Nitrilotris(methylenephosphonic) acid as a complexing agent in sorption of heavy metal ions on ion exchangers

doi:10.1016/j.cej.2012.10.054

Chemical Engineering Journal

Volumes 215–216, 15 January 2013, Pages 948-958

https://doi.org/10.1016/j.cej.2012.10.054 Get rights and content

Abstract

In this work the strongly basic anion exchanger Amberlite IRA 402, the weakly basic anion exchangers Purolite A 100 and Purolite A 103 as well as the chelating ion exchangers Purolite S 920 and Purolite S 930 were used to investigate the influence of phase contact time, pH and metal(II) concentration on the sorption of the heavy metal complexes of Cd(II), Pb(II), Cu(II) and Zn(II) with nitrilotris(methylenephosphonic acid), NTMP. These types of complexes are often found in industry where NTMP is used. The studies were carried out in the M(II):NTMP = 1:2 system. The sorption capacity of the studied ion exchangers increases with the increase of the initial M(II) ions concentration and the sorbate/ion exchanger ratio. It was found that sorption capacity increases with the increasing temperature and initial pH of metal solution. Equilibrium sorption tests show that chelating ion exchangers as well as the strongly basic anion exchanger have a larger capacity and affinity for sorption of Cd(II), Pb(II), Cu(II) and Zn(II) complexes with NTMP than weakly basic anion exchangers. It was found that the Langmuir and Hill models were more representative to describe complexes sorption than the Freundlich, and Dubinin–Radushkevich ones whereas the kinetic process followed the pseudo second-order pattern.

Highlights

• Different ion exchangers were used in removal of heavy metals from solutions. • The different factors affecting the metal ions loading in the presence of NTMP. • The pH, contact time and system composition were studied.

Introduction

In recent years the organic chemicals possessing phosphonates functional groups, among them, phosphonates-based chelating agents are of great interest. They are often structure analogues of aminopolycarboxylates for example: NTA (nitrilotriacetic acids) and NTMP (nitrilotris(methylenephosphonic) acid, EDTA (ethylenediaminetetraacetic acid) and EDTMP (1,2-diaminoethanetetrakis(methylenephosphonic acid) or DTPA (diethylenetriaminepentaacetic acid) and DTPMP (diethylenetriaminepentakis (methylenephosphonic acid). They are used in a growing number of applications to prevent formation of precipitates, to depress metal ions activity and to increase the total dissolved metal ion concentrations. In many of these applications their molecular charge, protonation level, ability to bind metal ions are significantly important [1], [2]. Moreover, they can form stable and water soluble complexes with metal ions as hybrid inorganic–organic materials useful for intercalation, catalysis, sorption and ion exchange. Therefore phosphonates can be also applied for chemical water treatment, oil drilling, formulation of detergents and corrosion control [3], [4], [5], [6], [7]. For example, many water treatment chemical formulations contain NTMP as an important ingredient owing to the following advantages:

•
Multifunctional performance from a single raw material.
•
Superior cost/performance in scale inhibition.
•
Synergistic performance from formulated mixtures.

Phosphonates are used in both consumer and institutional laundry detergents applications. In consumer laundry products they perform special functions such as stain removal, bleach stabilization and anti-encrustation. They find use as co-builders, synergistic boosters for stain removal in combination with phosphonates and anti-encrustation additives. During their use in the above-mentioned fields of industry, the synthetic phosphonate chelating agents are brought into contact with toxic metal ions. Therefore the investigations connected with the exploration of the processes of generation of toxic metal ion-phosphonate complexes, their speciation and sorption behavior in aqueous environmental media as well as rates of complex dissociation and ligand breakdown are very important.

One of the phosphonates used on a large scale is nitrilotris(methylenephosphonic) acid, NTMP whose formula can be also represented as the zwitter-ion form due to a different way of proton binding [8], as presented below:The solid state of NTMP is crystal powder, soluble in water, easily deliquescent, suitable for usage at low temperatures. At high concentration, it has good corrosion inhibition. NTMP is used in industrial circulating cool water system and oilfield water pipeline in the thermal power plant and the oil refinery plant. NTMP can decrease scale formation and inhibit corrosion of metal equipment and pipeline. It can be used as a chelating agent in weaving and dyeing industries and as a metal surface treatment agent.

In literature there are a lot of papers describing metal complexes with NTMP in the solid phase. For example, in the paper by Clearfield [9] the series of complexes of metal ions Mn(II), Co(II), Ni(II), Zn(II) and Cd(II) with NTMP in the system M(II):NTMP = 1:1 of the composition [MNH(CH₂PO₃H)₃(H₂O)₃] was presented. It was found that three water molecules and three oxygen atoms from two phosphonate anions of H₃NH(CH₂PO₃H)₃ are octahedrally coordinated to the metal ion, as a result of which eight-membered rings are formed. It was also stated that hydrogen bonding controls formation of the layers obtaining a three dimensional structure [10]. In the case of Pb(II) ions, two types of complexes with NTMP were prepared by mixing Pb(CH₃COO)₂ with NTMP. In the paper by Cabeza et al. [11] the [AlN(CH₂PO₃H)₃]⋅H₂O complex was also described. In the case of Cu(II) ions, the anhydrous complexes with NTMP were not obtained whereas for Mn(II) ions the appropriate complexes were prepared when the ratio of M(II):NTMP was 1:10 or greater. Moreover, Martinez-Tapia et al. [12] using the X-ray analysis found that in the metal ion-NTMP crystal there occur stresses due to which these structures are very difficult to obtain at normal temperature.

Metal–organic compounds with open frameworks, such as metal phosphonates could be also considered as excellent ion sorbents and ion exchangers due to their great variety of chemical and structural compositions as well as high thermal and radiation resistance. Metal phosphonate open framework materials are located between the porous zeolite like materials and the metalorganic framework (MOF) materials. However, compared with their phosphate analogues, the organic moiety of metal phosphonates can be designed to provide different networks and specific properties. Their structures depend on the metal type, the function of the organic ligand and the reaction conditions. For instance, in the papers by Bortun et al. [13], [14], [15], [16] the sorption behavior of tin(IV) nitrilotris(methylene)triphosphonates was investigated. These synthetic hybrid inorganic–organic sorbents are characterized by high thermal and radiation stability, chemical stability at pH below 8–10, resistance to oxidation, high ion exchange capacity, good kinetics of sorption and high selectivity for Cd(II), Pb(II) as well as Li(I) and Cs(I), moderately high affinity for Cu(II) and Co(II) and extremely low for Cr(III) and Hg(II). In the case of 1 M NaNO₃ or NaCl the affinity series was found to be: Pb(II) > Cu(II) > Cr(III) ≈ Co(II) > Cd(II) > Hg(II). Therefore, they can be successfully used for industrial and nuclear waste water treatment, selective recovery of noble metals and toxic metals, for separation at elevated temperatures and in the presence of strong oxidants that is under the conditions when common ion exchangers cannot be used.

In the literature there are also some papers dealing with the application of metal-phosphonates as corrosion inhibitors. Demadis et al. [17] described the Zn(II)–NTMP hybrid [ZnNH(CH₂PO₃H)₃(H₂O)₃]_x as an inhibitor for the corrosion of steel. It was found that the corrosion rate of the sample was 2.5 mm/year whereas for the Zn–NTMP protected sample only 0.9 mm/year.

Taking into account the above-mentioned possibilities in the presented paper the studies of the sorption of heavy metal ions, i.e. Cd(II), Pb(II), Cu(II) and Zn(II) in the presence of nitrilotris(methylenephosphonic acid) (NTMP) on the strongly basic anion exchanger Amberlite IRA 402, the weakly basic anion exchangers Purolite A 100 and Purolite A 103 as well as the chelating ion exchangers Purolite S 920 and Purolite S 930 were carried out. Synthetic ion exchangers are known for selective adsorption and removal of metal ions from waters and waste waters. The influence of pH, metal(II) concentration and temperature on the sorption of heavy metal complexes with nitrilotris(methylenephosphonic acid) was studied. Different adsorption isotherm models and mathematical equations describing kinetics of sorption were also proposed to describe these processes.

Section snippets

Materials

The polystyrene anion exchangers with different basicity of functional groups, i.e. Amberlite IRA 402, Purolite A 100, Purolite A 103 as well as the chelating ion exchangers Purolite S 920 and Purolite S 930 were used (Table 1). For the experiments, the resins were first pretreated with 1 M HCl and 1 M NaOH to remove impurities from their synthesis. Nitrilotris(methylenephosphonic acid) (NTMP) was supplied by Sigma–Aldrich. All other reagents used were of analytical grade.

Solutions preparation

The solutions of M(II)

Characterization of the ion exchangers after the sorption process

The characteristics of ion exchangers used in the investigations are shown in Table 1. Fig. 1 presents the FT-IR spectra of the strongly basic anion exchanger Amberlite IRA 402 before and after the sorption of Cu(II)–NTMP complexes at different pH values (pH 3, 5, 7 and 12). Analogous spectra were recorded for the other studied ion exchangers. Their analysis was limited to 900–1200 cm⁻¹, where the bond between phosphorous and oxygen is active. Other bands are associated with the structure of the

Conclusions

The commercially available chelating ion exchangers Purolite S 930 and Purolite S 920 containing O, N and S donor atoms as well as the strongly basic anion exchanger Amberlite IRA 402 were used for the removal of heavy metal complexes of Cd(II), Pb(II), Cu(II) and Zn(II) with NTMP. The FT-IR spectroscopy and the SEM analysis were employed to characterize their structure and morphology before and after the sorption process. Their sorption properties towards metal complexes with NTMP were

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NTMP is capable of preventing corrosion of metal equipment and reducing scale formation. To this end, It is used in the dyeing and weaving industries as a metal surface treatment agent or a chelating agent [17]. Kołodyńska et al. investigated the adsorption capacity of NTMP as a complexing agent for the removal of metal ions and discovered that it is a positive function of the metal solution’s initial pH and temperature [17].
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Chemical Engineering Journal

Abstract

Highlights

Introduction

Section snippets

Materials

Solutions preparation

Characterization of the ion exchangers after the sorption process

Conclusions

References (26)

Recent advances in metal phosphonate chemistry II

Curr. Opin. Solid State Mater. Sci.

Hydrolytic stability of amorphous titanium and zirconium

Mater. Res. Bull.

Crystal growth and characterization of zinc-(amino-tris-(methylenephosphonate)) organic–inorganic hybrid networks and their inhibiting effect on metallic corrosion

Inorg. Chem. Commun.

Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods

Water Res.

In vitro biosorption of ochratoxin A on the yeast industry by-products: comparison of isotherm models

Bioresour. Technol.

Insights into the modeling of adsorption isotherm systems

Chem. Eng. J.

Investigation into the effect of phosphonate inhibitors on barium sulfate precipitation

J. Cryst. Growth

Complexes of nitrilotrimethylphosphonic acid with cobalt, nickel, copper and zinc

Polyhedron

An ATR-FTIR study of different phosphonic acids adsorbed onto boehmite

Spectrochim. Acta

Divalent cations speciation with three phosphonate ligands in the pH-range of natural waters

Talanta

Ion exchange on resins with temperature-responsive selectivity III. Influence of complex formation stoichiometry on temperature dependence of resin selectivity

J. Chromatogr.

Cited by (15)

The immobilization of Sr(ll) and Co(ll) via magnetic easy-separation organophosphonate-hydroxyapatite hybrid nanoparticles

Synthesis of magnetic Fe<inf>3</inf>O<inf>4</inf>@SiO<inf>2</inf>-(-NH<inf>2</inf>/-COOH) nanoparticles and their application for the removal of heavy metals from wastewater

Extra strong Cu<sup>2+</sup>-doped intumescent char to protect epoxy resin against fire

Erbium adsorption from aqueous solutions using RSM-based optimization of the phosphate functional group in modified nano titania

The ratiometric detection and mechanism of three typical phosphonates by quercetin-based fluorescent probe with low detection limits

Size-dependent magnetic properties of iron oxide nanoparticles