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Capacity loss in an organically fouled anion

exchanger
ARTICLE in DESALINATION MARCH 2006
Impact Factor: 3.76 DOI: 10.1016/j.desal.2005.07.012

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Yasemin Kaya

Istanbul University

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Istanbul University

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Desalination 189 (2006) 303307

Capacity loss in an organically fouled anion exchanger

Z. Beril Gnder*, Yasemin Kaya, Ilda Vergili, Hulusi Barlas
Environmental Engineering Department, Faculty of Engineering, Istanbul University, 34320 Avcilar-Istanbul, Turkey
email: bgonder@istanbul.edu.tr
Received 27 April 2005; accepted 29 July 2005

Abstract
One of the most important contaminants that ion-exchange resins are exposed to is fouling by organic materials.
Especially, anion-exchange resins are more sensitive to fouling by organic materials. The fouling of anion-exchange
resins by organic materials is primarily caused by the degradation of products of cation ion exchangers and humic and
fulvic acids. Organic fouling causes product water with low quality and few anion exchangers and shortens the service
time. Also the need for rinsing water and the use of regeneration chemicals increase. Operating capacity losses
occurring due to the fouling of anion-exchange resin by humic acid were quantitatively determined. SAK254 (Spektraler
Absorptions Koeffizient = spectral absorption coefficient), DFZ436 (DurchsichtsFarbZahl = indexes of transparency),
conductivity and sulfate measurements were made to determine capacity losses, which were obtained as 21%, 23%,
25% and 30% after the fouling studies of anion-exchange resin by the amounts of 0.13, 0.25, 0.5 and 1.0 mg/L humic
acid, respectively. It was found that even small concentrations of humic acid resulted in a considerable amount of
capacity losses in anion-exchange resin.
Keywords: Organic fouling; Humic acid; DFZ436; SAK254; Operating capacity

1. Introduction
Very high quality water is needed through
various stages of processing in many industries
(e.g., semiconductor, pharmaceutical, chemical,
etc.). Ion-exchanger systems currently have widespread use for this purpose. Some problems are
encountered during their use (loading, backwashing and regeneration), which affect the

performance of ion-exchange resins. The most

important one amongst these problems is the
fouling of ion-exchange resins [1,2].
Fouling with organic materials is the most
important one that ion-exchange resins encounter.
Organic fouling is an irreversible fixation of organic materials to the ion-exchange resin. Especially, anion exchange resins are more sensitive to
fouling with organic materials [3].

*Corresponding author.
0011-9164/06/$ See front matter 2006 Elsevier B.V. All rights reserved

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Z. Beril Gnder et al. / Desalination 189 (2006) 303307

The fouling of anion-exchange resins by

organic materials is primarily caused by the
degradation products of cation exchangers and
humic and fulvic acids. Organic fouling results in
production of low-quality (high conductivity, low
pH), low amounts of water and some great problems such as early breakthrough and long washing periods after regeneration. The capacity of the
ion-exchanger bed decreases and water with
desired quality is not produced due to the fouling
that was not removed fully by means of regeneration and backwashing [3,4].
Natural waters contain organic, inorganic and
biological compounds in various ratios. Organic
materials have a high share amongst these compounds. Sources of organic materials in these
waters are decomposition products of wood and
leaves or industrial and domestic wastes [5].
Organic materials are largely composed of humic
materials. Humic materials are classified into
three groups according to their solubilities in
water [6]: (1) humin, that is the part which is not
soluble at any pH value; (2) humic acid, that is
the part which is not soluble in (pH <2) acidic
medium but is soluble at high pH values; (3) fulvic acid, that is the part which is soluble in all pH
values.
It is believed that the chemical structure of
these three fractions are alike. They appear to
differ in molecular weight and functional group
content. Fulvic acid probably has a lower molecular weight but more hydrophilic functional
groups than humic acid [7].
According to McCoy [8], soluble organic
materials such as humic and fulvic acids foul
anion-exchange resins primarily with ion exchange. The chloride ions or hydroxyl anions
within the humic acid structure are exchanged
with the chloride, sulfate or hydroxyl anion on
the quarternary amine that is grafted to the backbone of the anion-exchange resin molecule [9].
These fouling materials do not diffuse into the
resin due to their molecular dimensions. They
rather prevent ions moving into the resin by

accumulating physically onto the resin surface

and blocking the ion-exchange points [4].
Organic materials make ion-exchange resin
hydrophobic. Because of this, the moisture content of resins which fouled by organic materials
decreases. This is a case which is to be avoided
because it results in the decrease of porosity
volume. As a result, the diffusion rate of counter
ions and operating capacity decrease while the
washing period and rinse water needed increase.
Organic materials may also cause silicate leakage
in anion exchangers where the silicate removal
process is carried on. Silicate accumulates at the
bottom of the anion-exchanger bed because the
flow of water into resin is slowed down due to the
blockage of resin pores by organic materials
having high molecular weights [10].
There are some methods used for the purpose
of cleaning of anion-exchange resins fouled by
organic metarials. Washing with a caustic salt
solution is the most used amongst other methods.
This cleaning procedure is implemented by using
10% salt solution containing 2% NaOH of three
times volume of bed volume [11].
The application of pretreatment processes is
proposed before the ion-exchange system in order
to protect the resins against organic fouling.
Coagulationflocculation, adsorption with actived
carbon, membrane processes and oxidation/ biofiltration processes are used as pretreatment
processes in the removal of organic materials
[12]. In addition, the most resistant resin type
must be chosen against fouling with organic
materials. Acrylic-based resins are more resistant
than styrene-based resins because they have a
larger hydrophilic structure and ease the passage
of high molecular organic materials from the
resin due to their aliphatic structure. Organic
materials could be removed effectively from the
acrylic-based resins during regeneration [13].
2. Materials and methods
Changes in resin capacity were determined

Z. Beril Gnder et al. / Desalination 189 (2006) 303307

quantitatively by searching fouling of resin with

humic acid which is a fraction of humic material.
Lewatit M 500, frequently used in demineralisation applications, was chosen as the strongly
basic anion exchanger. Technical specifications
of the resin (Lewatit M 500), provided from
Bayer Leverkusen, are given in Table 1.
A laboratory-scale glass column with a 2 cm
diameter and 45 cm height was used throughout
the experiments. The column was filled with a
strong anion-exchange resin of 50 mL in volume.
Synthetic water, prepared by dissolving Na2SO4
in distilled water with appropriate amounts resulting 150 mg/L SO42! content, was used. The synthetic water was supplied to the system by using
a peristaltic pump (Prominent) and the feed rate
was adjusted to V = 5.0 m/h (specific flow rate =
31 bed volume/h). A humic acid solution was
used in the fouling studies. This solution was
prepared according to the Urano method: 1 g
humic acid was dissolved in 100 mL 0.1 N NaOH
solution and then distilled water was added up to
1 L after waiting for 1 day [14].
The following method was used for the determination of changes occuring in ion-exchange
capacity in the studies performed for the fouling
Table 1
Technical specifications of the strongly basic anion
exchanger (Lewatit M 500)
Properties

Strongly basic
anion exchanger

Ionic form
Functional group

Cl!
Quarternary amine,
Type 1
Gel
1.4
0.47
40
NaOH
100
24

Structure
Total capacity, min. eq /L
Bead size, mm
Flow rate, max. m/h
Regenerant
Regenerant level, g/L
Regenerant con., %

305

of ion-exchange resins. The method is based upon

the comparison of resin after being regenerated
with a new resin sample [15,16]. In this study this
method is taken as a reference.
Changes in resin capacity during the fouling
of the anion-exchange resin were determined by
using humic acid in the amounts of 0.13, 0.25, 0.5
and 1.0 mg/L. The amount of 15 mg/L SO42! value
was taken as the breakthrough point and column
loading was continued until this value was
reached at the outlet. SAK254 (Spektraler AbsorptionsKoeffizient = spectral absorption coefficient)
[17], DFZ (Durchsichts Farbzahl = indexes of
transparency) [18] and conductivity measurements were performed for the samples taken from
the column outlet during fouling.
SAK254 and DFZ436 measurements were made
by using Jenway UV-Vis (model 6105) and
Pharmacia LKB-Novaspec II spectrophotometers,
respectively. Conductivity measurements were
carried out by a WPA CM35 conductivity device.
Sulphate measurements were implemented
according to the turbidimetric method as defined
in Standard Methods [19].
A 4% NaOH (12 bed volume/h) solution of
300 mL (6 bed volume) in volume was used for
the strong anion-exchange resin regeneration.
Cocurrent regeneration was carried out in the
study. The regenerated resin was backwashed
with distilled water until the conductivity of the
effluent was less than 1 S/cm.

3. Results and discussion

A strong basic anion-exchanger was fouled
with 0.13, 0.25, 0.5 and 1.0 mg/L humic acid and
raw water was passed through after regeneration.
The capacity of the ion exchanger was calculated
by obtaining breakthrough curves belonging to
the cycles of raw water passed through fresh ionexchanger resin and through ion-exchanger resin
fouled with humic acid and subsequently regenerated (see Figs. 14).

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Z. Beril Gnder et al. / Desalination 189 (2006) 303307

Fig. 1. Breakthrough curves obtained from the fouling of

strong anion exchanger with 0.13 mg/L humic acid.
(a) raw water, (b) raw water containing 0.13 mg/L humic
acid, (c) raw water after regeneration.

Fig. 2. Breakthrough curves obtained from the fouling of

strong anion exchanger with 0.25 mg/L humic acid.
(a) raw water, (b) raw water containing 0.25 mg/L humic
acid, (c) raw water after regeneration.

Fig. 3. Breakthrough curves obtained from the fouling of

strong anion exchanger with 0.5 mg/L humic acid.
(a) raw water, (b) raw water containing 0.5 mg/L humic
acid, (c) raw water after regeneration.

Fig. 4. Breakthrough curves obtained from the fouling of

strong anion exchanger with 1.0 mg/L humic acid.
(a) raw water, (b) raw water containing 1.0 mg/L humic
acid, (c) raw water after regeneration.

The capacity loss was found to be 21% for the

fouling of anion-exchange resin with 0.13 mg/L
humic acid. In this case, organic material causes
high capacity losses even in small amounts. The
capacity losses were found to be 23% and 25%
for the humic acid amounts of 0.25 and 0.5 mg/L,
respectively. A 30% capacity loss was observed
as the humic acid amount reached 1.0 mg/L
value. The capacity losses are shown in Fig. 5.
Capacity losses increased as the humic acid
amounts increased. The reason for this is that
humic acid which is a high molecular organic
material blocks the pores of anion exchange resin
which in turn prevents ions moving into the resin.

This situation could not to be ceased even by the

regeneration process [4].
DFZ436 and SAK254 parameters measured for
the samples taken from the outlet of the ionexchange column were evaluated during fouling
studies. DFZ was measured as zero for the
samples taken up to 15 mg/L SO4= value which
was chosen as the breakthrough point during the
fouling studies made with 0.13, 0.25, 0.5 and
1.0 mg/L humic acid values. In other words, no
colour was observed in the samples taken from
the column outlet. SAK254 values were determined to be zero for samples taken up to the
breakthrough point during the fouling of anion-

Z. Beril Gnder et al. / Desalination 189 (2006) 303307

Fig. 5. Capacity losses occurring in strong anion

exchange.

exchange resin with 0.13 and 0.25 mg/L humic

acid. When the humic acid amount was 0.5 mg/L,
SAK254 values were observed for the samples
taken from column outlet after the passage of
15.3 L water fouled by humic acid (bed volume
= 306). SAK254 value was measured as 0.9 m!1 at
the breakthrough point. When the humic acid
amount was 1.0 mg/L, SAK254 values were
observed for the samples from the column outlet
after the passage of 14.5 L water fouled by humic
acid (bed volume = 290), and this value became
2.6 m!1 at the breakthrough point. The reason for
this is the blockage of ion-exchange points
existing in ion-exchangers structure by a large
amount of humic acid. As a result, the capacity of
resin decreases.

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