MIXED METAL OXIDE-HYDROXIDE BIOPOLYMER COMPOSITE BEADS AND A PROCESS THEREOF

Abstract

The present invention provides mixed metal oxide-hydroxide biopolymer composite beads for fluoride removal from groundwater and a process for the preparation thereof. The beads developed in the instant invention relate to novel granular adsorption medium which comprises two or more metal oxide-hydroxide/hydroxide/oxide nanoparticles and calcium alginate as supporting medium. The said mixed metal oxide-hydroxides and biopolymer composite (MBC) beads are useful for the treatment of fluoride containing drinking water by both batch and continuous mode operations. The MBC beads also showed arsenic sorption performance from spiked water by batch mode.

Claims

1. A mixed metal oxyhydroxide biopolymer composite beads for fluoride removal from drinking water wherein, the said beads comprising: (a) 15 to 55 (w/w) % of a metal content; (b) 10 to 35 (w/w) % of a biopolymer; remaining being oxygen and hydrogen.

2. The mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the metal is in the form of binary or ternary mixed metal oxide hydroxide nanoparticles.

3. The mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the metal is selected from the group consisting of Fe, Al, Cu, Mn, La, Zr, Ce and Mg.

4. The mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the mixed metal content comprises Fe and Al in the range of 6:1 to 1:6.

5. The mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the mixed metal content comprises Fe:Al:Z in the range of 1:1 to 6:0.1 to 0.7, wherein Z is a metal selected from the group consisting of Cu, Mn, La, Zr, Ce and Mg.

6. The mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the biopolymer is sodium alginate.

7. The mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the beads exhibit the characteristic propertiesSurface areas: 40 to 100 m.sup.2/g; Pore Volume: 0.25 to 0.45 cm.sup.3/g; and Pore size: 100 to 180 .

8. The mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the beads exhibit fluoride and arsenic removal efficiencies to the extent of >90% from contaminated groundwater at pH range of 5 to 8, and at temperature ranging from 10 to 35 degrees.

9. The mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the beads show fluoride adsorption capacities of 5 to 20 mg/g and arsenic adsorption capacities of 500 to 1000 g/g, and 100 to 200 g/g for arsenate and arsenite, respectively.

10. A process for the preparation of mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the steps comprise: (i) preparing mixed metal oxyhydroxide nanoparticles by co-precipitation and/or deposition precipitation method by taking iron and aluminium (binary system) or iron and aluminium along with any one or combinations of elements selected from the group comprising of lanthanum/zirconium/cerium/copper/manganese/magnesium (ternary system) inorganic precursor salt solutions at temperature ranging from 10 to 40 degree at pH of 6 to 10 using NaOH and/or KOH as precipitating base; (ii) washing the mixed metal oxyhydroxide nanoparticles as obtained in step (i) to remove unwanted impurities; (iii) simultaneously preparing the biopolymer solution by dissolving 0.5 to 5.0% w/v sodium alginate solution in distilled water under vigorous stirring; (iv) dispersing the washed mixed metal oxide hydroxide nanoparticles as obtained in step (ii) in aqueous medium at concentration ranging from 4.0 to 6.0% w/v and contacting with the biopolymer solution as obtained in step (iii) maintaining the biopolymer to mixed metal oxide hydroxide in a weight ratios ranging from 1:1 to 1:3 to obtain homogeneous mixture of mixed metal oxyhydroxide biopolymer composite; (v) contacting the mixed metal oxyhydroxide biopolymer composite as obtained in step (iv) with a chelating agent by dropwise addition to obtain spherical gel beads followed by curing of the beads in the same bath for a period of 4 to 48 hours; (vi) washing the beads obtained in step (v) with water repeatedly followed by protonation by soaking them in acidified water for a period of 4 to 48 hours; (vii) washing the protonated beads as obtained in step (vi) thoroughly until the pH of the wash water is in the range of 5 to 6 followed by drying the beads at a temperature in the range of 60 to 65 degree until complete drying to obtain the desired mixed metal oxyhydroxide biopolymer composite beads.

11. The process as claimed in claim 10, wherein the concentration of inorganic precursor salt solutions are in the range of 0.1 to 1.0 molar solutions for iron and aluminium; 0.05 to 0.1 molar solutions of Ce/La/Zr/Cu/Mn/Mg; and 2-6 molar solutions of alkali NaOH/KOH/NH.sub.3.

12. The process as claimed in claim 10, wherein the chelating agent is selected from 1 to 5% w/v CaCl.sub.2).

13. A process for the removal of arsenic and fluoride from water using the mixed metal oxyhydroxide biopolymer composite beads as claimed in claim 1, wherein the steps comprise: (a) contacting fluoride/arsenic ions containing water with mixed metal oxide hydroxide biopolymer composite beads, in the pH range of 5-8, at a temperature of 20-35 C.; at an agitation speed of 140-160 rpm; for a period of 1-24 hrs to obtain fluoride/arsenic ions depleted water; (b) contacting fluoride ions containing groundwater with mixed metal oxide hydroxide biopolymer beads loaded fixed bed column/reactor in up-flow mode with required residence time to get fluoride ions free water; (c) contacting the fluoride and arsenic ions containing exhausted mixed metal oxide hydroxide biopolymer composite beads with sodium hydroxide solution at pH 10-11 for 78 hrs for desorption followed by activation with hydrochloric acid/acetic acid; at a pH 2.5-3.5; for a 24 h in 2-3 batches to get regenerated beads.

Description

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

[0080] The following figures provide a further explanation and better understanding of the invention as claimed. The invention may be better understood by references to one or more of these figures in combination with the description of specific embodiments presented herein.

[0081] FIG. 1. Represents a schematic representation of process steps in preparation of Mixed metal oxyhydroxide Biopolymer Composite (MBC) beads.

[0082] FIG. 2A. Represents the SEM images of Mixed metal oxyhydroxides Biopolymer (MBC) beads prepared by the method of the present invention.

[0083] FIG. 2B. Represents the morphology of the bead surface at higher magnification.

[0084] FIG. 3. Represents the X-ray Photoelectron Spectroscopy (XPS) survey spectra of MBC beads before and after fluoride adsorption. The presence of adsorbed fluoride is confirmed by a new F is peak at 683.5 eV, along with other key elements on MBC beads surface.

DETAILED DESCRIPTION OF THE INVENTION

[0085] The terminology used to express herein for describing the methodology is for particular aspects only and is not intended to be limiting. Although any metal salts, methods and materials similar to those described here can be used for the materials preparation. Considering the ease of method of preparation simple operational steps were followed, if there of number of additional steps that can be included with any specific embodiment or with combination of embodiments of the methods of the invention.

[0086] The terms metal oxyhydroxide and metal oxide hydroxide shall be used interchangeably.

[0087] For the preparation of a novel adsorption medium for fluoride removal from water, at first a series of mixed metal oxyhydroxide biopolymer composite beads samples were prepared by coprecipitation and/or deposition precipitation method. For iron source, precursor salt was taken from anhydrous FeCl.sub.3/Fe(NO.sub.3).sub.3.Math.9H.sub.2O/FeSO.sub.4.Math.7H.sub.2O any one or in combinations thereof. For aluminium source any salt from Al(NO.sub.3).sub.3.Math.9H.sub.2O/Al.sub.2SO.sub.4.Math.16H.sub.2O/AlCl.sub.3 either alone or in combinations was taken. The La, Mg, Mn, Cu, Ce and Zr precursors taken were from any of nitrate/sulfate/chloride salts of these elements. The precipitant used was any one or combinations of NH.sub.3/NAOH/KOH and the pH requisite values are in-between 6.5-9.5 for mixed metal oxyhydroxides synthesis. Alginic acid sodium salt was used as biopolymer support here. All the experiments were performed at ambient temperatures.

Methodology Adopted for Development of the Product/Process

A. Preparation of Binary Mixed Metal Oxyhydroxide Biopolymer Composite Beads

[0088] A series of binary AlFe oxyhydroxide/oxides/hydroxide systems were synthesized in any selected elemental mass/molar ratios ranging between 6:1 to 1:6 by following simple co-precipitation/deposition precipitation/precipitation method at temperature below 32 C.

[0089] Adsorbent beads containing Fe:Al (2:1) mixed metal oxyhydroxide biopolymer composite beads were synthesized in 2 steps the details of which are given below.

[0090] Step 1 [0091] a) Preparation of iron oxide nanoparticles was done by precipitation/co-precipitation technique at pH 9.2-9.5 by taking 3.24 g of iron(III) chloride anhydrous and 2.78 g of iron(II) sulfate heptahydrate salt in 200 mL distilled water at 27 C. (5) temperature by using sodium hydroxide as precipitant. Further, the precipitates were stirred for 30-60 minutes and washed free of unwanted impurities with lukewarm/normal distilled water for 4-5 times. [0092] b) Dispersion of nanoparticles in the 200 mL distilled water and addition of 9.78 g aluminium sulfate hexadecahydrate precursor salt to it under vigorous stirring. The pH was raised to 7.5-8.0 value by slow addition of potassium hydroxide solution under stirring. Obtained mixed metal oxyhydroxide particles were further stirred for 30-60 minutes and then washed with distilled water by taking them in centrifuge bottles for 5-6 times until free from unwanted ions and pH of neutral. The metal nanoparticles were dispersed in 25-30 mL of distilled water.

[0093] Step 2 [0094] (a) Biopolymer solution was prepared by taking 2.5 g alginic acid sodium salt in 100 mL distilled water within the range of 1.5-2% w/v ratios under vigorous stirring until it is thoroughly mixed. [0095] (b) Mixed metal oxyhydroxides nanoparticles prepared in the step 1 were added to this solution slowly under vigorous stirring and continued till the homogeneous mix is formed. The sodium alginate content to mixed metal oxyhydroxide was maintained between 1:2-1:2.5 w/w ratio. [0096] (c) Mixed metal oxyhydroxides-Biopolymer Composite homogenous mixture was introduced drop wise into gelation bath containing requisite CaCl.sub.2) solution having strength in the range of 1.5-2% w/v through a thin nozzle with ID 0.6-1.0 mm connected to a peristaltic pump tubing with a flow rate of 10-15 mL min.sup.1. The gel beads curation time was chosen between 4-24 h in the same solution for. [0097] (d) The gel beads were rinsed with distilled water thoroughly 3-4 times and protonated with solution containing HCl/HNO.sub.3/H.sub.2SO.sub.4/CH.sub.3COOH any one or in combinations for period range of 4-48 h. The beads were then rinsed with distilled water and dried at room temperatures and/or under sun light until they are completely dried and then stored in an airtight container for further use. Binary metal oxide systems of Fe:Al in different weight ratios between of 2:1, 1:1, 1:2, 1:4 and 1:6 were synthesized. [0098] (e) Preliminary batch adsorption studies were conducted by taking binary metal oxide/hydroxides adsorbent materials for fluoride removal under similar conditions and results of the best materials are given in the Table-1.

B. Preparation of Ternary Mixed Metal Oxyhydroxides Biopolymer Composite Beads

[0099] Ternary mixed metal oxyhydroxide systems were prepared by taking one of the best optimized combinations of Fe:Al along with one of the metal precursor salt selected from the group consisting of Ce, La, Zr, Cu, Mg, Mn (nitrate/chloride/sulfate salts). Ternary mixed metal oxyhydroxides containing biopolymer beads of Fe:Al:Ce; Fe:Al:Zr; Fe:Al:La; Fe:Al:Mg; Fe:Al:Cu; and Fe:Al:Mn were prepared by following the same method of preparation by taking metal precursors solutions in desired amounts along with aluminium precursor salt solution in step-2, (b). The metal content Z (Ce, La, Cu, La, Mg, Mn) to Fe:Al system can by any one value between 1-10 wt %. The details of the process for preparation of Fe:Al:Ce (1:2:0.3) mixed metal oxyhydroxide containing biopolymer beads are as follows:

[0100] Step 1 [0101] (a) Same as described in step-1 of A. [0102] (b) The nanoparticles obtained from step-1 of A was dispersed in required 200 mL volume of distilled water and to this 39.5 g of aluminium precursor salt along with requisite 1.55 g of cerium(III) nitrate hexahydrate precursor salt was added under stirring. The mixture was vigorously stirred for 30-60 minutes, and the solution pH was slowly raised to 8.0 by using alkali. The contents were stirred further for 30-60 minutes and then washed with distilled water by taking them in centrifuge bottles for 4-5 times. The prepared mixed metal oxyhydroxide nanoparticles are dispersed in 100 mL distilled water.

[0103] Step 2 [0104] (a) Biopolymer solution was prepared by mixing 5.56 g of sodium alginate in 180 mL of distilled water under mechanical stirring [0105] (b) Bead preparation is same as explained in step 2 of A.

[0106] A schematic diagram for process of preparation of MBC beads is given in FIG. 1.

C. Conditions and Apparatus for Batch Sorption Experiments:

[0107] The batch adsorption experiments were conducted by taking known amount of adsorbent sample in a 125 mL polyethylene plastic vial along with 50/100 mL of fluoride/arsenic solution of known concentrations. The pH of the solutions were adjusted by using 0.1N HCl and 0.1N NaOH solutions and the contents were kept for agitation in a temperature controlled water bath shaker for required time and then the solids were separated and fluoride concentration in the solutions was determined. The adsorption capacity g.sub.c (mg g.sup.1) of the adsorbent was calculated from the equation q.sub.c=[(C.sub.iC.sub.f)*V]/W where C.sub.f the equilibrium concentration (mg/L), C.sub.i is initial adsorbate concentration (mg/L), V is volume of the solution (L) and W is the weight of adsorbent (g). Batch adsorption experiments were carried out in triplicate and the average values are reported. ORION Ion Selective Electrode and combination pH electrodes were used for fluoride and pH measurements. Arsenic analysis in the water samples was carried out on Metrohm 884 Professional VA instrument using scTRACE Gold sensor (US EPA SW-846 Test Method 7063 by Anodic Stripping Voltammetry (ASV)). Acid digested mixed metal oxyhydroxide biopolymer composite bead samples were subjected for chemical analysis by ICP-OES, icap7600, (Thermo Fisher Scientific), ORION AquaMate 8000 UV-Vis spectrophotometer and UNICUBE, Elementar CHNS Elemental analyzer was used for analysis of C, H, N, and S content in the beads. Standard Reference Materials were used for all chemical analysis. TYPE I water was used for all standards preparation, fluoride and arsenic stock solutions preparation and calibrations.

D. Characterization of the Materials

[0108] The The X-Ray Diffraction (XRD) patterns of mixed metal oxyhydroxide biopolymer composite beads prepared at various different experimental conditions and compositional variations were recorded by using Phillips Powder Diffractometer Model PW3710 with Cu K_ radiation at a scan speed of 1.2 min.sup.1 over a range of 10-80. The peak position and patterns were analyzed by comparing with X' pert High Score software. For FeAl containing binary systems, peaks at 30.26, 35.60, 43.10, 57.20 and 62.72 attributed to crystal planes of iron oxide at (102), (114), (212), (220), (232), and (228) and matched well with reference code: 98-009-2356. Two broad peaks at 18.45 and 20.28 2 values corresponding to (002) and (110) planes elucidated Gibbsitic A1 (Ref. Code: 00-007-0324). The broadened XRD peaks imply that the crystallite size of the FeAl mixed metal oxyhydroxide particles are very small, and the mean crystallite size calculated from the Scherrer formula shows that nanocrystals are of an average size of 26.5 nm.

[0109] Fourier Transform Infra-Red (FT-IR) spectra of raw beads and fluoride and arsenic adsorbed beads were taken by using Varian-Australia, model 800 spectrophotometer. The FTIR spectrum of pure MBC beads showed broad intense characteristic bands at 3200-3500 and 1611 cm.sup.1 corresponding to OH stretching and bending vibrations of absorbed water as well as strong asymmetrical stretching vibration bonds in carboxyl groups. Characteristic broad band between 520-650 cm.sup.1 can be attributed to M-O (FeO and AlO) vibrations. As beads are composite material, slight shift in the band positions were noticed when compared to pure Fe and Al systems. A small band at 1420 cm.sup.1 may be due COO asymmetric and symmetric stretching due to biopolymer. The FTIR spectra of fluoride and arsenic adsorbed MBC bead showed significant changes in band intensities of hydroxyl and carboxylic groups, indicating involvement of these functional groups in fluoride or arsenic ions uptake.

[0110] The Field Emission Scanning Electron Microscope with EDS (Make CarlZeiss, model: SUPRA GEMINI55) was used to study the surface morphology and element dispersion of the prepared mixed metal oxyhydroxide biopolymer composite beads. The overall shape, and size of developed beads can be seen in FIG. 3A, the adsorbent beads were irregular granules with average size of about 1 mm (0.2). The high magnification images (3B) confirmed the porous nature of the bead surface. Energy-Dispersive X-ray (EDX or EDS) analysis confirmed the presence of iron, aluminium, carbon and oxygen content in the bead.

[0111] Brunauer-Emmett-Teller (BET) adsorption-desorption isotherm study and the BET surface area measurements of the samples were taken on Quantasorb, Quantachrome Corporation, USA. The beads showed characteristic features of Type-IV isotherms with its hysteresis loop indicating the mesoporous surface and multilayer adsorption. The BET surface areas noted for the samples ranged between 40-105 m.sup.2/g, pore volume 0.25-0.44 cm3/g; and pore diameter values of 115.97-291.17 . The pH.sub.pzc of selected sample was determined by solid addition method was found to be 5.2-5.6.

[0112] X-Ray Photoelectron Spectroscopic studies were used to investigate the qualitative and quantitative information on the surface elemental analysis and mechanism of the fluoride removal on the MBC bead surface. For this, XPS spectra of raw MBC04 beads was taken before and after fluoride adsorption and is shown FIG. 3. All the characteristic peaks such as Fe 2p, Al 2p, C1s, F1s and O 1s are noted on the surface of the adsorbent. It was also noted that the fluoride adsorption did not affect the binding energies on the peak positions of key elements.

EXAMPLES

[0113] The following examples are given by way of illustration only and therefore should not be construed to limit the scope of the present invention in any manner.

Example-1

[0114] This example describes the synthesis of binary metal oxyhydroxide nanoparticles-biopolymer composite bead structures through a simple wet chemistry route. Iron and aluminium in 1:1 weight ratio was taken for the metal oxyhydroxide nanoparticle composite adsorbent prepared and the sample is denoted as MBC02.

[0115] The Method of Preparing Mixed Metal Oxyhydroxide Biopolymer Composite Bead Samples Comprise Following Steps:

[0116] Step 1: 16.22 g of iron (III) chloride anhydrous and 13.9 g of ferrous sulfate heptahydrate were weighed and put in a 500 mL capacity beaker containing 200 mL distilled water. The salt contents were mixed thoroughly using a laboratory mixer/magnetic stirrer at 300 rpm. To this solution, 4M NaOH solution was added slowly in a drop-wise manner with vigorous stirring to facilitate the co-precipitation until pH reached 9.2-9.5 at room temperature 27 C. (5). The precipitate was stirred for 30 minutes more, followed by washing with distilled water 5-6 times to remove unwanted impurities and/or until the pH of the supernatant reaches near neutral.

[0117] Step 2: In another 1 L beaker, the precipitate obtained in step-1 was dispersed in 500 mL distilled water and to this 97.9 g of aluminium sulfate hexadecahydrate precursor salt was added under stirring. Contents were stirred for 1 hour and then under a condition of mechanical stirring of 500-700 rpm, 6N potassium hydroxide solution was added dropwise. The pH of the suspension was allowed to rise gradually to 7.5-8 at room temperature 27 C. The precipitates were further stirred for 30 minutes and allowed to settle.

[0118] Step 3: The products obtained in Step-2, were transferred into 500 ml centrifuge bottles for washing at 2000-3000 rpm for 5 min. The supernatant solution was decanted and the precipitates were taken in distilled water, mixed thoroughly with glass rod before every wash. This procedure was repeated 4-5 times using distilled water till the pH of the centrifugal supernatant was near neutral. After the process described above was completed, the obtained products were dispersed in 100 mL of distilled water in a 500 mL beaker and labelled as solution A.

[0119] Step 4: In a 2000 mL capacity beaker, 16.76 g of sodium alginate was weighed and dissolved in 500 mL distilled water and the contents were stirred vigorously at room temperature 27 C. (5) for 5-6 h or till a homogeneous mixture without lumps was obtained and labelled as solution-B.

[0120] Step 5: The solution-A was transferred into solution-B, and the total volume of the mix was adjusted to 850 mL and/or the strength of the sodium alginate was maintained between 1.8-2% w/v. The sodium alginate to FeAl mixed metal oxide hydroxides w/w ratio was maintained in-between 1:2-1:2.5. The contents were stirred vigorously at 800-1000 rpm until a uniform homogeneous mixture is formed. Here the stirring speed and time required to get uniform homogeneous mixture of mixed metal oxyhydroxides and biopolymer composite depends on the contents amount/weight/volume.

[0121] Step 6: In a 1 L beaker, 16 g of Calcium Chloride was taken in 900 mL distilled water and stirred until completely dissolved. The strength of the gelation medium was chosen between 1.5-2% w/v and is labelled as Solution-C.

[0122] Step 7: FeAl mixed metal oxyhydroxide and biopolymer precipitate mixture solution as prepared in Step 5 was added drop-wise into CaCl.sub.2) solution (i.e., Solution-C) using a multi-channel peristaltic pump. Precision pump tubing with an inner diameter of 0.8 mm was used at a flow rate of 10-15 ml/min and dropping was done from a height of 1-1.5 cm above solution-C level. Gel beads in the solution were slowly mixed with a glass rod to avoid the formation of lumps. All these steps were carried out at a temperature of 27 C.

[0123] Step 8: The spherical gel beads thus obtained were allowed to cure in gelation medium for 4-24 h. The beads were then rinsed with distilled water 4-5 times and then protonated with 500 mL of acidified (0.05-0.1N HCl/HNO3) distilled water for 4-24 h. The beads were rinsed thoroughly 5-6 times or till the washed water pH is near neutral and then transferred onto trays with blotting paper to remove surface moisture. The beads were dried in a hot air oven at 65-80 C. till they are completely dry or can also be dried under sunlight. The dried MBC beads are stored in an air-tight container for further use.

Example-2

[0124] This example describes the synthesis of iron and aluminium binary mixed metal oxyhydroxide biopolymer composite beads structures having Fe:Al weight ratio of 1:2.5 by simple wet chemistry route and denoted as MBC03. All the steps were carried out at room temperature 27 C.(5). The method of preparing mixed metal oxyhydroxide biopolymer composite beads comprise following steps:

[0125] Step 1: 3.26 g of iron (III) chloride anhydrous and 2.78 g of ferrous sulfate heptahydrate were weighed and put in a 500 mL capacity beaker containing 200 mL distilled water. The salt contents were mixed thoroughly using a laboratory mixer/magnetic stirrer at 200 rpm. To this solution, 4M NaOH solution was added slowly in a drop-wise manner with vigorous stirring to facilitate the co-precipitation until pH reached 9.2-9.5 at room temperature 27 C. (5). The precipitate was stirred for 30 minutes more, followed by washing with distilled water 5-6 times to remove unwanted impurities.

[0126] Step 2: In another 1 L beaker, the precipitate obtained in Step-1 was dispersed in 500 mL distilled water and to this 49 g of aluminium sulfate hexadecahydrate precursor salt was added under stirring. Contents were stirred for 1 hour and then under a condition of mechanical stirring of 500-700 rpm, 6N potassium hydroxide solution was added dropwise. The pH of the suspension was allowed to rise gradually to 7.5-8 at room temperature 27 C. (5). The precipitates obtained were further stirred for 30 minutes more at that pH and allowed to settle.

[0127] The weight ratio of Fe:Al in the metal oxyhydroxide nanoparticle composite adsorbent prepared for fluoride removal was 1:2.5.

[0128] Step 3: The products obtained in Step-2, were washed with distilled water by following the same procedure as mentioned in Step 3 of Example-1. After the process described above was completed, the obtained products were dispersed in 500 mL of distilled water in a 1000 mL capacity beaker and labelled as solution A.

[0129] Step 4: In a 2000 mL capacity beaker, 5.9 g of sodium alginate was weighed and dissolved in 200 mL distilled water and the contents were stirred vigorously at room temperature 27 C.(5) for 5-6 h or till a homogeneous mixture without lumps is obtained and labelled as solution-B.

[0130] Step 5: The solution-A was transferred into solution-B, and the total volume of the mix was 350 mL and the strength of the sodium alginate was maintained between 1.5-2% w/v. The sodium alginate to FeAl mixed metal oxyhydroxides w/w ratio was maintained in-between 1:2-1:2.5. The contents were stirred vigorously at 800-1000 rpm until a uniform homogeneous mixture is formed.

[0131] Step 6: In a 1 L beaker, 8.9 g of Calcium Chloride was taken in 500 mL distilled water and stirred until completely dissolved. The strength of the gelation medium was chosen between 1.5-2% w/v and is labelled as Solution-C.

[0132] Step 7 and Step 8 are the same as discussed in Example-1.

Example-3

[0133] This example describes the synthesis of iron and aluminium binary mixed metal oxyhydroxide biopolymer composite beads structures having Fe:Al weight ratios of 1:3 by simple wet chemistry route and is denoted as MBC04. All the steps were carried out at room temperature 27 C. (5).

[0134] Step 1: 5.43 g of iron (III) chloride anhydrous and 4.63 g of ferrous sulfate heptahydrate were weighed and put in a 500 mL capacity beaker containing 200 mL distilled water. The salt contents were mixed thoroughly using a laboratory mixer/magnetic stirrer at 200 rpm. To this solution, 4M NaOH solution was added slowly in a drop-wise manner with vigorous stirring to facilitate the co-precipitation until pH reached 9.2-9.5 at room temperature 27 C. (5). The precipitate was stirred for 30 minutes more, followed by washing with distilled water 5-6 times to remove unwanted impurities.

[0135] Step 2: In another 1 L beaker, the precipitate obtained in Step-1 was dispersed in 500 mL distilled water and to this 97.9 g of aluminium sulfate hexadecahydrate precursor salt was added under stirring. Contents were stirred for 1 hour and then under a condition of mechanical stirring of 500-700 rpm, 6N potassium hydroxide solution was added dropwise and the pH of the suspension was allowed to rise gradually to 7.5-8 at room temperature 27 C. (+5). The precipitates obtained were further stirred for 30 minutes more at that pH and allowed to settle. The weight ratio of Fe:Al in the metal oxyhydroxide nanoparticle composite adsorbent prepared for fluoride removal was 1:3.

[0136] Step 3: Same as discussed Example-1. The obtained products were dispersed in 500 mL of distilled water in a 1000 mL beaker and labelled as a solution A.

[0137] Step 4: In a 2000 mL capacity beaker, 11.2 g of sodium alginate was weighed and dissolved in 400 mL distilled water and the contents were stirred vigorously at room temperature 27 C. (5) for 5-6 h or till a homogeneous mixture without lumps is obtained and labelled as solution-B.

[0138] Step 5: The solution-A was transferred into solution-B, and the total volume of the mix was 600 mL and the strength of the sodium alginate was maintained between 1.5-2% w/v. The sodium alginate to FeAl mixed metal oxyhydroxides w/w ratio was maintained in-between 1:2-1:2.5. The contents were stirred vigorously at 800-1000 rpm until a uniform homogeneous mixture is formed.

[0139] Step 6: In a 1 L beaker, 16 g of Calcium Chloride was taken in 900 mL distilled water and stirred until completely dissolved. The strength of the gelation medium was chosen between 1.5-2% w/v and is labelled as Solution-C.

[0140] Step 7 and Step 8 are same as discussed in Example-1.

Example-4

[0141] This example describes the synthesis of iron and aluminium binary mixed metal oxyhydroxide biopolymer composite beads structures having Fe:Al weight ratios of 1:4 by simple wet chemistry route and is denoted as MBC05. All the steps were carried out at room temperature 27 C. (5).

[0142] Step 1: 3.26 g of iron (III) chloride anhydrous and 2.78 g of ferrous sulfate heptahydrate were weighed and put in a 500 mL capacity beaker containing 200 mL distilled water. The salt contents were mixed thoroughly using a laboratory mixer/magnetic stirrer at 200 rpm. To this solution, 4M NaOH solution was added slowly in a drop-wise manner with vigorous stirring to facilitate the co-precipitation until pH reached 9.2-9.5 at room temperature 27 C. (5). The precipitate was stirred for 30 minutes more, followed by washing with distilled water for 5-6 times to remove unwanted impurities.

[0143] Step 2: In another 1 L beaker, the precipitate obtained in Step-1 was dispersed in 500 mL distilled water and to this 78.5 g of aluminium sulfate hexadecahydrate precursor salt was added under stirring. Contents were stirred for 1 hour and then under a condition of mechanical stirring of 500-700 rpm, 6N potassium hydroxide solution was added dropwise. The pH of the suspension was allowed to rise gradually to 7.5-8 at room temperature 27 C. (5). The precipitates obtained were further stirred for 30 minutes more at that pH and allowed to settle.

[0144] Step 3: Same as discussed Example-1. The obtained products were dispersed in 500 mL of distilled water in a 1000 mL beaker and labelled as solution A.

[0145] Step 4: In a 2000 mL capacity beaker, 8.4 g of sodium alginate was weighed and dissolved in 350 mL distilled water and the contents were stirred vigorously at room temperature 27 C. (5) for 5-6 h or till a homogeneous mixture without lumps is obtained and labelled as solution-B.

[0146] Step 5: The solution-A was transferred into solution-B, and the total volume of the mix was 500 mL and the strength of the sodium alginate was maintained between 1.5-2% w/v. The sodium alginate to FeAl mixed metal oxyhydroxides w/w ratio was maintained in-between 1:2-1:2.5. The contents were stirred vigorously at 800-1000 rpm until a uniform homogeneous mixture is formed.

[0147] Step 6: In a 1 L beaker, 10.7 g of Calcium Chloride was taken in 600 mL distilled water and stirred until completely dissolved. The strength of the gelation medium was chosen between 1.5-2% w/v and is labelled as Solution-C.

[0148] Step 7 and Step 8 are same as discussed in Example-1.

Example-5

[0149] This example describes the method of preparing ternary metal oxyhydroxide biopolymer composite bead adsorbent comprising of Fe:Al:La in weight ratios of 1:2.5:0.35 for fluoride removal from water, and the sample is denoted as MBC06.

[0150] The sample preparation comprises the following steps:

[0151] Step 1: 3.26 g of iron (III) chloride anhydrous and 2.78 g of ferrous sulphate heptahydrate were weighed and put in a 500 mL capacity beaker containing 200 mL distilled water. The salt contents were mixed thoroughly using a laboratory mixer/magnetic stirrer at 200 rpm. To this solution, 4M NaOH solution was added slowly in a drop-wise manner with vigorous stirring to facilitate the co-precipitation until pH reached 9.2-9.5 at room temperature 27 C. (5). The precipitate was stirred for 30 minutes more, followed by washing with distilled water for 5-6 times to remove unwanted impurities.

[0152] Step 2: In another 1 L beaker, the precipitate obtained in Step-1 was dispersed in 500 mL distilled water and to this 49 g of aluminium sulfate hexadecahydrate precursor salt was added under stirring. To this, 1.1 g of Lanthanum nitrate hexahydrate precursor salt was added and continued the stirring for 1 hour and then under a condition of mechanical stirring of 500-700 rpm, 6N potassium hydroxide solution was added dropwise. The pH of the suspension was allowed to rise gradually to 8 at room temperature 27 C. (5). The precipitates obtained were further stirred for 30 minutes more at that pH and allowed to settle.

[0153] Step 3: Same as discussed Example-1. The obtained products were dispersed in 500 mL of distilled water in a 1000 mL beaker and labelled as solution A.

[0154] Step 4: In a 2000 mL capacity beaker, 6.5 g of sodium alginate was weighed and dissolved in 200 mL distilled water and the contents were stirred vigorously at room temperature 27 C. (5) for 5-6 h or till a homogeneous mixture without lumps is obtained and labelled as solution-B.

[0155] Steps 5, 6, 7, and 8 are the same as discussed in Example-2.

Example-6

[0156] In this example, ternary metal oxyhydroxide biopolymer composite bead adsorbent comprising of Fe:Al:Zr in weight ratios of 1:2.5:0.35 was prepared for fluoride removal from water and the sample is denoted as MBC07.

[0157] Step 1: Iron oxide nanoparticles were prepared by following the procedures given in Step-1 of Example-5.

[0158] Step 2: In another 1 L beaker, the precipitate obtained in Step-1 was dispersed in 500 mL distilled water and to this 49 g of aluminium sulfate hexadecahydrate and 1.095 g of zirconium sulfate hydrate precursor salts were added and continued stirring for 1 hour and then under a condition of mechanical stirring of 500-700 rpm, 6N potassium hydroxide solution was added dropwise. The pH of the suspension was allowed to rise gradually to 8 at room temperature 27 C. (5). The precipitates obtained were further stirred for 30 minutes more at that pH and allowed to settle.

[0159] Step 3: Washing of the precipitate is same as discussed in Example-1. The obtained products were dispersed in 500 mL of distilled water in a 1000 mL beaker and labelled as a solution-A.

[0160] Step 4: In a 2000 mL capacity beaker, 6.5 g of sodium alginate was weighed and dissolved in 200 mL distilled water and the contents were stirred vigorously at room temperature 27 C.(5) for 5-6 h or till a homogeneous mixture without lumps is obtained and labelled as solution-B.

[0161] Steps 5, 6, 7, and 8 are the same as discussed in Example-2.

[0162] Defluoridation performance of different Metal oxyhydroxide Biopolymer Composite (MBC) bead samples as prepared in Examples 1 to 6 are listed in Table 1. The performance of the prepared granules compared with commercial activated alumina (AA) beads purchased from a local vendor. The activated alumina granules were treated with 2% acid (H.sub.2SO.sub.4/HCl) solution to bring the pH 5.5-6.0 then used for fluoride and arsenic adsorption experiments. Synthetic fluoride spiked water was prepared by dissolving 0.221 g of NaF salt (oven dried at 110 C. for 2 h) in 1000 mL deionized water. Requisite 10 ppm F.sup. water was prepared by making dilutions and pH was adjusted to near 7.2 (0.1). It is clear from the results (Table 1) that the binary and ternary mixed metal oxyhydroxides containing biopolymer composite beads showed higher removal performance at neutral pH as compared to commercial activated alumina granules under similar experimental conditions.

TABLE-US-00001 TABLE 1 Fluoride adsorption performance results of mixed metal oxyhydroxides beads along with commercial activated alumina granules (Conditions: Initial fluoride: 9.88 mg/L; Bead dose: 4 g/L; Solution pH: 7.2(0.1); time -24 h; temperature 29 C.) Metal weight ratios in Final concentration Fluoride Biopolymer solution of fluoride in the percent Sample ID of 1.5-2 wt % in all solution, mg/L removal MBC02 Fe:Al(1:1) 3.45 65.0 MBC03 Fe:Al (1:2.5) 2.80 71.7 MBC04 Fe:Al(1:3) 2.56 74.1 MBC05 Fe:Al(1:4) 2.00 79.8 MBC06 Fe:Al:La (1:2:0.3) 2.14 77.4 MBC07 Fe:Al:Zr (1:2:0.3) 2.09 77.9 Commercial 5.80 40.8 Activated alumina granules

Example-7

[0163] For defluoridation performance of adsorbent MBC03 bead sample as prepared in Example-2 was taken for real-life groundwater treatment in this example. Fluoride-containing groundwater was collected from a fluoride endemic village in Odisha, was analysed for important water parameters by using different instrumental techniques and the results are listed in Table 2. A batch adsorption experiment was conducted at different adsorbent dose variations of 0.5-4.0 g/L of groundwater. The rest of the procedure is similar as described in Example-6. Results are listed in Table 3.

TABLE-US-00002 TABLE 2 Analysis of groundwater sample collected from fluoride endemic region Parameter Characteristic Value pH 7.46 F.sup., mg/L 2.96 TDS, mg/L 415.4 Conductivity, S/cm 483.11 Alkalinity, mg/L 293.5 Total Hardness, mg/L 139.8 SO.sub.4.sup.2, mg/L 52.83 Cl.sup., mg/L 14.6 Ca, mg/L 16.1 Na, mg/L 47.9

TABLE-US-00003 TABLE 3 Performance evaluation of adsorbent beads for treatment of fluoride- containing groundwater collected from fluoride endemic village, Odisha, India (Conditions: fluoride-2.94 mg/L; pH-7.46; time: 16 h; MBC03 bead dose: 0.5-4.0 g/L; Temperature 29 C.). Activated Adsorbent MBC03 adsorbent bead alumina granules dose (g/L) Final, F.sup. mg/L % Removal Final F.sup. mg/L % Removal 0.5 2.40 17.24 2.71 6.55 1.0 2.31 20.34 2.55 12.10 2.0 1.64 43.45 2.36 18.62 3.0 1.12 61.38 2.25 22.41 4.0 0.91 68.72 2.08 28.28 5.0 0.62 79.0 1.80 38.8 6.0 0.11 96.00 1.45 50.6

Example-8

[0164] The arsenic removal performance of Mixed metal oxyhydroxide Biopolymer Composite (MBC02 to MBC06) bead samples as prepared in Example-1 to 6 are discussed in this Example. Arsenic (III) and Arsenic (V) 100 mg/L stock solutions were prepared by taking 0.1734 g of NaAsO.sub.2 in 1000 mL and 0.416 g Na.sub.2HasO.sub.4 in deionized water. The arsenic concentrations in ppb (parts perbillion) levels were prepared by appropriate dilutions and used in the studies. Arsenic(V) removal performance of the different adsorbent samples is reported in Table 4. The performance of the selected MBC adsorbent at different dose variations for removal of arsenic(III) and arsenic (V) species is reported in Table 5.

TABLE-US-00004 TABLE 4 Arsenic (V) adsorption performance studies of different mixed metal oxyhydroxides beads along with commercial activated alumina granules (Conditions: Initial Arsenic(V) conc.,: 81.14 g/L; adsorbent Bead dose: 3 g/L; Solution pH: 7.42(0.1); Time: 24 h; Temperature 29 C.) Final concentration of Sample ID As(V) in the solution, g/L Percent removal MBC02 13.62 83.2 MBC03 6.97 92.4 MBC04 6.20 92.5 MBC05 6.94 91.4 MBC06 6.14 92.4 MBC07 5.92 92.7 Commercial Activated 12.80 84.2 alumina granules

TABLE-US-00005 TABLE 5 Arsenite and Arsenate removal performance of MBC03 adsorbent beads as a function of adsorbent dose variation (Conditions: Arsenite 492 g/l, Arsenate: 494 g/l; Contact Time: 24 h; Temperature: 26 C.; pH-7.13; the volume of the water taken 50 mL) MBC Arsenite Removal Arsenate Removal Dose Final Arsenite % Arsenite Final Arsenate % Arsenate g/L Concentration Removal Concentration Removal 2 443.21 10.28 245.80 50.84 4 226.60 54.13 68.55 86.29 6 178.25 63.91 14.08 97.18 8 176.78 64.21 nd 100 10 158.42 67.93 nd 100 16 112.25 77.27 nd 100 24 12.87 97.39 nd 100 28 4.040 99.18 nd 100 *ndnot detectable

Example-9

[0165] Regeneration experiments on fluoride and arsenic loaded Metal oxyhydroxide Biopolymer Composite (MBC03) adsorbent is discussed in this example. The used Mixed metal oxyhydroxides-Biopolymer Composite (MBC) beads loaded with fluoride were subjected to selected eluents. For this study, fluoride-loaded beads were prepared by treating 1 L of 50 mg/L F.sup. containing water with 4 g of the bead at pH 7.1 by batch experiment. The contents were agitated for 24 h at room temperature (27 C.) and the supernatant was analyzed for the remaining fluoride concentration value was found to be 12.5 mg/L with calculated adsorption capacity 9.4 mg/g. The fluoride-loaded MBC beads were used for conducting sequential desorption batch experiments in which the exhausted beads were periodically exposed to eluent mediums in three stages. The conditions such as pH near 2.5-3.0 with acids and pH range of 10-11 with alkali were carefully chosen with acid and alkali respectively. Highly acidic, pH<2.5 and alkaline pH >11 were found to be not suitable as the bead structure gets destructed and chances of dissolution of adsorbent metal ions into the water. Results are shown in Table 6.

TABLE-US-00006 TABLE 6 Regeneration performance of Fluoride desorption (Conditions: Initial fluoride concentration: 37.5 mg/L; MBC03 adsorbent dose: 100 mg/100 mL of eluent, contact time: 24 h; temperature ambient (28-29 C.). Regeneration media Percent of desorption 8-10 mM CH.sub.3COOH 35-62% 1.5-3 mM HCl 17-62% 0.2-0.5 mM NaOH 32-75.5%.sup.

[0166] For regeneration studies on arsenic loaded MBC beads, batch adsorption experiment was conducted by taking 50 mL of 1000 g/L arsenic solution containing As(III)500 g/L+As(V)500 g/L with 250 mg of MBC03 beads, the contact time was 24 h, pH adjusted at 7.15(0.1) at a temperature of 29 C. The analysis of the supernatant solution showed a total arsenic concentration of 253.73 g/L. The beads were washed, dried, and used for desorption experimental conditions as mentioned for fluoride. The results are presented in Table 7.

TABLE-US-00007 TABLE 7 Adsorption and desorption and regeneration performance of used MBC beads Conditions: Dose; 250 mg/100 ml of eluent, Shaking Time: 24 h; Temp: 27 C. Regeneration Media % Desorption 0.2-0.5 mM NaOH 30-67 8-10 mM CH.sub.3COOH 45-80

Example-10

[0167] Column adsorption performance of adsorbent as prepared in Example-2 was taken for continuous mode defluoridation of water. In a 30 cm Perspex column, with 1 cm inner diameter was packed with MBC03 beads. The void volume of the beads packed column was approximately 7 mL. The column was run in an up-flow mode using a peristaltic pump with a flow rate of 1.2 mL/min and an influent F.sup. concentration of 2.9 mg/L, at a pH of 7.32. The calculated residence time of the column was 0.317 h; samples were collected periodically and analyzed for the residual F.sup. concentrations. About, 16.1 g of commercially purchased activated alumina granules were packed in the same size column and continuous column runs were performed for defluoridation. All the other column parameters were maintained under similar conditions. The breakthrough concentration was fixed at 1.5 mg/L. The defluoridation capacities of the MBC beads and purchased activated alumina granules at different time intervals are presented in Tables 8 and 9 for MBC and AA, respectively.

TABLE-US-00008 TABLE 8 Defluoridation performance evaluation of MBC and Activated alumina granules with groundwater (Conditions: Feed water F.sup. conc., 2.9; Feed water pH: 7.4; Flow rate: 72 mL/h; Bed height: 30 cm) Column with MBC Column with Activated adsorbent, 12.9 g alumina granules, 16.1 g Sampling F, mg/L Percent F, mg/L Percent Sl. No time (h) Concn. removal Concn removal 1 1 0.04 98.57 0.16 94.6 2 24 0.08 97.27 0.40 86.6 3 48 0.15 95.00 0.85 71.4 4 72 0.21 93.10 1.20 60.0 5 96 0.37 87.80 1.38 53.3 6 120 0.52 82.60 1.55 47.6 7 144 0.82 72.73 1.71 40.2 8 168 0.97 67.67 9 192 1.19 60.34 10 216 1.26 57.99 11 240 1.34 54.67 12 264 1.44 53.72 13 288 1.48 51.99 14 312 1.56 50.67 15 336 1.72 47.99

TABLE-US-00009 TABLE 9 Comparison of real-life groundwater defluoridation performance of MBC beads and Commercial activated alumina granules. Volume of the water treated at Breakthrough Loading Adsorbent breakthrough, L capacity, mg/g MBC Beads 20.74 4.66 Commercial activated 7.92 1.43 alumina beads

Example-11

[0168] After 3-4 cycles of reuse, the fluoride removal performance of the adsorbent beads dropped, indicating that the exhausted media need to be disposed off safely. This example explains the Toxicity Characteristic Leaching Procedure (TCLP) test on fluoride saturated MBC03 beads and determines the extent of leaching/mobility of the adsorbed fluoride ions present in the beads to the environment when disposed of as solid waste. For this experiment, standard operating procedure (SOP-8131) based on Environmental Protection Agency (EPA) SW-846 Test Method 1311 was followed. The experiment was carried out by following two steps:

[0169] Step-1: About 5 g of used MBC beads were crushed to <1 mm and was taken in a 500 mL beaker along with 96.5 mL of reagent water and covered with a watch glass. The contents were kept for vigorous stirring for 5 minutes using a magnetic stirrer. The pH of this solution was recorded as 5.46, further 3.5 mL of 1N HCl was added, stirred, and covered with a watch glass, and heated at 50 C. for 10 minutes. The solution showed pH<5.0, therefore extraction Fluid #1 was selected for the second step. The required extraction Fluid #1 was prepared by taking 5.7 mL of glacial CH.sub.3CH.sub.2OOH to 500 mL of reagent water. To this, 64.3 ml of 1N NaOH was added, and diluted to a volume of 1 L, the pH of this fluid was adjusted to 4.930.05.

[0170] Step-2: The requisite volume of extraction Fluid #1 was taken in a Polypropylene bottle along with the bead material for extraction. The Teflon tape was on the threads of the bottle to close tightly. The extraction bottle was kept for 18 h under agitation at 30 rpm, at a temperature of 25 C. After the extraction period, the solids were separated by a glass fiber filter and the final fluoride concentration in the liquid was analyzed. The TCLP test was triplicated and reported. The fluoride concentrations in the extracted liquid were found to be in the range of 0.5-3 mg/L. The observed values are well within the permissible limit (50 mg/L) as per Central Pollution Control Board, India and United States, Environmental Protection Agency guidelines.

Advantages of the Invention

[0171] A distinct advantage of the metal oxyhydroxide biopolymer composite adsorbent for fluoride removal from water is that they are hydraulically conductive and easily separable, no requirement of external energy/force/devices for the solid-liquid separation. Additional aspects of the present invention is simple method of preparation, and do not require elevation of temperature or pressure.

[0172] Another advantage is that unwanted sludge formation can be avoided.

[0173] The dry beads stored at room temperatures showed no alteration after 24 months.

[0174] Developed adsorbent bead showed higher removal efficiency for fluoride groundwater at pH of 7-7.3.

[0175] Working pH range is 4.5-8.0 for de-fluoridation of water using MBC adsorbent beads.

[0176] In the pH range of 4.5-8.0, there is no release of adsorbent metal ions into the treated water.

[0177] The pH of the treated water is well within the acceptable range of drinking water.

[0178] The MBC beads are easy to transport and store when required.

[0179] The MBC beads are stable and do not swell or revert back to gel state in the aqueous medium.

[0180] The MBC beads can be used either in batch purification or in continuous flow purification system.

[0181] The used beads can be regenerated for 3-4 cycles under controlled pH conditions

[0182] The exhausted MBC beads safe for land fill disposal.