World Academy of Science, Engineering and Technology

International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:2, No:11, 2008

Removal of Boron from Waste Waters by Ion-

Exchange in a Batch System
Pelin Demirivi, and Glhayat Nasn-Saygl

anthropogenic water-soluble boron compounds are discharged

AbstractBoron minerals are very useful for various industrial to aqueous environment. Boron is normally in very low
activities, such as glass industry and detergent industry, due to its amounts in soil and irrigation waters, but it accumulates very
mechanical and chemical properties. During the production of boron fast in soils irrigated with boron-containing wastewaters
compounds, many of these are introduced into the environment in the because of difficulty of washing it. Boron compounds passing
form of waste. Boron is also an important micro nutrient for the
to soil, surface waters and ground waters form many
plants to vegetate but if it exists in high concentrations, it could have
toxic effects. The maximum boron level in drinking water for human
complexes with heavy metals, such as Pb, Cd, Cu, Ni, etc. and
International Science Index, Chemical and Molecular Engineering Vol:2, No:11, 2008 waset.org/Publication/11190

health is given as 0.3 mg/L in World Health Organization (WHO) these complexes are more toxic than heavy metals forming
standards. The toxic effects of boron should be noted especially for them. Although little amount of boron is a nutrient for some
dry regions, thus, in recent years, increasing attention has been paid plants, its excessive amount affects badly the growth of many
to remove the boron from waste waters. In this study, boron removal agricultural products. The World Health Organization (WHO)
is implemented by ion exchange process using Amberlite IRA-743 has given a recommendation of below 0.3 mg/L boron for the
resin. Amberlite IRA-743 resin is a boron specific resin and it quality of drinking water [9].
belongs to the polymerizate sorbent group within the aminopolyol There is a small range between boron deficiency and boron
functional group. Batch studies were performed to investigate the toxicity in plants [10]. Boron has been shown to play a role in
effects of various experimental parameters, such as adsorbent dose,
carbohydrate metabolism, sugar translocation, pollen
initial concentration and pH, on the removal of boron. It is found
that, when the adsorbent dose increases removal of boron from the germination, hormone action, normal growth and functioning
liquid phase increases. However, an increase in the initial of the apical meristem, nucleic acid synthesis, and membrane
concentration decreases the removal of boron. The effective pH structure and function [11].
values for removal of boron are determined between 8.5 and 9. In aqueous environments, boron is mainly present as boric
Equilibrium isotherms were also analyzed by Langmuir and acid and partially as borate ions according to the dissociation
Freundlich isotherm models. The Langmuir isotherm is obeyed better reaction (Ka =61010, pKa 9.1) as shown in the following
than the Freundlich isotherm. equation [9]:

KeywordsAmberlite resin, boron removal, ion exchange, B(OH)3(aq) +H2O B(OH) 4 (aq) +H(aq)+
isotherm models.
Among several methods of boron removal from aqueous
I. INTRODUCTION
solutions, the use of boron-selective resins seems to have still

D EVELOPMENT of the ecologically and economically

appropriate technology to remove the toxic compounds
of boron from different waters is a pressing goal over the
the highest importance. Some studies on application of flying
ashes or natural sorbents, inorganic adsorbents show boron-
selective resins based on macroporous polystyrene matrices
entire world. This is due to a wide spreading of this element in with N-methyl glucamine ligand as the best sorbent. Simonnot
both natural waters and waste waters [1]-[6]. Boron has a et al. have reviewed the methods of boron removal from
number of minerals, in nature mostly calcium and/or sodium drinking water. Among them, they have pointed that the use of
borates, such as colemanite (2CaO.3B2O3.5H2O), ulexite boron-selective resins is the most efficient one [12]-[21].
(Na2O.2CaO.5 B2O3.16H2O), tinkal (Na2O. 2B2O3.10H2O), Numerous researchers studied boron removal and/or recovery
etc. [7], [8]. from wastewaters. Amberlite IRA 743, a boron specific resin,
There is a variety of application including various boron was used in boron removal from geothermal waters containing
fertilizers, insecticides, corrosion inhibitors in anti-freeze 19 mg/L boron and it was found that 99% of boron from
formulations for motor vehicle and other cooling system, geothermal water could be removed [22].
buffers in pharmaceutical and dyestuff production, and the use This study focuses on boron removal by means of ion
of boron compounds for moderator in nuclear reactor, where exchange process. Batch experiments were studied to
determine the effects of several parameters such as, initial
Pelin Demirivi is with the Chemical Engineering Department, Istanbul solution concentration, pH, and amount of adsorbent on boron
Technical University, Istanbul, 34469, Turkey (e-mail: demircivi@itu.edu.tr). removal from wastewater. Langmuir and Freundlich isotherm
Glhayat Nasn-Saygl is with with the Chemical Engineering models were used for the evaluation of findings.
Department, Istanbul Technical University, Istanbul, 34469, Turkey
(corresponding author ; phone: +90 212 2856839; fax: +90 212 2853425; e-
mail: nasun@itu.edu.tr).

International Scholarly and Scientific Research & Innovation 2(11) 2008 325 scholar.waset.org/1999.2/11190
 World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:2, No:11, 2008

II. EXPERIMENTAL 100,00

In this study, Amberlite IRA-743 resin was procured from 90,00
Merck DarmstadtGermany. Boric acid which contains 56.3% 80,00
B2O3 was supplied from Eti Maden. The other chemicals used
70,00
were of analytical reagent grade supplied by Merck

Efficiency (%)
60,00
DarmstadtGermany. 20 mg/L
Boron stock solution (1000 mg/L) was prepared by 50,00
40 mg/L
weighing in analytical balance and dissolving an appropriate 40,00 60 mg/L

quantity of boric acid (H3BO3) in distilled water, and the 30,00

working solutions were prepared by diluting this solution. In 20,00

this work, 20 mg/L, 40 mg/L and 60 mg/L boron solutions 10,00
were prepared and used in batch experiments. To observe the 0,00
effect of adsorbent dosage on boron removal, different 0,00 2,00 4,00 6,00 8,00 10,00 12,00

amounts of Amberlite resin were used (0,1-10 g). In order to Amount of Amberlite resin (g)

investigate the effect of pH, initial pH of solution was varied

from 2 to 10. Fig. 1 Effects of adsorbent amount and initial concentration on
The experiments were carried out using the batch method. boron removal efficiency
International Science Index, Chemical and Molecular Engineering Vol:2, No:11, 2008 waset.org/Publication/11190

Batch ion exchange experiments were conducted using

various amounts of resin with 50 ml of solutions containing Isotherms of the adsorption system were shown in Fig. 2
boron ions of desired concentrations at constant temperatures which demonstrated boron removal increased with increasing
in 250 ml flasks. pH was adjusted to the desired level with the amount of adsorbent. Increasing resin/solution ratio that
NaOH and HCl solutions. The samples were agitated at means increasing the resin-solution contact surface causes
constant speed with magnetic stirrer during 24 h and then higher boron removal efficiency.
filtered to get the clear solution. The clear solution was
analyzed in order to determine its boron content by using 3,5

volumetric method. The pH values at equilibrium after 24 h

3,0
were measured. All experiments have been taken at the room
temperature. 2,5

2,0
III. RESULTS AND DISCUSSION
q (mg/g)

1,5 20 mg/L
A. Effect of Adsorbent Quantity and Initial Boron
40 mg/L
Concentration 1,0
60 mg/L
The effect of adsorbent quantity was examined by using 0,5
various amounts of Amberlite IRA-743 resin. In experiments,
initial boron concentration was kept constant. Then 0,0
0 10 20 30 40 50 60
experiments were repeated for various boron concentrations
C (mg/L)
while the resin amount was kept constant. The results are
shown graphically in Fig. 1 and Fig. 2. Initial and final boron
concentrations were measured by using volumetric method. In Fig. 2 Adsorption isotherm (c0: 20-60 mg/L; m: 0,1-10 g)
order to obtain the sorption capacity (q), the amount of ions
adsorbed per unit mass of adsorbent (mg/g) was given in (1): B. Isotherm Model
The relationship between the amount of boron adsorbed and
q = [(c0 c ) / m] V (1) the boron concentration remaining in solution is described by
where c0 and c are the initial and final boron concentration an isotherm. The analysis of the isotherm data is important to
(mg/L) in the solution, m the amount of the adsorbent used (g) develop an equation which accurately represent the results and
and V the volume of the aqueous phase (L). The yield or which could be used for design purposes. In order to
amount of boron retained is given in (2): investigate the sorption isotherm Langmuir and Freundlich
isotherm models were analyzed to quantify adsorption
capacity of Amberlite resin. Langmuir isotherm model is
[
Removal efficiency = (c0 c ) / c 0 100 ] (2) based on assuming a monolayer sorption onto a surface with a
fixed number of well defined sites. The isotherm is given in
(3):
Fig. 1 shows that the removal efficiency increased with
increasing amount of adsorbent. It can also be seen that the
efficiency decreased with increasing boron concentration. q = (K L c ) / (1 + a L c ) (3)
Maximum efficiency (98.86%) was obtained by using 7.01 g
adsorbent and 20 mg/L initial boron concentration.

International Scholarly and Scientific Research & Innovation 2(11) 2008 326 scholar.waset.org/1999.2/11190
 World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:2, No:11, 2008

Rearranging the Langmuir equation gives (4), which is TABLE II

FREUNDLICH ISOTHERM DATA
linear.
c (mg/L) KF n R2
c / q = (1 / K L ) + (a L / K L ) c (4) 20 0,53 1,2 0,91

q : equilibrium concentration of adsorbate in solid phase 40 0,32 1,49 0,89

(mg/g)
c : equilibrium concentration of asdorbate in liquid 60 0,34 2,01 0,88
phase (mg/L)
KL/ aL : sorption capacity (mg/g)
According to the correlation coefficients of both isotherm
The coefficients KL and aL can thus be determined by models, Langmuir isotherm best represents the equilibrium
plotting c/q versus c. Langmuir isotherm model correlation adsorption of boron on the Amberlite resin.
coefficients are given in Table I: C. Effect of pH
TABLE I The removal processes and reactivity of boron in solutions
LANGMUIR ISOTHERM DATA are influenced by pH in a significant way. In this section, the
International Science Index, Chemical and Molecular Engineering Vol:2, No:11, 2008 waset.org/Publication/11190

c (mgL-1) KL (1/g) aL (1/mg) R2 effect of pH on boron removal was analyzed and found that
pH is a considerably important control parameter for boron
20 0,85 0,19 0,91 removal processes. The experimental results obtained are
shown in Fig. 3. It can be seen that boron selectivity is
40 0,42 0,12 0,97 efficient at pH 8.5-9. The amount of boron adsorbed depends
on the distribution of B(OH)3 and B(OH)4- which are
60 0,28 0,11 0,97 controlled by pH of the solution. It is the point at which the
borate ion predominance starts to increase according to the
acid-base equilibrium of boric acid. These two species
Freundlich isotherm model gives an expression compete for the adsorption on the resin. The tetrahedral
encompassing the surface heterogeneity and the exponential B(OH)4- becomes dominant species at pH between 9 and 10
distribution of active sites and their energies. The isotherm is for total boron concentration less than 3000 mg/L. It is also
derived to model the multilayer adsorption and relates the known that, the Amberlite resin shows high selectivity for the
uptake of solute onto the exchanger to the solution boron at basic pH and works as a chelating resin in basic
concentration, as shown in (5): media in its free amine form. The boron complexation at basic
1 pH is carried out by the hydroxyl groups which have different
affinity for the species B(OH)3 and B(OH)4- [23]-[25].
q = KF c n
(5)

The equation may be linearized by taking the logarithm of

100,00
both sides of (5) and can be presented as shown in (6):

log q = log K F + (1 / n ) log c

80,00
(6)
Efficiency %

60,00
q : equilibrium concentration of adsorbate in solid phase
20 mg/L
(mg/g) 40 mg/L
40,00
c : equilibrium concentration of asdorbate in liquid phase 60 mg/L
(mg/L)
KF, n : Freundlich constants related to the adsorption 20,00

capacity and intensity

0,00
0,00 2,00 4,00 6,00 8,00 10,00
The numerical value of 1/n < 1 indicates that adsorption
pH
capacity is only slightly suppressed at lower equilibrium
concentrations. The values of KF and n can be calculated from Fig. 3 Effect of pH on boron removal efficiency
the intercepts and slopes of the plots of each isotherm. The
correlation coefficients data of Freundlich isotherm model are
given in Table II: IV. CONCLUSION
In the present study, the removal of boron from aqueous
solution was investigated by using Amberlite IRA-743 resin.
The following results are determined from the experiments;

International Scholarly and Scientific Research & Innovation 2(11) 2008 327 scholar.waset.org/1999.2/11190
 World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:2, No:11, 2008

All the batch analyses showed that Amberlite IRA-743 [21] Kabay, N., Sarp, S., Yuksel, M., Arar, . & Bryjak, M., Removal of
boron from seawater by selective ion exchange resins, Reactive &
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Functional Polymers, 67, pp. 16431650, 2007.
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2005.
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respectively. Amount of resin is proportional with boron boron from aqueous solution by using neutralized red mud, Journal of
removal efficiency due to increase in the resin surface area. Hazardous Materials, 2006.
Compared to the Freundlich isotherm, the Langmuir isotherm [25] Lou, J., Modelling of boron sorption equilibrium and kinetic studies of
ion exchange with boron solution, PhD Thesis, Oklahoma State
model represented the measured sorption data well. This University, USA, 1997.
indicates that the monolayer adsorption occur.

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