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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 Demirçivi, and Gülhayat Nasün-Saygılı

anthropogenic water-soluble boron compounds are discharged
Abstract—Boron 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 =6×10−10, pKa 9.1) as shown in the following
than the Freundlich isotherm. equation [9]:

Keywords—Amberlite 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 Demirçivi 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
Gülhayat Nasün-Saygılı 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

86%) was obtained by using 7. boron removal efficiency International Science Index. 20 mg/L. In experiments. 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).5 2. In 20.5 various amounts of Amberlite IRA-743 resin. The results are shown graphically in Fig. The isotherm is given in (3): Fig. International Scholarly and Scientific Research & Innovation 2(11) 2008 326 scholar.1-10 g).5 20 mg/L A. No:11. All experiments have been taken at the room temperature.1-10 g) order to obtain the sorption capacity (q).00 6.00 were prepared and used in batch experiments. Molecular.2/11190 .00 4.00 B2O3 was supplied from Eti Maden. Initial and final boron concentrations were measured by using volumetric method.00 2. 2.00 60 mg/L quantity of boric acid (H3BO3) in distilled water.00 Darmstadt–Germany.00 amounts of Amberlite resin were used (0.00 10.00 In this study. filtered to get the clear solution. Fig. It can also be seen that the efficiency decreased with increasing boron concentration. In Fig.00 40 mg/L weighing in analytical balance and dissolving an appropriate 40. q = (K L c ) / (1 + a L c ) (3) Maximum efficiency (98. World Academy of Science. To observe the 0. The clear solution was analyzed in order to determine its boron content by using 3.0 60 mg/L The effect of adsorbent quantity was examined by using 0. 2 boron ions of desired concentrations at constant temperatures which demonstrated boron removal increased with increasing in 250 ml flasks. 1 Effects of adsorbent amount and initial concentration on The experiments were carried out using the batch method. initial boron concentration was kept constant. Then 0. 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.00 were of analytical reagent grade supplied by Merck Efficiency (%) 60. 2008 waset. m: 0. EXPERIMENTAL 100. The pH values at equilibrium after 24 h 3. Chemical and Molecular Engineering Vol:2. 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. 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.5 volumetric method. RESULTS AND DISCUSSION q (mg/g) 1.org/1999. Effect of Adsorbent Quantity and Initial Boron 40 mg/L Concentration 1. The yield or which could be used for design purposes. The other chemicals used 70.00 effect of adsorbent dosage on boron removal. 1 shows that the removal efficiency increased with increasing amount of adsorbent. the amount of ions adsorbed per unit mass of adsorbent (mg/g) was given in (1): B.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. 2 Adsorption isotherm (c0: 20-60 mg/L. 40 mg/L and 60 mg/L boron solutions 10. In order to Amount of Amberlite resin (g) investigate the effect of pH.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. Materials and Metallurgical Engineering Vol:2.00 working solutions were prepared by diluting this solution. 1 and Fig. The analysis of the isotherm data is important to (mg/L) in the solution. initial pH of solution was varied from 2 to 10. Increasing resin/solution ratio that NaOH and HCl solutions. Boric acid which contains 56. 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.3% 80. No:11. 2.00 Merck Darmstadt–Germany. 20 mg/L Boron stock solution (1000 mg/L) was prepared by 50. Engineering and Technology International Journal of Chemical. 2008 II. pH was adjusted to the desired level with the amount of adsorbent. and the 30.0 were measured. different 0.00 12.00 this work. Nuclear.0 III.01 g adsorbent and 20 mg/L initial boron concentration. Amberlite IRA-743 resin was procured from 90.00 8.waset.

The amount of boron adsorbed depends on the distribution of B(OH)3 and B(OH)4.85 0. It is also derived to model the multilayer adsorption and relates the known that. coefficients are given in Table I: C. 2008 waset. The correlation coefficients data of Freundlich isotherm model are given in Table II: IV.00 4. Nuclear.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 0.2 0. No:11.becomes dominant species at pH between 9 and 10 distribution of active sites and their energies.89 (mg/g) c : equilibrium concentration of asdorbate in liquid 60 0. 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. The tetrahedral encompassing the surface heterogeneity and the exponential B(OH)4.which are 60 0. 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.waset. q = KF ×c n (5) The equation may be linearized by taking the logarithm of 100. the International Science Index.00 0.2/11190 . No:11.00 6.00 capacity and intensity 0. It can be seen that boron selectivity is 40 0. Engineering and Technology International Journal of Chemical.49 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.00 q : equilibrium concentration of adsorbate in solid phase 20 mg/L (mg/g) 40 mg/L 40. Molecular. c (mg/L) KF n R2 c / q = (1 / K L ) + (a L / K L ) × c (4) 20 0. 3.01 0. In this section.12 0.32 1. The experimental results obtained are shown in Fig.19 0.00 2. Materials and Metallurgical Engineering Vol:2.00 c : equilibrium concentration of asdorbate in liquid phase 60 mg/L (mg/L) KF.00 The numerical value of 1/n < 1 indicates that adsorption pH capacity is only slightly suppressed at lower equilibrium concentrations.[23]-[25]. 3 Effect of pH on boron removal efficiency the intercepts and slopes of the plots of each isotherm. The values of KF and n can be calculated from Fig.00 10.28 0. n : Freundlich constants related to the adsorption 20.42 0.org/1999.97 efficient at pH 8. 2008 Rearranging the Langmuir equation gives (4).97 controlled by pH of the solution.11 0.00 both sides of (5) and can be presented as shown in (6): log q = log K F + (1 / n ) log c 80. International Scholarly and Scientific Research & Innovation 2(11) 2008 327 scholar. the removal of boron from aqueous solution was investigated by using Amberlite IRA-743 resin.34 2. Langmuir isotherm model correlation adsorption of boron on the Amberlite resin. It is the point at which the borate ion predominance starts to increase according to the acid-base equilibrium of boric acid.53 1.00 8. 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. The isotherm is for total boron concentration less than 3000 mg/L. World Academy of Science. The following results are determined from the experiments. Chemical and Molecular Engineering Vol:2.00 (6) Efficiency % 60. These two species Freundlich isotherm model gives an expression compete for the adsorption on the resin.5-9.91 q : equilibrium concentration of adsorbate in solid phase 40 0. CONCLUSION In the present study. as shown in (5): media in its free amine form.91 removal processes. Langmuir isotherm best represents the equilibrium plotting c/q versus c. which is TABLE II FREUNDLICH ISOTHERM DATA linear.

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