOCK

- Caused by
- sudden changes in solution concentration
- resin fouling

- Results in
- differential expansion of the resin
- resin breakage
- resin shelling

- Prevented by
- avoiding sudden changes of concentration
- regular resin cleaning
- selecting correct resins e.g. higher DVB matrix
 RESIN FOULING PROBLEMS:
PUROLITE TECHNICAL SERVICE

How Purolite can help

– Puredesign gives warning levels for

organic and silica load
– Analysis and assessment of fouled resin
– Advice on prevention of fouling
problems
– Advice on cleaning treatment
– Comprehensive brochures describing
cleaning methods