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Ind. Eng. Chem. Res.

2007, 46, 4577-4583


Laboratory Study of Boron Removal by Mg/Al Double-Layered Hydroxides
Jia-Qian Jiang,*,† Yonglan Xu,† Kieran Quill,‡ John Simon,‡ and Keith Shettle‡
School of Engineering (C5), UniVersity of Surrey, Guildford, Surrey GU2 7XH, and Borax Europe Ltd., 1A Guildford Business Park, Guildford, Surrey GU2 8XG

This paper is concerned with the preparation and use of Mg/Al double-layered hydroxides for boron removal from waste liquor. The structure of the DLHs synthesized is proposed to be Mg2AlNa1.4(OH)7.57Cl0.03(NO3)0.8‚ x(H2O) which does not contain any carbonate anions. For treating model waters with various starting boron concentrations (5-500 mg/L), the maximum boron percentage removal was >80% for DLH-60 and >90% for DLH-450. The boron removal capacity is 5.4-17.3 mg of B/g for DLH-450 and 1.2-13 mg of B/g for DLH-60, respectively. The raw water’s pH does not affect the boron removal performance. After six cumulative regenerations, boron percentage removal with regenerated DLHs decreased to about 40%. Overall, DLH-450 has a greater boron removal capacity than DLH-60 for both freshly prepared and regenerated materials. For the treatment of industrial effluent ([B]0 ) 17 mg/L), 86.6% boron removal was achieved at the dose of 36 g/L for DLH-60 and 93.5% at the dose of 16 g/L for DLH-450. Arsenic can be completely removed by both DLHs. The main mechanism of boron removal with DLH-60 is proposed to be anion exchange while that with DLH-450 is adsorption. For DLH-450, both Langmuir and Freundlich isotherm models fit well for the experimental results.
Introduction Boron is a naturally occurring element bound to oxygen in the form of borates, which are extensively used in the manufacture of glass wool, ceramics, borosilicate glass, flame retardants, detergents, wood preservatives, antifreeze, and micronutrient fertilizers. High boron doses cause reproductive and developmental effects in several species (rats, mice, and rabbits).1,2 Based on the animal reproductive effects, various environmental regulation organizations have set up standards or guidelines to regulate the boron concentration in drinking water. In the revised European Community Drinking Water Directive,3 boron concentration should be less than 1.0 mg/L. The recent updated World Health Organization (WHO) guidelines4 for drinking water quality retain the recommended guideline value of boron at 0.5 mg/L. Recently, the U.S. Environmental Protection Agency (USEPA) published the second version of the Contaminant Candidate List5 where the boron is included and its concentration is recommended not to exceed to 1 mg/L. There are a range of technologies that could be used for removing boron/borate from wastewaters, such as electrocoagulation,6,7 which has recently attracted a lot of interest, chemical precipitation,8 ion exchange,9 and reverse osmosis.10 All these techniques consist of advantages and disadvantages and the selection of these processes should be based on the treatment efficiency and operating cost. Nevertheless, the exploration of alternative techniques to treat borate-containing wastewaters has re-drawn interest with the implementation of more stringent wastewater discharge regulations and drinking water standards. Double-layered hydroxides (DLHs) or hydrotalcites are a class of synthetic anionic clays, and their structure can be represented by the general formula M(II)1-xM(III)x(OH)2(An-)x/n‚mH2O in which both divalent (M(II)) and trivalent cations (M(III)) give
* To whom correspondence should be addressed. Fax: +44 1483 450984. E-mail: † University of Surrey. ‡ Borax Europe Ltd.

positively charged sheets. The positive charge is balanced by intercalation of anions (An-) in the hydrated interlayer regions. The interlayer anion together with the stoichiometric coefficient (x) may be varied over a wide range, giving a range of isostructural materials. DLHs have been used for adsorption of various anions, such as F-, Br-, NO3-, and HPO42-. One formula of DLHs is Mg6Al2(OH)16CO3‚4H2O,11 which sorbs anions in solution and returns to the DLH structure. However, the results showed that, after the first heating and rehydration cycle, the formula of DLH becomes disordered, with its sorption capacity reduced by 50%. Obviously, DLH with carbonate anions cannot be reversibly exchanged and this limits its use. Zhang and Reardon12 have investigated the removal of B, Cr, Mo, and Se oxyanions from high pH waters by two DLHs, hydrocalumite (Ca4Al2(OH)12(OH)2‚6H2O) and ettringite (Ca6Al2(OH)12(SO4)3‚26H2O). The study shows that hydrocalumite and ettringite are capable of reducing the concentrations of borate, chromate, molybdate, and selenate from solutions. Hydrocalumite in particular can reduce the oxyanion concentration levels to below drinking water standards. However, the most important limitation in using these calcium aluminates to control oxyanion levels in water is pH. High pH conditions must be maintained in treatment of the environment because both hydrocalumite and ettringite are unstable at low pH. Gabrisova et al.13 indicate that pH values greater than 10.7 are required to stabilize ettringite and greater than 11.6 to stabilize hydrocalumite. In the present work, we aim to prepare a different formula of DLH materials to solve the limitations of using Mg/Alcarbonate-DLH, hydrocalumite, and ettringite as detailed above, and then to explore the use of DLHs for borate treatment systematically, to propose boron removal mechanisms and to assess the regeneration efficiencies. Materials and Experimental Methods Preparation of Mg-Al DLH Compounds. Magnesium and aluminum were selected as basic metals to prepare Mg-Al DLHs. One hundred forty milliliters of a mixed solution containing 0.2 mol of Mg(NO3)2‚6H2O (Fisher, UK) and 0.1

10.1021/ie0703639 CCC: $37.00 © 2007 American Chemical Society Published on Web 05/26/2007

the DLH products were dried at 60 °C for 24 h and 450 °C for 2 h. During this process.9.39 × 10-2 As3+ 0.4 Effluent: pH ) 7. a standard . After 4 h of vigorous shaking.8 SO42316. The solid phase was washed by deionized water several times and then heated at either 60 °C for 24 h or 450 °C for 2 h. However. mass of the ith ion in the DLH product (g) ) dose in the preparation residual mass in the supernatant ) dose in the preparation (g) 0. conductivity ) 880 µS/cm. Initial pH of the boron model water ([B]0 ) 10 mg/L) was adjusted to 4-11 by 5 M NaOH or 1 M HCl. Characterization of DLHs Products. Chem. The mass of each ion can be converted to moles which can be used to estimate the formula of the DLH product. After 4 h of shaking and centrifugation. For all DLHs. The DLH was mixed with model water in the tubes via a shaker with a shaking speed of 300 rpm for 4 h and then centrifuged.65 × 10-2 Mg2+ 18. respectively. Twenty-five milliliters of 100 mg/L boron model water with 0. 2007 Table 1. after first regeneration. The quality characteristics of an industry effluent sample can be seen in Table 1. 13. The boron removal mechanisms by DLHs were carried out using boron model water with various concentrations. The mixture was then centrifuged and the supernatant was analyzed for the measurement of anions concentration. etc. the thick slurry was aged at 85 ( 3 °C for 2 h. Then the residual mass of each ion in the supernatant was calculated. And then. The supernatant was withdrawn and concentrations of Cl-. respectively. The solid phase was washed by distilled water two times. Res. resulting in the density of the DLHs sample. Then 10 mL of HT samples was filled in the cylinder and weighed. The composition of DLHs was determined by mass balance protocol. the reaction temperature was controlled at 45 ( 3 °C. Two hundred milligrams of DLH was weighed and added into 25 mL of 10 mg/L boron model water (the initial pH was adjusted to 7 by 1 M NaOH) with vigorously shaking. The mass difference between two measurements is calculated. the gained DLH materials were named as DLH-60-1 or DLH-450-1. nitrate. Finally.7 g of DLH-60 or 0. The changes in concentrations of boron. mol of AlCl3‚6H2O(Fisher. The samples were outgassed overnight under nitrogen.334 (L)*[the i th ion] (mg/L)/1000 (mg/g) * 0.7 Cl111.334 L ) the total volume of each supernatant Surface areas of DLHs products were measured with a Micrometrics Gemini Apparatus.0 Al3+ 1.97 Ca2+ 110.). The solid products were separated by centrifugation (3500 rpm for 5 min) and washed six times with deionized water. the model water was made by mixing a given amount of boric acid with 1 L of 0. UK) (the molar ratio of Mg to Al was 2:1) was slowly added into 300 mL of a 2. Five and 1 M sodium hydroxide solutions were used to adjust the initial pH value. Model Water. After reaction. Metrohm Ltd. The volume of supernatant of synthesis slurry was accurately measured and recorded. Adsorption Isotherm. Twenty-five milliliters of such water was mixed with 750 mg of DLH.0 M NaOH solution by a peristaltic pump for 1 h and under vigorous mechanical stirring. Mechanisms of Boron Removal with DLHs. boron concentrations of the treated samples were measured. the supernatant of the solution was collected for the analysis of concentrations of boron and other elements and the data were used for obtaining boron reduction isotherms and for the estimation of removal mechanisms. In this work. Since the DLHs regenerated with 5 M NaNO3 resulted in a relatively better boron removal in comparison with that regenerated by either NaCl or Na2SO4. Quality Characteristics of the Industry Effluenta parameter (mg/L) a B 17. which is divided by 10 mL. Densities of DLHs products were measured. Experimental Setup for Boron Removal. A volumetric cylinder with 10 mL capacity was weighed and the mass of the cylinder was recorded.0 Na + 74. And then 25 mL of 5 M NaNO3 was added into the tubes and mixed completely with shaking for 4 h. water samples were withdrawn and the boron concentration was measured. Concentrations of cations and anions in the supernatant were analyzed by an inductively coupled plasma atomic emission spectrophotometer (ICP-AES) and an ion chromatograph (IC. Eng. 5 M NaNO3 was selected as the reagent for subsequent regeneration tests. Industry Effluent. based on the mass difference between ion dosed in the preparation and ion residuals in the supernatant. Finally. respectively. the supernatant was collected for the analysis of anions and cations by ICP and IC. 46. Twenty-five milliliters of boron model water samples ([B]0 ) 0-70 mg/L) were mixed with 200 mg of DLH. No. Same as previously stated. and B were analyzed and recorded. Surface areas were determined using the Brunauer-Emmett-Teller (BET) equation using nitrogen as the adsorbate. the regenerated DLHs were named as DLH-60-2 or DLH-450-2.44 mM) sodium chloride (prepared using deionized water with GR grade NaCl) to make the boron concentration in a range from 5 to 500 mg/L. Adsorption Kinetics. the composition of the DLHs can be estimated using the following equation. X-ray diffraction (XRD) patterns were obtained for randomly orientated samples using a Siemens D5000 diffraction system and the data was processed using Siemens Diffrac Plus processing software.2 NO38. Figure 1 shows the overall processes of adsorption and regeneration. NO3-. Vol. Fe ions 3.3 g of DLH-450 were mixed with a shaking speed of 300 rpm for 4 h and then centrifuged. Various doses of DLH-60 and DLH-450 were added into 50 mL screw-top plastic tubes filled with 25 mL of model water with boron concentrations ranging from 5 to 500 mg/L. The particle size of DLHs was observed by a high-resolution scanning electron microscope (SEM) (Philips FEI FEG XL30). After 4 h of vigorous shaking at room temperature (25 °C). a hydrotalcite structure is confirmed by the XRD analysis. And then they were crushed to powders named as DLH-60 and DLH-450.. Overall Processes of Regeneration. The regenerated DLHs were used for the boron removal tests following the same procedure as detailed above.7 PO43 1. water samples were withdrawn and boron concentrations were measured. For different time intervals (30 min to 4 h).26 g/L (4. Results and Discussion XRD Analysis of DLHs.4 T.4578 Ind. Effect of pH on the Boron Removal Efficiency. and for each subsequent regeneration. and chloride were used to interpret the possible mechanisms.

anions. while the original DLH60 does not.4(OH)7. Regeneration process for DLH-60 (DLH-450).03(NO3)0. Effect of DLH Dose on Boron Removal. Res. Chem.and Cl. No. the formula of DLHs prepared for this study can be proposed as Mg2AlNa1. the structure of the DLH-60 changes. Density of DLHs. Figure 3 shows two pictures taken by a high-resolution scanning electron microscope (SEM). . 2007 4579 Figure 1. we can speculate that the boron removal mechanisms with DLH-60 and DLH-450 are very different and this will be discussed in a later section. a type of Al(OH)3. Figure 2. In addition to this. Particle Size of DLH-60 and DLH-450.anion but DLH prepared in this study consists of NO3. Composition of DLH Products. It can be seen that both DLHs have an average size less than 100 nm in diameter. Then. It can be seen that the surface area of DLH-60 was much smaller than that of DLH-450. However. Table 3 displays surface areas of DLHs. DLH-60-1 consists of bayerite. Based on the mass balance results shown in Table 2. Surface Areas of DLHs. hydrotalcite consists of CO32. boron percentage removal increased with increasing doses until a maximum value was reached (>80% for the DLH-60 and >90% for DLH-450). 13.90 g/cm3. The density of DLH-60 is 1.8‚x(H2O) where the OH content was established based on the results of mass balance and electronic balance. after regeneration.Ind. while boron removal efficiency of both DLHs was not significantly different (15% in difference).57Cl0. For both DLHs. this does not change the surface area significantly as shown later. ranging from 5 to 500 mg/L.09 g/cm3 and DLH-450 is 0. XRD analysis of DLH-60. Figure 2 presents an example of the XRD results for DLH-60. 46. Boron removal performance with DLH-60 and DLH-450 was studied at pH 7 via model waters with various boron starting concentrations. Eng.. Vol.

4580 Ind.18 boron % removal 84 97 Table 4.1 17. and RL ) 0.14 0.9602 Kf 2.8958 0. Al almost did not release into the solution. Table 2.08 a Obtained by XRF measurement results. 13. at given dose ranges of the DLH. The adsorption capacity of DLH-450 ranges from 16.04 0. the constant q signifies the adsorption capacity 0 (mg/g) and b is related to the energy of adsorption (L/mg).20 0. Adsorption study was conducted using DLH-450 and the isotherms were developed based on the results achieved. 2007 Figure 3.70 13.9226 0. 0 < RL < 1. and NO3. right: DLH-450. which develop a variable charge through protonation-deprotonation reactions. The removal of boron/borate can occur by anion exchange with both the intercalated and surface anionic charge of the DLH.03 R2 0. indicating that the main structure of DLH-60 (AlOHx)n remained unchanged. Filtrate pHt remained constant around 8. Al.80 residual in the supernatant (g) 0. RL ) 1.75 g of HT-60 and 0.67 3. After 4 h of vigorous shaking.65 24.03 10.20 0.10a 4.04 0. Boron removal vs DLHs’ dose. DLHs have surface groups that can establish chemical bonds with boron/borate molecules. unfavorable. Eng. Table 3.805 4.00 0. Mass variations of boron. indicating that DLH has a high buffering capacity.14 The net positive charge on the DLHs is balanced by anions close to the planar surface and interlayer in the DLH. Besides exchanging ions. concentrations of Mg2+ and NO3.. Similarly.9657 0. Surface Areas of DLHs samples DLH-60 DLH-450 surface area (m2/g) 31. and amphoteric charges resulting from surface hydroxyl groups (broken edges).710 Freundlichb n 1. Figure 4. Composition of DLH content in DLH ion Mg2+ Al3+ Na+ ClNO3dose in the preparation (g) 4.60 6. which is mainly an electrostatic process.10 the supernatant can be seen in Table 5. Kf and n are adsorption isotherm constants.3 mg of B/g of adsorbent for three starting boron concentrations studied.82 (g) 4. and boron concentrations and filtrate pHs were determined. the Freundlich equation is adequate for use. respectively. boron percentage removal with DLH-450 was 50% higher than that with DLH-60.80 10. b In Freundlich equation. irreversible.98 (mol) 0.873 3. T ) 25 °C. water samples were filtrated. The DLHs have a permanent positive charge originating from the isomorphic substitution of bivalent (Mg2+) by trivalent (Al3+) ions.80 2.3 g of HT-450. It can seen from Table 4 that both Langmuir and Freundlich equations fit the adsorption results and they can be used to propose the adsorption capacity of DLH-450 on the boron removal. No. favorable. Table 4 is illustrated by plotting various isotherms results with Langmuir and Freundlich equations.864 4. Most of the chloride was washed away during the washing procedure.986 4. Res. the fitness of using the Freundlich equation to describe the adsorption can be assessed by the constant. It can be seen that. However.003 0.11 0.30 130. The fitness of using Langmuir equation to describe the adsorption process can be assessed by a term “RL”. pH-Dependent Experiments.9226 0. pH0 ) 7. n. Mg. The parameter RL indicates the shape of the isotherm accordingly: RL > 1. Adsorption Isotherm.06 RL 0.42 19. linear. 46. Chem. Figure 4 shows an example of the comparative boron removal by DLH-60 and DLH-450 for model waters with two starting boron concentrations. Langmuir and Freundlich Constants for DLH-450 Langmuira [B]0 (mg/L) 100 250 500 q0 (mg/g) 16. being indicative of the capacity and intensity of adsorption. The amount of NO3.1 to 17.5 for DLH-450.255 R2 the supernatant increased while the mass of borate decreased after 4 h of mixing.9225 a In Langmuir equation.0 17.6 for DLH-60 and 10.80 2. If 1 < n < 10. Boron Removal Mechanisms with DLHs.3 b (L/mg) 0.released was greater or similar to the amount of boron removed for the . [B]0 )10 and 500 mg/L.26 0. SEM image of two DLHs: Left: DLH-60. Vol. which is a dimensionless constant and is defined as RL ) 1/(1 + bC0) (where b is a constant in the Langmuir equation and C0 is boron equilibrium concentration). Twenty-five milliliters of 10 and 100 mg/L boron model water was adjusted to its initial pH to between 3 and 11 by either 5 M NaOH or 1 M HCl and then mixed with 0.

during the treatment.49 0.45 0. The mass balance was made based on the boron removed in adsorption and boron released in . the maximum amount of Mg releasing is about 4% of the original Mg content for a dose of DLH-60 (e.22 NO3(mmol) 0 1. but most possibly by a physicochemical adsorption due to its relatively high surface area (see Table 3) and this is confirmed by the adsorption isothermal data presented in Table 4. The subsequent regeneration study has confirmed this (see later section). A few NO3-’s releasing from DLH-450 in the treatment (Table 6) can be judged that DLHs calcined at 450 °C lose their layered structure and become oxides.91 0. Table 5. For higher boron starting concentration (sample 6. The similar complexes between OH ligands and borate or boric acid were proposed previously when hydroxycaroxylic acids were tested to complex and precipitate boric acid. the DLH-60 has to be regenerated with nitrate salts to repossess an anion exchange capacity.21 0. The resulting supernatant was collected and concentrations of boron and other components were analyzed. Dose ) 28 g/L [B] pH0 (mg/L) (mmol) (mg/L) 0 3. 46. This is evident by XRD spectra of DLH450. and excess nitrate release indicates that.00 0. DLH-450 (0. Table 6 shows the boron removal with DLH-450 and the released amount of NO3.67 × 10-4 ∆NO3(increased) (mmol) 0. and then the high boron percentage removal (95.3 g) was mixed with 25 mL of model water ([B]0 ) 100 mg/L) for shaking at 300 rpm for 4 h.23 DLH-450 10.30 × 10-3 removed or 0.65%) with DLH-450 cannot be attributed to the anion exchange.25 × 10-5 1.53 0.02 0. 13. mainly for DLH-450.01 0.30 0.42 0.22 released ion samples with relative low boron starting mass/concentrations (samples 1-5. 5 to 100 mg/L) which is adequate to exchange with borate in the interlayer of DLH-60.60 4. and then the released Mg ions contributed to the borate removal via the proposed Mg-B precipitation. Chem.11 × 10-4 1. Only a few NO3-’s were released from DLH-450.25 × 10-5 9. the majority of anions (NO3-) release during the calcination process.g.38 DLH-60 dose ) 50 g/L.40 0.16 0.18 0.30 × 10-3 1. DLH-450 for Boron Removal from 100 mg/L Boron Model Water.12 0.15 A desorption test was carried out to validate the above adsorption mechanism by DLH-450. Eng. No.19 0.00 100. Results shown in Table 5 also raise the concern of whether the DLH-60 is stable or not for long-term use for water and wastewater treatment. XRD analysis of DLH-450.65 model water 7.23 0. 2007 4581 Figure 5. after one use. under conditions of shaking at 300 rpm for 4 h. the released NO3. Under most study conditions and for the model water. However. nitrate release is higher than that required for the exchange of boron.. Res. DLH-60 could be stable for a long-term use. The mixture with desorpted DLH-450 was then separated and concentrations of boron and others in the supernatant were analyzed.01 0. 50 g/L). pH0 ) 7.60 0.02 0. Mass Difference in the Model Water before and after Treatment with DLH-60a mass of B model in the ∆B ∆Mg water model water (removed) (increased) sample (mmol) (mmol) (mmol) 1 2 3 4 5 6 a ∆Al (increased) (mmol) 9.30 × 10-3 B% removal 0 95.Ind. Vol. The proposed boron removal mechanisms are presented in Figure 6 which includes anion exchange for DLH-60 and borate sorption via ligand complexion. Nevertheless.58 1.02 9.25 × 10-5 6.. and the mixture was separated by centrifugation.was less than the amount of boron removed. thus.17 0. anion exchange seems to be the main mechanism of boron removal by DLH60 with the evidence of the mass difference of samples 1-5 shown in Table 5.23 0. the Mg releasing for each use is not significant.48 × 10-5 9. where the intensity of DLHs structure decreased significantly with increasing in the basal spacing and oxide structures appear (Figure 5).11 0. [B]0 ) 500 mg/L). OH ligands exist in all edges of the DLH and they are ready to complex with borate and thus remove boron from solutions. Table 6. The separated DLH-450 was washed and then mixed with 25 mL of 5 M Na2SO4.46 0. Therefore.

For the treatment of industrial effluent ([B]0 ) 17 mg/L). This suggests that the oxide structure of DLH-450 could be reverting back to a double-layer hydrotalcite structure.9 B% 86.4 4. As the adsorbed nitrate in the saturated DLH-450 will release in the regeneration under the same calcination process at 450 °C. Industry Effluent Results. DLH-450 dose: 16 g/L. DLH-450 possesses a greater boron removal capacity.1 10.6% and 93. a 5M NaNO3 was selected as the regeneration reagent for further studies.7 59. Na. Figure 6.3 1. Raw materials were denoted as DLH-60 or DLH-450 while regenerated DLH samples were denoted as DLH-60-1-6 or DLH-450-1-6. and NO3. A comparison with DLH-60. Table 7 shows that arsenic can be removed completely by both DLHs. Boron removal capacity with DLH before and after regeneration. Table 7 also shows that DLH-450 slightly reduced NO3concentration in the industrial effluent (from 8. Arsenic can be completely removed by both DLHs. The boron removal capacity for DLH450 is 5. the DLH-60 still can achieve about 69% removal of boron.8 SO42(mg/L) 316. after the fourth regeneration.8 Na+ (mg/L) 74. due to the adsorption of NO3-. Table 7) for the industrial effluent vs 0.03(NO3)0. Preliminary Trials of the Regeneration of DLH-60. DLH-60 has to be regenerated with nitrate salts to repossess an anion exchange capacity and this will not affect the long-term use of DLH-60.57Cl0. the boron percentage removal increased with increasing doses of both DLH-60 and DLH-450 until a maximum value was reached (>80% with DLH-60 and >90% with DLH-450). Eng. Conclusions The following collusions can be made through this study: The XRD results confirm that all prepared or regenerated DLH materials used for this study have a similar structure to the conventional hydrotalcites but without carbonate anions. respectively.0 206. in industrial effluent.6 mmol for the model water. Table 6 shows obviously that.2 × 103 7. No.8‚x(H2O) The density of DLH-60 is 1. Boron removal increased with DLH doses. less Mg. Chem. The structure of the DLHs synthesized is proposed to be Mg2AlNa1. 13.1 As3+ (mg/L) 0. for the raw and each stage-regenerated DLHs. Figure 7.2 0 0 NO3(mg/L) 8. In comparison. the efficiency of the regenerations was in a range between 45 and 65%.5% by the dose of 16 g/L for DLH-450.97 × 10-2 Ca2+ (mg/L) 110. For cumulative six regenerations.18 m2/g. It is worth noting that the boron removal with new DLH450 is extremely high.5% of boron can be removed at a dose of 36 g/L for DLH-60 and 16 g/L for DLH450. . For treating model waters with various starting boron concentrations (5-500 mg/ L). after regeneration. desorption.29 PO43(mg/L) 1.4582 Ind. boron removal increased with DLH doses: 86.7 0. sulfate.6 mmol (equivalent to 4200 mg/L. Res. Regeneration Results.4(OH)7. Figure 7 compares the boron removal capacities with raw and six regenerated DLHs. The surface area of DLH-60 is 31. it appears that the stability of the regenerated DLH-450 will not be affected.9 8. Generally. and Na2SO4 were selected as regeneration solutions.1 pH 7.97 × 10-2 <1. 97%. and phosphate were removed via the anion exchange mechanism with nitrate. the high buffer capacity of DLHs was hardly changed.2-13 mg of B/g.0 2.5 235. around pH 8.90 g/mL.2 for DLH-60 and pH 10 for DLH-450. As stated previously. NaNO3.1 mg/L).was observed in treating industrial effluent with DLH-60 in comparison with the treatment of model water (Table 5): 1. After six cumulative regenerations. this decreased to 54%.36 0.. A much larger release of NO3. This is because. boron percentage removal with the regenerated DLHs decreased to about 40%.6% by the dose of 36 g/L for DLH-60 and 93. results show that this does not affect the overall boron removal performance with DLH450 for the batch study conditions.5 Note: DLH-60 dose: 36 g/L. The selection of a regenerated solution was based on both the high regeneration efficiency and a high boron removal efficiency of the regenerated DLH.8 148.4-17. NaCl. Then.were released and more Ca was removed with DLH-450. Another feature of using the DLHs is that.09 g/mL and DLH-450 is 0. The raw water’s pH does not affect the boron removal performance with DLHs. Quality Characteristics of the Industry Effluent Treated by DLHsa parameter industry effluent DLH-60 DLH-450 a boron (mg/L) 17.6 93. respectively. but after the third regeneration. and the pH remained constant in the treated waters. which shows that 96% boron can be adsorbed (or removed) in the adsorption and 90% of boron binding with DLH-450 can be released to Na2SO4 solution in the desorption. 2007 Table 7. the final pH of water treated by DLH-450 increased to about 11. DLHs structure and boron removal schemes. as high as 86. not only boron but also arsenic.97 <1.4 110.2 Mg2+ (mg/L) 18. However. Vol. the boron removal performance of DLH-60 and DLH-450 decreased gradually. 46.8 441.4 to 7.3 mg of B/g and that for DLH-60 is 1. Nevertheless. respectively. after various regenerations.3 m2/g and that of HT-450 is 130.

Mo. EnViron.. K. 280 (2). Chem.. 350. K. K. Chem. Y. Brussels. Simon. 37. TR-74-7. J.S. Mg. 1. N. M. 34. M. Desalination 2004.. Vol. Shettle. H. (6) Jiang. 2004. Technol. N.. Milestone. 2007 ReVised manuscript receiVed April 9. Quill. Removal of B. (2) European Food Standards Agency. World Health Organisation: Geneva. 3. 80. J. R. Chem. 431. 1196. 1. Addendum to Vol. 189. Yoshinari.. C. T. 1995. 1023. 2981. 2004. Eng. Demircioglu. 2.. Recommendations of Boron. 3rd ed.. 419. Sahu. 1998.. J. Simon. R. 1991.. S. 2003. 2004. A. M. Acknowledgment The authors are grateful for the financial support from the Borax Europe Ltd. Vol. Opinion Of The Scientific Panel on Dietetic Products. Reardon. de Pauli. Technol. The Complexation of Borate from Solution by Hydroxycarboxylic Acids.. 1979. Mordogan. K. Xu. A. (14) Delgado.. Cl-. Q. and Se from Wastewater by Incorporation into Hydrocalumite and Ettringite. J. Recommendations. Cr. 2005. On the Quality of Water Intended for Human Consumption. The views of this paper are not necessary representing that of the Borax Europe Ltd. II. Eng. E. The main mechanism of boron removal with DLH-60 is to be anion exchange while that with DLH-450 is adsorption. Technol. M. (4) Guidelines for Drinking-Water Quality. 34. L. pp 15-29. Res. For DLH-450. K. J. Stability of Calcium Sulphoaluminate Hydrates in Water Solutions with Various pH Values. The Drinking Water Contaminant Candidate List 2. Technical Report No. Quill. Y. 53 (11). F. Sep. Removal of Boron (B) from Waste Liquors. 2006. Boron..Ind. 46. 2007 IE0703639 .. Shettle. Tsuyoshi. N. (12) Zhang. B. 2006. EnViron. EnViron. both Langmuir and Freundlich isotherm models fit well with the experimental results. Y. Masaru. Removal of Boron from Wastewater of Geothermal Power Plant by Selective Ion-Exchange Resins. EFSA. Sci. M.. W. 2947. Technol. J. DLH-450 has a greater boron removal capacity than DLH-60 for both freshly prepared and regenerated materials. R. Chen. and NO3were released and more Ca and Fe were removed with DLH-450.. (8) Choi. 2007 Accepted April 21. Overall. Column sorption-elution studies. ReceiVed for reView March 9. 1974. H. No. J. EPA: Washington DC.... Ind. Sci. Kabay. Res. 13. Na. (11) Parker. Fact Sheet EPA 815-F-05-001. 1998. Borax Technical Ltd. (13) Gabrisova.. After six cumulative regenerations.. Colloid Interface Sci... Newman. less Al. Literature Cited (1) Guidelines for Drinking-Water Quality 2nd ed. The Use of Hydrotalcite as an Anion Absorbent. (5) U. U. (9) Badruk. K. Ulibarria. boron percentage removal with regenerated DLHs decreased to about 40%. 73. Ipekoglu. A.-W. L330/41. EC Official Journal. Environmental Protection Agency. Q. 2007 4583 Comparison with DLH-60. Vidaurreb. Havlica. Avena. Nutrition and Allergies on a Request from the Commission Related to the Tolerable Upper Intake LeVel of Boron (sodium borate and boric acid). Boron removal performance with DLHs decreased gradually after each step of regeneration. 167. M. (7) Jiang.. (15) Farmer. Mechanism of Boron Removal with Electrocoagulation. J. B. Boron Removal in RO Seawater Desalination. Cement Concrete Res. (10) Masahide. Xu. 13. pp 4-6. M. 21. and Addendum to Vol. (3) Council of European Communities Directive (CECD) 98/83. Surface-Charging Behavior of Zn-Cr Layered Double Hydroxide... Evaluation of Boron Removal by Adsorption on Solids. P. Water Sci. World Health Organisation: Geneva.. 1999. J.: London. J... Sci.