Journal of Ecological Engineering Received: 2018.03.

02
Accepted: 2018.05.15
Volume 19, Issue 4, July 2018, pages 136–142 Published: 2018.07.01
https://doi.org/10.12911/22998993/89662

Using Ion Exchange Process in Removal of Selected Organic

Pollution from Aqueous Solutions

Jadwiga Kaleta1, Dorota Papciak1, Alicja Puszkarewicz1

Rzeszów University of Technology, The Faculty of Civil and Environment Engineering and Architecture,
1

Department of Water Purification and Protection, ul. Poznańska 2, 35-084 Rzeszów, Poland
* Corresponding author’s e-mail: [email protected]

ABSTRACT
Surfactant and phenol were removed using AMBERLITE IRA 900 Cl ion-exchange resin, which is a strong alkali.
In the process, the tests were carried out under non-flow conditions, the effect of contact time and ionite dose on the
surfactant and phenol exchange was determined. The tests under the through-flow conditions were realized in three
consecutive cycles, preceded by regeneration and rinsing. The obtained results served for determination of ion-
exchange capabilities of the studied ionite. The usable ion-exchange capabilities of the resin obtained after the sec-
ond and third ionite operation cycle were lower by about 10% (surfactant) and 14.29–17.86% (phenol) than those
after the first cycle. It shows that the process of sorption occurred simultaneously with the ion-exchange process.

Keywords: detergent, phenol, ion-exchange

INTRODUCTION An effective method of detergents removal

is adsorption. In the process of granular acti-
Detergents, as well as phenol and its com- vated carbon adsorption, 31.7–67.4% of anionic
pounds belong to the group of organic compounds and non-ion SAAs were removed [Cserhati et al.
which are dangerous to human health. Detergents 2002]. The adsorption capacity of granular ac-
constitute a commonly used name for surface- tivated carbon produced in Poland towards an-
active agents (SAAs), which mix with the surface ionic SAAs was between 11 and 17 mg/g [Kaleta
water and groundwater through the municipal 2008]. Meanwhile, the activated carbon dust re-
and/or industrial wastewater. The compounds moved 34–38% of anionic SAAs, and 68–98% of
hinder the self-purification processes of waters cationic SAAs [Basar et al. 2004]. Other sorbents
and accumulate in living organisms [Sarkar and used for SAAs sorption were: activated oxygen
Das 2001, Kida and Koszelnik 2015]. and mineral clays.
SAAs belong to the group of very durable and The ultrafiltration process was found to be
slowly biodegradable compounds. In the water very effective in anionic surfactant removal in a
intended for human consumption, they are pres- wide range of concentrations, the retention coef-
ent as a result of insufficient water purification. ficient amounted to 82–90% [Kowalska 2008].
The compounds facilitate absorption of other tox- The anionic surface-active agents were effec-
ic substances (such as pesticides and polycyclic tive in the ion exchange process of gel and macro-
aromatic hydrocarbons) from the digestive tract porous anion-exchange resins [Kowalska 2009].
to the blood through the decrease of surface ten- The source of phenol in the natural waters can
sion. They have a harmful effect on skin, causing be products of degradation of organic substances,
its dryness, cracking, irritation, and various kinds as well as industrial wastewater, i.a. from coking
of eczema. They destroy mucosa of the digestive plants and chemical industry. Phenols are toxic
tract, which causes gastritis [Kaleta 2008]. substances, which negatively influence the water

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environment. At concentration over 5 mg/dm3, RESEARCH SUBJECT

they are toxic to the aquatic fauna and flora; they
also hinder the water self-purification processes The research focused on the removal of an
[Piekutin 2011, Puszkarewicz et al. 2015]. anionic surface-active agent and phenol. The pol-
Phenol is a strong toxin. It has transfixing ef- lution is being limited in water for human con-
fect on the nervous and cardiovascular systems. sumption (Table 1).
It damages the respiratory tract, causes denatur- According to the World Health Organisation
ation of proteins, and results in skin irritation. The (WHO) recommendations, the maximum con-
water chlorination process creates chlorophenols, centration of anionic surface-active agents in the
toxic compounds that cause the water intended water intended for consumption is 0.2 mg/dm3.
for consumption to have unpleasant smell and In the water intended for human consumption,
changed taste [Kaleta 2006]. WHO also limits by-products of chlorination,
The most effective method of water puri- among them 2,4,6 – trichlorophenol, the maxi-
fication of phenols and their products is the ad- mum concentration of which is 0.01 mg/dm3
sorption of activated carbons [Oghenejoboh et [Guidelines 2017].
al. 2016]. The adsorption capacity of activated The research was conducted on model solu-
carbons produced by Gryfskand Sp. z o.o. com- tions, called also initial solutions, which were
pany in Hajnówka, Poland, is between 35 and prepared on the basis of distilled water. The
50 mg/g [Kapica et al. 2002, Kaleta 2006]. The means of control determination were indicators
spherical activated carbons, received in the pro- of the pollution types under research.
cess of agglomeration of granular hard coking Model solution of the detergent (D) was pre-
coal with vegetables oils (rapeseed and flaxseed) pared by adding distilled water to the Aerosol
are characterised with a higher adsorption value OT-100 anionic surface-active agent (chemical
(between 70 and 150 mg/g) [Lorenc–Grabowska formula C2H37NaO7S) in an amount that results
and Gryglewicz 2002]. in detergent concentration in the solution equal to
An attempt has been made to replace activat- 20.00 g/m3. Determination of the detergent was
ed carbons with other adsorbents, such as: granu- carried out using the method involving methylene
lar coke, bituminous coal, peat, calcium carbon- blue. The method consisted in creating blue or-
ate, bog iron ore, natural and modified zeolites, ganic compound as a result of reaction of methy-
bentonites, and modified clays. These adsorbents, lene blue with anion-exchange surface-active
despite their lesser adsorption capacity, may re-
agent. The created compound was extracted with
place activated carbons under certain conditions
chloroform in alkaline environment, and the in-
[Nayak and Singh 2007, Kaleta et al. 20013,
tensity of the blue hue, measured photometrically
Dudzik and Werle 2015].
at the wavelength equal λ=652 nm, was propor-
Phenolic compounds were effectively re-
tional to the concentration of detergents.
moved by Amberlite XAD resin. Its sorption ca-
The phenolic pollution was investigated on the
pacity was higher for chlorophenol (2.27 mmol/g)
example of the most often occurring compound,
than for phenol (1.50 mmol/g). Resin regenera-
which is phenol (C6H5OH). Phenol was dissolved
tion was conducted through extraction (elution)
in distilled water, transforming into model solu-
with methanol as a solvent. After subsequent de-
tion (F) with the concentration of 20.00 g/m3.
sorption processes, the adsorption capacity did
not change [Abburi 2003/B]. Determination of the phenol concentration was
An effective method of removal of organic carried out using an indirect method through the
pollution from water is MIEX process (Magnetic absorption measurement (with the wavelength of
Ion Exchange Process), in which selective ion-ex- λ=254 nm) by means of a Schimadzu UV-1601
change resins of strongly alkaline function groups,
working in a chloride cycle were used. The resins, Table 1. The admissible concentration of surfactant
produced in the form of “magnetic” microions, and phenol in natural waters, mg/dm3 (Council Regu-
under appropriate hydraulic conditions under- lation No. 203, item 1718 of 27 November 2002)
went agglomeration and separation from the puri- Category Category Category
fied water. The MIEX method was utilised along Type of pollution
A1 A2 A3
with the coagulation process in order to maximize Surfactant 0,2 0,2 0,5
the effect of water purification process [Mołczan Phenols
0,001 0,005 0,1
and Biłyk 2006, Kabsch-Korbutowicz 2013]. (phenolic index)

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Journal of Ecological Engineering Vol. 19(4), 2018

Visible Spectrophotometer. Quartz cuvettes with ion exchanger was removed, infiltrated, and the
1 cm absorption layer were used. Before carrying control determination was carried out.
out the actual measurements, a model curve was In order to determine the influence of the ion
created, and the correlation between phenol con- exchanger dose on the ion exchange process,
tent F and absorbency A was determined by the 1 dm3 of a model solution and ion exchanger dos-
following formula (1): es increasing from 0.5 to 7.0 g/dm3 were added
to 8 bottles. The contact time was 30 min. After
F= tg 35 · A tg 35 = 0.700,
(1) 30 min of sedimentation, control determination of
that is F=0.700 · A decanted and infiltrated solutions was carried out.
The results obtained in this series of tests were
A strongly alkaline AMBERLITE IRA900 used to calculate the exchange capacity of the
Cl resin was used in the ion exchange process ion exchanger.
(Table 2). It is a macroporous type I resin, con- The exchange capacity of the ion exchanger
sisting of quaternary amine groups. It allows to in a moist state (Zcw) was calculated by the fol-
remove all anions from the water, including the lowing formula (2):
poorly decomposed ones, e.g. silica. The macro- (𝐶𝐶𝐶𝐶 − 𝐶𝐶𝐶𝐶) ∙ 𝑉𝑉
porous structure of the resin resembles a sponge. 𝑍𝑍𝑍𝑍𝑍𝑍 = (2)
𝐺𝐺
That feature, combined with a strong alkalinity,
allows to remove large organic particles. where: Co – initial concentration of the model so-
lution, mg/dm3,
Ck – final concentration of the model so-
RESEARCH METHODOLOGY lution, mg/dm3,
V – volume of the of the model solution
used in tests, dm3,
Tests conducted under non-flow (static) G – mass of the moist ion exchanger, g,
conditions Zcw – the exchange capacity of the moist
Before the tests were conducted, the ion ex- ion exchanger, mg/g.
changer had been soaked in distilled water for 24 In order to calculate the exchange capacity
hours. An appropriate amount of the swelled ion of the dry ion exchanger, the moisture of the ion
exchanger was placed in a bottle of 10% NaCl. exchanger sample used in the research was de-
The bottle contents were shaken for 30 min; then termined (p). The exchange capacity of the ion
the ion exchanger was drained and rinsed with exchanger in a dry state (Zcs) was calculated by
distilled water until the disappearance of Cl- ions. the following formula (3):
The regenerated and rinsed resin was used for
further tests. The kinesis of the ion exchange pro- 100 ∙ 𝑍𝑍𝑍𝑍𝑍𝑍
𝑍𝑍𝑍𝑍𝑍𝑍 = (3)
cess was determined using the following method: 100 − 𝑝𝑝
3 g of the ion exchanger were added to 8 bottles, where: Zcs – exchange capacity of the ion ex-
each of them containing 1 dm3 of an appropri- changer in a dry state, mg/g,
ate model solution. The samples were shaken for p – percent of moisture content in the ion
10–180 min, and then underwent 30 minutes of exchanger sample.
decantation. Afterwards, the solution above the
Determining exchange capacity of the ion
Table 2. Characteristics of AMBERLITE IRA900 Cl exchanger under flow (dynamic) conditions
Designation Unit Value The useful (working) exchange capacity was
Bulk density g/dm3 640–710 determined using laboratory ion exchanger col-
Granulation m >500 umns made of organic glass with the diameter of
Effective diameter m 600–800 15 mm and height of 600 mm.
Coefficient of
- <1,8 In order to conduct the tests, a 20 g sample
homogeneity
of the swelled (soaked) ion exchanger was trans-
Humidity % 58–64
Total ion
ferred to the ion exchanger column. Then, about
exchange val/dm3 1,0 1.5 dm3 of the regenerant solution (10% NaCl)
capacity was flushed through the ion exchanger at the

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speed of 5 m/h, downwards. Afterwards, the ion 100 ∙ 𝑍𝑍𝑍𝑍𝑍𝑍

exchange bed was rinsed with distilled water un- 𝑍𝑍𝑍𝑍𝑍𝑍 = (5)
100 − 𝑝𝑝
til the disappearance of the regenerant solution in
the outflow. where: Zus – exchange capacity determined un-
The actual tests consisted of flushing the der dynamic conditions in the dry state,
appropriate model solution through the ion ex- mg/g,
changer at the speed of 10 m/h. After each flow p – moisture content, %.
of 1 dm3 of the model solution through the ion
exchanger had finished, the samples were col-
lected and control determination was carried out. RESULTS
The ion exchange cycle was stopped when the
concentration of the detergent in the outflow in- The ion exchange proceeded very quickly. In
creased above 0.6 mg/dm3, and of phenol above the case of the detergent, it decreased by 95.55%
0.2 mg/dm3 (cycle I). after 30 minutes of contact with the ion exchang-
Then, the ion exchanger underwent the re- er. After 30 minutes of contact, the phenol was
generation and rinsing again; then it was used for reduced by 97.50%. A longer contact time did
another filtration cycle (cycle II) in the way de- not yield better results in the case of the analysed
scribed above. The whole sequence was repeated kinds of pollution (Table 3). The assumed opti-
one more time (cycle III). mal time of contact between the ion exchanger
The useful (working) exchange capacity of and purified solutions was 30 min.
the moist ion exchanger was calculated with the An increase of the ion exchanger dose up to
following formula (4): 4.0 g/dm3 resulted in an improvement of the de-
tergent removal effectiveness to 95.55%. A larger
𝑉𝑉𝑉𝑉 ∙ ∆𝐶𝐶 amount of the ion exchanger increased the ef-
𝑍𝑍𝑍𝑍𝑍𝑍 = (4)
𝐺𝐺𝐺𝐺 fectiveness of the ion exchange process only by
0.05 % (Table 4).
where: ∆C – difference between the concentra-
In the case of phenol, the ion exchanger sam-
tions of the removed ions (initial con-
ple that yielded satisfactory result of 97.50% re-
centration minus concentration puncture
duction, amounted to 3.0 g/dm3. Similarly to the
point), mg/dm3,
detergent removal process, a larger amount of the
Vr – volume of outflow from the column
ion exchanger caused only a slight effectiveness
until puncture point, dm3,
increase of the ion exchange process (Table 4).
Gj – mass of the ion exchanger in
In order to calculate the exchange capacity
the column, g,
of the resin under non-flow conditions, a dose of
Zuw – exchange capacity of the moist ion
4.0 g/dm3 was used in the case of the detergent,
exchanger, determined in the flow condi-
tions, mg/g. and a dose of 3.0 g/dm3 in the case of the phenol
(Table 5). The moistness of the regenerated and
Considering the percentage content of mois- rinsed ion exchanger used for tests under static
ture, the useful exchange capacity of the ion ex- conditions was 64%.
changer in a dry state was calculated by the fol- On the basis of tests conducted under flow
lowing formula (5): (dynamic) conditions, the puncture curve of the

Table 3. Effect of contact time the ion exchange

Concentration of Decreasse of Concentration of Decreasse of phenol,
Contact time, min
surfactant, mg/dm3 surfactant, % phenol, mg/dm3 %
10 0.96 95.20 0.87 95.65
20 0.91 95.45 0.63 96.85
30 0.89 95.55 0.50 97.50
60 0.89 95.55 0.50 97.50
80 0.90 95.50 0.50 97.50
100 0.90 95.50 0.49 97.55
120 0.89 95.55 0.50 97.50
180 0.90 95.50 0.49 97.55

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Table 4. Influence of ionite doses on the removal of surfactant and phenol

Concentration of Decreasse of Concentration of Decreasse of phenol,
Ionite doses, g/dm3
surfactant, mg/dm3 surfactant, % phenol, mg/dm3 %
0.5 1.52 92.40 0.94 95.30
1.0 1.50 92.50 0.82 95.90
2.0 1.12 94.40 0.68 96.6
3.0 0.90 95.50 0.50 97.50
4.0 0.89 95.55 0.50 97.50
5.0 0.88 95.60 0.50 97.50
6.0 0.89 95.55 0.49 97.55
7.0 0.88 95.60 0.49 97.55

Table 5. Ion exchange capacity determined under The ion-exchange capacity of anion exchang-
static conditions er under the flow conditions was higher than the
Ion exchange capacity, mg/g ion-exchange capacity determined under the non-
Type of pollution
Ionite moisture Ionite dry flow conditions. The differences in ion exchange
Surfactant 4,78 13,28 capacity values are related to the method of deter-
Phenol 6,50 18,05 mining the ion exchange balance. In the ion ex-
change process carried out under non-flow condi-
tions, the equilibrium is determined once. The ex-
ion exchange process were constructed for the change process carried out under flow conditions
detergent and the phenol (Figure 1 and Figure 2). due to the batching of the model solution allows to
The drawn graphs were used to determine the use- establish new equilibrium states. This results in a
ful exchange capacity of the used ion exchanger better use of the ion exchange capacity. The useful
(Table 6). exchange capacity determined for detergent dur-
The anion-exchanger puncture point for ing the second and the third filtration cycles were
the detergent was determined at the level of smaller than the ones received in the 1st cycle of
0.1 mg/dm3, and for the phenol it amounted to the ion exchange process by 10%. In the case of
0.00 mg/dm3. phenol, the ion-exchange capacity was smaller
Moistness of the ion exchanger samples than in the first filtration cycle by 14.29% in the
placed in the filtration columns amounted to 65%. second cycle, and by 17.86% in the third cycle.

Figure 1. Ion exchange breakthrough curves (isoplanes) – (initial surfactant concentration of 20.00 mg/dm3,
filtration rate of 10 m/h)

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Figure 2. Ion exchange breakthrough curves (isoplanes) – (initial phenol concentration of 20.00 mg/dm3, filtra-
tion rate of 10 m/h)

Table 6. Usable ion exchange capacity of AMBERLITE IRA900 Cl resin determined under flow conditions
Usable ion exchange capacity, mg/g
I – cycle II – cycle III – cycle
Type of pollution
Ionite Ionite
Ionite dry Ionite moisture Ionite dry Ionite dry
moisture moisture
Surfactant 9,90 26,77 8,91 24,08 8,91 24,08

Phenol 14,00 37,84 12,00 32,43 11,50 31,08

CONCLUSIONS run cycle, 31.42 mg/g in the second run cycle, and
the least, that is, 28.57 mg/g, in the third run cycle.
In the ion exchange process conducted using The useful ion-exchange capacity of the anion-
strongly alkaline, anion-exchange AMBERLITE exchanger was larger in the case of phenol than in
IRA900 Cl resin yielded good results in the re- the case of the detergent. The detergent, due to its
moval of both anionic detergent and phenol. larger particles, entered the channels of the ion
Anionic detergents, the largest group of the exchanger at a slower rate, and even partially ob-
surface-active agents (ca. 80%), decompose into structed the access to the place of ion exchange.
surface-active anions, which is why utilising Besides the ion exchange process of the mac-
them for the anion-exchange removal was effec- roporous AMBERLITE IRA900 resin, an ad-
tive. The useful capacity of ion-exchange resin sorption process took place as well, as proven
towards the detergent amounted to 25.60 mg/g for by the useful ion-exchange capacities achieved
the first run cycle, and 22.74 for the second and after second and third regeneration of the ion
the third run cycles. exchanger (after second and third cycle of the
Phenol is a weak acid which decomposes into ion exchanger filter). When designing an ion ex-
a phenolic ion and a proton. The phenolic anion change bed, one should use exchange the capacity
was removed through the ion exchange with an- values received in the further work cycles of the
ion-exchange resin used in the tests. The useful ion exchanger, since part of the pollution filtered
exchange capacity of the tested ion exchanger to- during the first run cycle is not removed during
wards phenol amounted to 37.14 mg/g in the first the regeneration process.

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