Magnetic polymer nanocomposite for removal of divalent heavy metal ions from water

Abstract

The magnetic polymer nanocomposite for removal of divalent heavy metal ions from water is magnetic nanocomposite having a core of magnetite (Fe.sub.3O.sub.4) in a shell of branched polyhydroxystyrene (BHPS), designated as Fe.sub.3O.sub.4@BHPS. The nanocomposite is synthesized by co-precipitation in alkali solution. Testing showed the nanocomposite reached 93% and 80% Pb(II) and Cd(II) adsorption, respectively, in 30 minutes, attaining equilibrium in 120 minutes. The maximum adsorption capacities of Pb(II) and Cd(II) at 298K were 186.2 and 125 mg/g, respectively. After adsorption, the nanocomposite with the heavy metal(s) adsorbed thereto was easily removed from aqueous solution by application of a magnetic field.

Claims

1. A method of making a magnetic polymer nanocomposite, comprising the steps of: dissolving FeCl.sub.3 and FeCl.sub.2 separately in HCl to form an Fe(III) solution and an Fe(II) solution, respectively; combining the Fe(III) solution and the Fe(II) solution to form a combined solution; adding a solution of branched polyhydroxystyrene (BPHS) in methanol and a solution of ammonium hydroxide to the combined solution dropwise to form a mixture; and stirring the mixture under nitrogen atmosphere to precipitate the magnetic polymer nanocomposite as Fe.sub.3O.sub.4 nanoparticles in a BPHS shell (Fe.sub.3O.sub.4@ BPHS).

2. The method of making a magnetic polymer nanocomposite according to claim 1, further comprising the step of removing the precipitated magnetic polymer nanocomposite by application of an external magnetic field.

3. The method of making a magnetic polymer nanocomposite according to claim 1, wherein said step of adding a solution of branched polyhydroxystyrene (BPHS) in methanol and a solution of ammonium hydroxide to the combined solution dropwise comprises adding a solution of branched polyhydroxystyrene (BPHS) in methanol and a solution of ammonium hydroxide to the combined solution dropwise until a pH of 10 is obtained.

4. The method of making a magnetic polymer nanocomposite according to claim 1, wherein said step of dissolving FeCl.sub.3 and FeCl.sub.2 separately in HCl to form an Fe(III) solution and an Fe(II) solution further comprises dissolving the FeCl.sub.2 in HCl in the presence of a flow of nitrogen gas to prevent oxidation of Fe(II).

5. The method of making a magnetic polymer nanocomposite according to claim 1, wherein said solution of ammonium hydroxide comprises a 28% NH.sub.4OH solution.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a reaction scheme for the synthesis of a magnetic polymer nanocomposite for removal of divalent heavy metal ions from water.

(2) FIG. 2 is a reaction scheme diagrammatically showing the adsorption of lead [Pb(II)] and cadmium [Cd(II)] ions by the magnetic polymer nanocomposite synthesized in FIG. 1.

(3) FIG. 3 is a composite of the Fourier transform infrared spectroscopy (FTIR) spectra of the intermediate products, viz., magnetite (Fe.sub.3O.sub.4) and branched polyhydroxystyrene (BPHS), and the product magnetic polymer nanocomposite of the reaction shown in FIG. 1.

(4) FIG. 4 is a plot of the X-ray diffraction (XRD) patterns of Fe.sub.3O.sub.4 and the magnetic polymer nanocomposite, Fe.sub.3O.sub.4@BHPS.

(5) FIG. 5A is a scanning electron micrograph (SEM) of branched polyhydroxystyrene (BPHS), and FIG. 5B is a SEM micrograph of the magnetic polymer nanocomposite.

(6) FIG. 6A is an energy dispersive X-ray (EDX) plot of the magnetic polymer nanocomposite; FIG. 6B is an energy dispersive X-ray (EDX) plot magnetic polymer nanocomposite after Pb(II) adsorption; and FIG. 6C is an energy dispersive X-ray (EDX) plot of the magnetic polymer nanocomposite after Cd(II) adsorption.

(7) FIG. 7 is a thermogravimetric analysis (TGA)/differential thermal analysis (DTA) plot of the magnetic polymer nanocomposite.

(8) FIG. 8A is a composite plot showing adsorption capacity as a function of initial pH for the adsorption of Pb(II) and Cd(II) by the magnetic polymer nanocomposite.

(9) FIG. 8B is a composite plot showing adsorption capacity as a function of contact time for the adsorption of Pb(II) and Cd(II) by the magnetic polymer nanocomposite.

(10) FIG. 8C is a composite plot showing adsorption capacity as a function of equilibrium concentration for the adsorption of Pb(II) by the magnetic polymer nanocomposite at different temperatures.

(11) FIG. 8D is a composite plot showing adsorption capacity as a function of equilibrium concentration for the adsorption of Cd(II) by the magnetic polymer nanocomposite at different temperatures.

(12) FIG. 9A is a chart showing regeneration of the magnetic polymer nanocomposite saturated with Pb(II) heavy metal ions by elution with 0.01M solutions of hydrochloric acid (HCl), nitric acid (HNO.sub.3), and sulfuric acid (H.sub.2SO.sub.4), respectively.

(13) FIG. 9B is a chart showing regeneration of the magnetic polymer nanocomposite saturated with Cd(II) heavy metal ions by elution with 0.01M solutions of hydrochloric acid (HCl), nitric acid (HNO.sub.3), and sulfuric acid (H.sub.2SO.sub.4), respectively.

(14) Similar reference characters denote corresponding features consistently throughout the attached drawings.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(15) The magnetic polymer nanocomposite for removal of divalent heavy metal ions from water is magnetic nanocomposite having a core of magnetite (Fe.sub.3O.sub.4) in a shell of branched polyhydroxystyrene (BHPS), designated as Fe.sub.3O.sub.4@BHPS. The nanocomposite is synthesized by co-precipitation in alkali solution. Testing showed the nanocomposite reached 93% and 80% Pb(II) and Cd(II) adsorption, respectively, in 30 minutes, attaining equilibrium in 120 minutes. The maximum adsorption capacities of Pb(II) and Cd(II) at 298K were 186.2 and 125 mg/g, respectively. After adsorption, the nanocomposite with the heavy metal(s) adsorbed thereto was easily removed from aqueous solution by application of a magnetic field.

(16) A method of removing a divalent heavy metal ions from aqueous solutions includes the steps of: (a) adding a magnetic polymer nanocomposite having a magnetite core and a branched polyhydroxystyrene shell (Fe.sub.3O.sub.4@BPHS) to an aqueous solution contaminated with a divalent heavy metal ions; (b) leaving the magnetic polymer nanocomposite in the aqueous solution for a period of time sufficient to saturate the magnetic polymer nanocomposite with the divalent heavy metal ions adsorbed on the nanocomposite; and (c) removing the saturated magnetic polymer nanocomposite from the aqueous solution by applying an external magnetic field. The method may further include the steps of: (d) eluting the magnetic polymer nanocomposite having the divalent heavy metal ions adsorbed thereon with a dilute solution of a strong acid in order to desorb the divalent heavy metal ions from the magnetic polymer nanocomposite; and (e) applying an external magnetic field to recover the magnetic polymer nanocomposite free from adsorbed divalent heavy metal ions for re-use.

(17) The magnetic polymer nanocomposite for removal of divalent heavy metal ions from water will be better understood with reference to the following examples.

Example 1

Synthesis of Magnetic Polymer Nanocomposite (Fe3O4@BPHS)

(18) In an exemplary synthesis, 2.36 g ferric chloride hexahydrate (FeCl.sub.3.6H.sub.2O) was dissolved in 100 mL 0.5M HCl solution in a 250 mL Erlenmeyer flask. In another 250 mL Erlenmeyer flask, 0.86 g ferrous chloride (FeCl.sub.2.4H.sub.2O) was dissolved in 100 mL 0.5M HCl solution under N.sub.2 gas flow for 20 min to prevent the oxidation of Fe(II). Then, the two solutions were mixed in a three-necked round bottom flask equipped with a mechanical stirrer at 80 C. under N.sub.2 gas flow to form a reaction mixture. After mixing, 0.5 g of branched polyhydroxystyrene (BPHS), in powder form, was dissolved in 30 mL methanol (CH.sub.3OH), and the methanolic BPHS solution was added dropwise, together with 20 mL of 28% NH.sub.4OH solution, to the reaction mixture under rigorous mechanical stirring (1000 rpm) for a period of 30 min until the pH of the reaction mixture reached around 10. The reaction mixture was then stirred for another 4 hrs under N.sub.2 atmosphere. Finally, a resulting black colloidal product was separated from the reaction mixture by application of an external magnetic field, and washed with deionized water and methanol to remove unreacted BPHS and other impurities. The precipitate was dried at room temperature over a watch glass for 48 hrs to obtain BPHS impregnated with magnetite nanoparticles, i.e., Fe.sub.3O.sub.4@BPHS. The synthesis scheme is shown diagrammatically in FIG. 1.

(19) The resulting product was characterized by Fourier transform infrared spectroscopy (FTIR), the spectra of the reactants and the products being compared in FIG. 3. In the spectrum of BPHS, a broad absorption peak is observed at around 3407 cm.sup.1 (presumably stretching of OH); 3022 cm.sup.1 (presumably stretching of ArCH); 2963 cm.sup.1 and 2831 cm.sup.1 (presumably asymmetric and symmetric stretching of CH, respectively); 1604 cm.sup.1 (stretching ArCC); 1507, 1448, and 1237 cm.sup.1 (bending OH, and CO). In the spectrum of Fe.sub.3O.sub.4@BPHS nanocomposite, 572 cm.sup.1 (FeO); 3398 cm.sup.1 (stretching OH); 3033 (stretching ArCH); 2936 cm.sup.1 and 2838 (asymmetric and symmetric stretching CH, respectively); 1603 (stretching ArCC), 1514, 1398, and 1220 cm.sup.1 (bending OH, and CO).

(20) The resulting product was also characterized by X-ray diffraction (XRD) the magnetite and the final product patterns being compared in FIG. 4. Observed characteristic peaks at 2=18.33, 30.2, 35.3, 43.2, 53.5, 57.3, 63.2 and 74.9 correspond to (111), (220), (311), (400), (422), (511), (440) and (533) indices, respectively, consistent with standard results for Fe.sub.3O.sub.4 in the Joint Committee on Powder Diffraction Standards database (JCPDS, file 19-0629), confirming the cubic spinel structure of pure Fe.sub.3O.sub.4. XRD results for Fe.sub.3O.sub.4@BPHS were qualitatively similar to those of Fe.sub.3O.sub.4, with no new peaks observed.

(21) The crystal sizes of Fe.sub.3O.sub.4 and Fe.sub.3O.sub.4@BPHS were determined from their respective XRD patterns by using Debye-Scherrer's equation, provided as equation (1):

(22) $\begin{array}{cc}{D}_S=K\frac{}{\left(\cos \right)},& \left(1\right)\end{array}$
where is the Bragg's peak, is the half-width of the diffraction peak, K is a constant that depends on the crystallite's morphology, and is the X-ray wavelength, assumed to be 0.154 nm. The (311) peak of the highest intensity was picked out to evaluate the crystal size. The crystallite sizes of Fe.sub.3O.sub.4 and Fe.sub.3O.sub.4@BPHS were found to be 11.8 and 14.5 nm, respectively.

(23) In addition, the resulting product was also characterized by SEM microscopy, FIGS. 5A and 5B comparing the BPHS reactant with the Fe.sub.3O.sub.4@BPHS product. A highly porous and uneven BPHS surface with no uniform sized pores was observed, as shown in FIG. 5A. FIG. 5B shows the Fe.sub.3O.sub.4@BPHS appears to take the form of a BPHS sheet impregnated with magnetite nanoparticles.

(24) Finally, the resulting product was characterized by thermogravimetric analysis (TGA)/differential thermal analysis (DTA), a plot of the product being shown in FIG. 7. A two-step weight loss within the temperature range 30-800 C. was observed. The first-step shows 6% weight loss due to the loss of physically absorbed water molecules, observed in the temperature range 30-280 C. The second-step shows 37% weight loss due to decomposition of the BPHS polymer component of the Fe.sub.3O.sub.4@BHPS, and was observed within a temperature range of 325-550 C.

(25) The surface area, pore volume and pore size of the exemplary Fe.sub.3O.sub.4@BHPS were determined through adsorption of nitrogen (N.sub.2) gas at 77 K using a Micromeritics Surface Area and Porosity analyzer (Gemini VII, 2390 Surface Area and Porosity analyzer). Prior to BET surface area measurement, the sample was degassed at 150 C. for 2 h. The surface area analysis of the exemplary Fe.sub.3O.sub.4@BPHS showed a Brunauer-Emmett-Teller (BET) surface area of 41.8 m.sup.2/g and an average pore diameter of 1.9 nm.

Example 2

Adsorption Experiments and Results

(26) Batch mode lead [Pb(II)] and cadmium [Cd(II)] adsorption experiments were carried out to test the efficacy of the Fe.sub.3O.sub.4@BPHS, synthesized as described in Example 1, as an adsorbent. In a 100 mL Erlenmeyer flask, 25 mL Pb(II) aqueous solution having an initial concentration (C.sub.o) of 25 mg/L was equilibrated with 0.015 g Fe.sub.3O.sub.4@BPHS over a thermostatic shaking assembly at 100 rpm operated at room temperature. At equilibrium, the saturated Fe.sub.3O.sub.4@BPHS nanocomposite was separated from the aqueous phase by an external magnetic field and the residual Pb(II) concentration was quantitatively determined by atomic adsorption spectrophotometry (AAS). Experimental parameters of pH, contact time, C.sub.o and temperature were varied. Similar batch mode adsorption experiments were conducted for Cd(II).

(27) The amount (q.sub.e, mg/g) and percentage (%) of Pb(II) and Cd(II) adsorption were calculated according to equation (2) and equation (3), respectively, as follows:

(28) $\begin{array}{cc}{q}_e,\mathrm{mg}\text{/}g=\left(C_o-C_e\right)\frac{V}{m}& \left(2\right)\\ \%\mathrm{adsorption}=\frac{C_o-C_e}{C_o}100,& \left(3\right)\end{array}$
where V is the volume of adsorbate solution (in L), m is the mass of Fe.sub.3O.sub.4@BPHS added (in g), and C.sub.o and C.sub.e (in mg/L) are the initial and equilibrium concentrations of Pb(II) or Cd(II) ions in solution, respectively.

(29) FIG. 2 is a reaction scheme diagrammatically showing the adsorption of lead [Pb(II)] and cadmium [Cd(II)] ions by the magnetic polymer nanocomposite synthesized in FIG. 1. FIG. 6A is an energy dispersive X-ray (EDX) plot of the magnetic polymer nanocomposite; FIG. 6B is an energy dispersive X-ray (EDX) plot magnetic polymer nanocomposite after Pb(II) adsorption; and FIG. 6C is an energy dispersive X-ray (EDX) plot of the magnetic polymer nanocomposite after Cd(II) adsorption. FIG. 6A shows C, O and Fe present in pristine Fe.sub.3O.sub.4@BPHS. FIGS. 6B and 6C show the presence of Pb(II) and Cd(II) in the Fe.sub.3O.sub.4@BPHS following adsorption experiments, respectively, confirming binding of the adsorbed heavy metals to Fe.sub.3O.sub.4@BPHS surface.

(30) FIG. 8A is a composite plot showing adsorption capacity as a function of initial pH for the adsorption of Pb(II) and Cd(II) by the magnetic polymer nanocomposite. Maximal Pb(II) and Cd(II) ion adsorption on the Fe.sub.3O.sub.4@BPHS nanocomposite was achieved for initial pH (pH.sub.i) values above 4 and 6, respectively; preferably between 5-7 and 6.5-9, respectively; and more preferably around 5.5 and 7.1, respectively. FIG. 8B is a composite plot showing adsorption capacity as a function of contact time for the adsorption of Pb(II) and Cd(II) by the magnetic polymer nanocomposite. The equilibration times for Pb(II) and Cd(II) ions adsorption on the Fe.sub.3O.sub.4@BPHS, i.e., the times for saturation, were at least 30 and 90 minutes, respectively; and preferably at least 90 and 120 min, respectively. FIG. 8C is a composite plot showing adsorption capacity as a function of equilibrium concentration for the adsorption of Pb(II) by the magnetic polymer nanocomposite at different temperatures. FIG. 8D is a composite plot showing adsorption capacity as a function of equilibrium concentration for the adsorption of Cd(II) by the magnetic polymer nanocomposite at different temperatures. The adsorption of Pb(II) and Cd(II) ions onto Fe.sub.3O.sub.4@BPHS was found to slightly decrease with increasing temperature over the range from 298-318K. The maximum capacity for Pb(II) and Cd(II) ion adsorption onto Fe.sub.3O.sub.4@BPHS was measured in the present exemplary experiments to be 186.2 mg/g and 125 mg/g, respectively at 298 K.

(31) Table 1 is the isotherm data for the adsorption of Pb(II) and Cd(II) on the magnetic polymer nanocomposite, Fe.sub.3O.sub.4@BPHS synthesized in Example 1.

(32) Table 2 is the kinetic data for the adsorption of Pb(II) and Cd(II) on the magnetic polymer nanocomposite, Fe3O4@BPHS when C.sub.o=25 mg/L.

(33) TABLE-US-00001 TABLE 1 Isotherm data for adsorption of Pb(II) and Cd(II) Isotherm models Langmuir Freundlich Metal Temperature q.sub.m b K.sub.F ions (K) (mg/g) (L/mg) R.sub.L R.sup.2 (mg/g)(L/mg).sup.1/n n R.sup.2 Pb(II) 298 163.9 0.085 0.319 0.964 19.64 2.10 0.981 308 158.7 0.058 0.465 0.962 14.67 2.00 0.975 318 129.9 0.064 0.438 0.904 12.49 1.94 0.972 Cd(II) 298 101.0 0.121 0.292 0.976 20.39 2.92 0.989 308 72.5 0.147 0.254 0.888 17.29 3.21 0.989 318 63.3 0.153 0.246 0.834 15.94 3.34 0.981

(34) TABLE-US-00002 TABLE 2 Kinetic data for adsorption of Pb(II) and Cd(II) Kinetic models Pseudo-first-order Pseudo-second-order q.sub.e,exp. q.sub.e,cal. q.sub.e,cal. Metal ions (mg/g) (mg/g) k.sub.1 (1/min) R.sup.2 (mg/g) k.sub.2 (g/mg-min) R.sup.2 Pb(II) 42.3 163.9 0.085 0.937 2.10 0.981 Cd(II) 41.2 101.0 0.121 0.929 20.39 2.92 0.989

Example 3

Regeneration Experiments and Results

(35) Pb(II) and Cd(II) ions were desorbed from saturated Fe.sub.3O.sub.4@BPHS nanocomposite by elution by a strong acid, such as HCl, H.sub.2SO.sub.4, or HNO.sub.3, in batch mode experiments. Samples of Fe.sub.3O.sub.4@BPHS, saturated with a divalent heavy metal ion (Pb.sup.+2 or Cd.sup.+2) removed from water or aqueous solution as described in Example 2, was treated with a 25 mL 0.01 M solution of one of the various eluents over a thermostatic shaker assembly shaken at 100 rpm for 24 hr to ensure complete elution of the adsorbed heavy metal ions by the acid. The solid and solution phases of the resulting mixture were magnetically separated, and the eluted heavy metal ions concentration was quantitatively determined by atomic absorption spectroscopy (AAS). The amount of heavy metal ions desorbed was calculated according to equation (3):

(36) $\begin{array}{cc}\%\mathrm{Desorption}=\frac{C_d}{C_{\mathrm{ia}}}100,& \left(4\right)\end{array}$
where C.sub.d is the concentration of the heavy metal ions desorbed by the eluent and C.sub.ia is the initial concentration of heavy metal ions adsorbed on the magnetic polymer composite, Fe.sub.3O.sub.4@BPHS. FIGS. 9A and 9B show the results of eluting the used magnetic polymer nanocomposite with a dilute solution of a strong acid.

(37) An adsorption/desorption scheme of Pb(II) and Cd(II) on Fe.sub.3O.sub.4@BPHS is shown in FIG. 2 using hydrochloric acid as an example, although 0.1 M nitric acid or 0.1 M sulfuric acid may be used instead of hydrochloric acid, as shown by FIGS. 9A and 9B.

(38) It is to be understood that the magnetic polymer nanocomposite for removal of divalent heavy metal ions from water is not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.