International Journal of Chemical Engineering and Applications, Vol. 6, No. 4, August 2015 Synthesis of Hydrotalcite from Bittern, and Its Removal Abilities of Phosphate and Nitrate Takaaki Wajima well as all its uses in general. Eutrophication is a peculiar Abstract—In this study, hydrotalcite was synthesized from form of water pollution, causing major alterations: abnormal bittern solution with addition of AlCl3 (Mg/Al molar ratio of the water colorations, loss of transparency and toxicity by the solution = 3), and its removal abilities of phosphate and nitrate presence of certain algae products [22]. The eutrophication from aqueous solution were examined. Hydrotalcite can be synthesized from bittern and seawater, and the product from process is caused by the increase in nutrients levels, bittern is higher content of hydrotalcite than that from seawater. particularly phosphorus and nitrogen, which exceeds the The product from bittern has a removal abilities of phosphate limiting threshold of the primary production and, and nitrate, which were higher than commercial hydrotalcite. consequently, ecosystem control mechanisms are not used The equilibrium adsorption capacity of the product for [23]. In order to prevent eutrophication, it is considered to phosphate and nitrate ions were measured and extrapolated using Langmuir and Freundlich isotherm models, and reduce the load of phosphorus and nitrate to water experimental data are found to fit Langmuir than Freundlich. In environment. One method is the removal of phosphate and the solution with 1 mM of phosphate or nitrate ions, adsorption nitrate ion by HT [24]-[28]. However, HT is an expensive of phosphate on the product was saturated within 30 min and material used as antacid, etc., and it is necessary to develop a almost constant after 30 min, while that of nitrate increase new process for inexpensive HT. within 15 min and then gradually decrease, due to the ion exchange reaction of chlorine and sulphate in the product. The bittern was the by-product from the refinement process of salt. Though the bitterns are regarded as waste material, Index Terms—Hydrotalcite, bittern, removal of phosphorus several kinds of ions (Mg2+, Ca2+, K+, Na+) are rich in bittern. and nitrate, anion exchange. Especially, magnesium ion is the most abundant cation species in bittern. In this study, HT was synthesized using bittern in I. INTRODUCTION consideration for the utilization of plant-producing Mg(OH)2, The hydrotalcite (HT) is classified as a layered double and the characteristics of removal for phosphate and nitrate by hydroxide (LDH) composed of metal complex hydroxide: the HT was examined for the application of water 2+ 3+ x+ n- x- [M 1-xM x(OH)2] [(A )x/n‧nH2O] (x = 0.2 - 0.33), where purification. M2+ and M3+ are divalent and trivalent metal ions, respectively, and An- is anionic species [1]. The structure of HTs consists of a positive charged brucite-like octahedral II. MATERIALS AND METHODS layer and a negatively charged interlayer containing anions and water molecules [2]. The positively charged layer is A. Seawater and Bittern formed by partial substitution of a trivalent metal for a Seawater and two bittern samples were used in this study. divalent one. The layers can be stacked, and the balancing Seawater was collected from the surface layer of Imari bay, interlayer anions can be exchanged with other anions. Saga prefecture, Japan. Two bittern was obtained from two HT have received increasing attention in recent years as Japanese salt making plants with different processes. ion-exchanger [3]-[8], catalyst [9], [10], precursor for catalyst Chemical compositions and pHs of these samples are shown + + 2+ 2+ - - [11]-[13] and antacids [14]-[16] in medical application. in Table I. The contents of Na , K , Mg , Ca , Cl , Br and 2- Extensive studies have been made on the method of SO4 in samples were determined by ion chromatography preparation and the physicochemical properties of HT (DX-120, Dionex), and pHs of the sample were measured by compounds [17]-[21]. pH meter (MA-130, Mettler toledo). Eutrophication is a water enrichment in nutrients that generally leads to symptomatic changes when the production TABLE I: CHEMICAL COMPOSITIONS AND PHS OF SEAWATER AND BITTERNS of algae and other aquatic vegetations are increased, Seawater Bittern-1 Bittern-2 degradation of fisheries and deterioration of water quality as Contents (g/L) Na+ 9.7 103.5 30.7 K+ 0.4 5.4 35.0 Mg2+ 1.3 14.8 43.9 2+ Ca 0.4 N.D. 24.6 Manuscript received August 9, 2014; revised November 12, 2014. This Cl- 18.5 204.1 250.8 work was supported by the Cooperative Research Program of the Institute of Br- N.D. N.D. 18.3 Ocean Energy, Saga University (14004A). 2- SO4 4.4 43.0 N.D. Takaaki Wajima is with Department of Urban Environment Systems, Graduate School of Engineering, Chiba University, Japan (e-mail: pH 7.7 7.4 6.8 [email protected]). N.D.: Not detected DOI: 10.7763/IJCEA.2015.V6.486 228 International Journal of Chemical Engineering and Applications, Vol. 6, No. 4, August 2015 B. Synthesis of Hydrotalcite (a) ○ ○: Hydrotalcite 1 M AlCl3 solution was added to 100 mL of seawater or bittern to adjust the Mg/Al molar ratio of 3 in the mixed ○ ○ ○ solution, and stirred at 50 oC for 24 h. During stirring, pH of (b) the solution was maintained at 10.5 by dropping10 w/v% ○ NaOH solution. After stirring, precipitates were filtered, o washed with distilled water, and then dried at 80 C to obtain ○ ○ ○ the product. The products were identified using X-ray Intensity (a.u.) (c) ●: Calcite [CaCO ] diffraction (XRD) (RINT-2500, Rigaku), and was observed 3 ■: Brucite [Mg(OH) ] 2 by scanning electron microscope (SEM) (S-2400, Hitachi). ○ ○ To determine chemical composition of the products, 25 mg of ■ ● ○ ○ the product was perfectly dissolved in 10 mL of 0.1 M HNO3 2+ 3+ 0 10 20 30 40 50 60 solution, the contents of Mg and Al were measured by θ α 2 [CuK (degree)] inductively-coupled plasma spectrometers (ICP-AES) Fig. 1. X-ray diffraction patterns of the products from (a) bittern-1, (b) - 2- bittern-2 and (c) seawater. (SPS3000, Seiko instruments), and those of Cl and SO4 were determined using ion chromatograph. The content of Table II shows chemical compositions of the products and CO3 in the product was analyzed by carbon/sulfur analyzer commercial hydrotalcite. As the HT has positive charged sites (EMIA1200, Horiba). Differential thermal analysis (DTA) / 3+ thermogravimetry (TG) (TG8120, Rigaku) was carried out in based on the Al in double hydroxide layer [21], the o o intercalated amount of anion should be theoretically equal to the temperature range 20 - 800 C at a heating rate of 10 C 3+ 3+ min-1 in flowing air. the Al amount in the HT. Namely, the amount of Al should be in accord with the anion exchange capacity of the HT. The C. Removal Tests of Phosphate and Nitrate anion exchange capacities of the products were estimated to Isotherm experiments of removals for phosphate and be 2.7 - 2.8 mmol/g, and that of commercial HT are also nitrate using the product from bittern-1 were performed as considered to be 2.0 mmol/g. Generally speaking, 1 mmol/g follows: 0.1 g of the product was added to 20 mL of the or more of anion exchange capacity should be required as a solution of NaH2PO4 or NaNO3 with 1 - 25 mM in 50 mL of standard for the practical use. So these exchange capacities centrifuge tube, and the slurry was shaken with reciprocal may be adequate large as an anion exchanger. shaker for 12 h. After shaking, the tube was centrifuged, and The amount of exchangeable anions in commercial HT is the concentrations of phosphate and nitrate in supernatant 2.1 mmol/g as CO3, which is almost same as anion exchange were measured using ion chromatograph. capacity of commercial HT (2.0 mmol/g). It is considered that - The adsorption amounts of phosphate and nitrate per exchangeable anion in HT present as monovalent HCO3 . The - 2- sample were calculated using the following equation; exchangeable anions in the products are mainly Cl , SO4 and - HCO3 , and the total amounts of exchangeable anions are 2.9 q (C0 C) V / w (1) mmol/g in the product from bttern-1 and 3.0 mmol/g in the product from bittern-2, respectively, which are almost same where C0 and C are the initial and final concentrations of as anion exchange capacities of the products. Therefore, these phosphate and nitrate in the solution (mmol/L), respectively, three anions are mainly exchangeable anions in the product. It V is the solution volume (L), and w is the mass of sample is noted that the product from seawater is low content of Cl added to the solution (g). and high content of CO3, due to the present of calcite in the Kinetics of removal reaction for phosphate and nitrate product. using the product were determined as follows; 50 mg of the The Mg/Al molar ratios of the products indicate 3.5 - 3.6, product was added to 100 mL of the solution of NaH2PO4 or and they may be higher than 3.0 of the set value in the HT NaNO3 with 1 mM in 200 mL baker, and the slurry was stirred preparation. It may be caused by the nature of the solution with magnetic stirrer for 120 min. During stirring, 2 mL of with different concentration of Mg2+ and some coexisting ions. aliquot was removed, and then filtered to obtain the filtrate, It is noted that Mg/Al molar ratio of commercial HT is 4.4.