• Journal of Korean Society of Water and Wastewater
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• v.28 no.2
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• pp.207-215
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• 2014

Wastewater containing heavy metals such as copper (Cu) and nickel (Ni) is harmful to humans and the environment due to its high toxicity. Crystallization in a fluidized bed reactor (FBR) has recently received significant attention for heavy metal removal and recovery. It is necessary to find optimum reaction conditions to enhance crystallization efficacy. In this study, the effects of crystallization reagent and pH were investigated to maximize crystallization efficacy of Cu-S and Ni-S in a FBR. CaS and $Na_2S{\cdot}9H_2O$ were used as crystallization reagent, and pH were varied in the range of 1 to 7. Additionally, each optimum crystallization condition for Cu and Ni were sequentially employed in two FBRs for their selective removal from the mixture of Cu and Ni. As major results, the crystallization of Cu was most effective in the range of pH 1-2 for both CaS and $Na_2S{\cdot}9H_2O$ reagents. At pH 1, Cu was completely removed within five minutes. Ni showed a superior reactivity with S in $Na_2S{\cdot}9H_2O$ compared to that in CaS at pH 7. When applying each optimum crystallization condition sequentially, only Cu was firstly crystallized at pH 1 with CaS, and then, in the second FBR, the residual Ni was completely removed at pH 7 with $Na_2S{\cdot}9H_2O$. Each crystal recovered from two different FBRs was mainly composed of CuxSy and NiS, respectively. Our results revealed that Cu and Ni can be selectively recovered as reusable resources from the mixture by controlling pH and choosing crystallization reagent accordingly.

• Journal of the Korean Society of Fisheries and Ocean Technology
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• v.52 no.3
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• pp.271-275
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• 2016

Recently, pollution problem in coastal water has become more serious and pollution including red tide serves as a main reason for reduction of fishes resources. Particularly, nutrients such as nitrogen and phosphorus are the most serious pollutants. Normally, biological wastewater treatment process is used in removing such nutrients. However, it is difficult to adopt the biological wastewater treatment process to a small-scale fish processing factory in case of using seawater as wash water. Thus, removing nutrients through struvite crystallization is investigated in this study for treating shrimp processing wastewater. Experiments were conducted by varying molar ratio of $Mg^{2+}:NH^4-N:PO^4-P$ from 1:1:1 to 2:1:1. It can be concluded that optimum molar ratio is 1:1:1. Struvite crystallization process is compared with chemical coagulation process using PAC and struvite crystallization process is proven as the more effective process in removing nutrients from wastewater. In view of results obtained from these experiments, struvite crystallization process is a promising method in removing nitrogen and phosphorus from wastewater; however, not so good in removing organics. Thus, struvite crystallization process is suitable as the pre-treatment process in treating shrimp processing wastewater and additional biological process is needed to remove organics.

• Membrane Journal
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• v.17 no.2
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• pp.93-98
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• 2007

The reliability of innovative membrane contactors technology (i.e. Gas/Liquid Membrane Contactors, Membrane Distillation/Crystallization) is today increasing for seawater desalination processes, where traditional pressure-driven membrane separation units are routinely operated. Furthermore, conventional membrane operations can be integrated with membrane contactors in order to promote possible improvements in process efficiency, operational stability, environmental impact, water quality and cost. Seawater is the most abundant aqueous solution on the earth: the amount of dissolved salts covers about 3% of its composition, and six elements (Na, Mg, Ca, K, Cl, S) account for more than 90% of ionic species. Recent investigations on Membrane Distillation-Crystallization have shown the possibility to achieve significant overall water recovery factors, to limit the brine disposal problem, and to recover valuable salts (i.e. calcium sulphate, sodium chloride, magnesium sulphate) by combining this technology with conventional RO trains. In this work, the kinetics of $CaSO_4{\cdot}2H_2O,\;NaCl\;and\;MgSO_4{\cdot}7H_2O$ crystallization is experimentally investigated in order to improve the design of the membrane-based crystallization unit.

• Journal of Pharmaceutical Investigation
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• v.41 no.1
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• pp.45-50
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• 2011

Nonclassical pathway of crystallization has been utilized to modify the properties and morphologies of inorganic and organic/inorganic materials. In here, the polymer-directed crystallization method has been applied to the pharmaceutical active ingredient to assess the applicability for as a particle engineering tool. The polymer-directed crystallization was successful to modifying the crystal size, habit and morphology, but it was not effective to discover the novel polymorphs of Sibutramine (SB). SB was selected as a model drug and polyacrylic acid (PAA), polyethylene imine (PEI) and chitosan (CHI) were added as a crystallization pathway modifier. SB was crystallized via drowning crystallization using methanol or ethanol as a solvent and water as a non-solvent. The significant interactions between polymer and the drug were confirmed by measuring the solubility of the drug in presence of polymer during the crystallization. The crystal forms of SB are characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and optical microscope (OM). The polymer-directed crystallization seems to be able to modify the crystal properties of pharmaceutical active ingredient, which is critical in determining the bioavailability, processability, and stability.

• Journal of Korean Society on Water Environment
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• v.21 no.1
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• pp.59-65
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• 2005

A phosphate recovery system from artificial wastewater was developed using a completely mixed phosphorus crystallization reactor, in which powdered converter slag was used as a seeding crystal. In preliminary test, the optimal pH range for meta-stable hydroxyapatite crystallization for high phosphorus concentration was observed to be 6.0 to 7.0, which was different from the conventionally known pH range (8.0~9.5) for effective crystallization in relatively low phosphorus concentration less than 5 mg/L. The average phosphorus removal efficiency in a lab-scaled completely mixed crystallization system for artificial wastewater with about 100 mg/L of average $PO_4-P$ concentration was shown to be 60.9% for 40 days of lapsed time. XRD analysis exhibited that crystalline of hydroxyapatite formed on the surface of seed crystal, which was also observed in SEM analysis. In EDS mapping analysis, composition mole ratio (=Ca/P) of the crystalline was found to be 1.78, indicating the crystalline on the surface of seed crystal is likely to be hydroxyapatite. Particle size distribution analysis showed that average size of seed crystal increased from $28{\mu}m$ up to $50{\mu}m$, suggesting that phosphorus recycling from wastewater with high phosphorus concentration can be successfully obtained by using the phosphorus crystallization recovery system.

• Journal of Korean Society on Water Environment
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• v.26 no.4
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• pp.664-672
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• 2010

This study was performed to evaluate the feasibility of industrial by-products such as converter slag, olivine, red mud and fly ash as a seed crystal of struvite crystallization for the removal of highly concentrated $NH_4-N$ and $PO_4-P$. In the kinetic experiments, more than 90% of $NH_4-N$ and $PO_4-P$ was eliminated by struvite crystallization within 30 minutes of reaction time. The pH range in meta-stable region of struvite crystallization was found to be pH 7.0~9.0 under the Mg:N:P=1:1:1 equi-molar condition with 100 mg/L of $NH_4-N$. Total removal efficiencies of $NH_4-N$ and $PO_4-P$ by both struvite precipitation and crystallization were increased with the increase of pH. Removal efficiencies of $NH_4-N$ and $PO_4-P$ were significantly enhanced by struvite crystallization using industrial by-products as a seed crystal compared with those by struvite precipitation without seed crystal. Red mud, converter slag, olivine and fly ash enhanced the removal efficiencies of $NH_4-N$ by 40.9%, 37.7%, 28.4% and 16.4%, respectively. Removal efficiencies of $PO_4-P$ for converter slag, red mud, fly ash, olivine were increased by 3.7 times, 2.6 times, 72.4% and 68.0%, respectively. Converter slag and red mud showed higher feasibility as a seed crystal than others for the removal of highly concentrated $NH_4-N$ and $PO_4-P$. In particular, converter slag might have a high capacity of phosphorus removal.

• Journal of Technologic Dentistry
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• v.14 no.1
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• pp.95-118
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• 1992

Glass ceramics for crown were prepared by adding 3$\sim$11 wt% TiO2 to the weight percent composition of 34.7 CaO, 27.8 SiO2, 18.3P2O5, 12.6MgO and 6.6 TiO2. The starting glasses were prepared by melting the powdered batch in alumina crucible at 1350$\sim$1400 for 1 hr and then quenching into a distilled water. The nucleation and crystallization of the crystalline glass ceramics for crown were studied by DTA, SME and X-ray diffraction analysis. Frit containing 9.11 wt% TiO2 had crystallization temperature of 850$\sim$1075 and major crystalline phase was identified by X-ray diffraction as diopside(CaO-MgO-2SiO2). Activation energies for the crystallization processes were obtained from DTA by varing rates for the fits, and were calculated from modified Ozawa and Kissinger equations. Activation energy for the crystallization processes of the S-4 frit was 489.6 KJ/mol.

• Korean Chemical Engineering Research
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• v.47 no.6
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• pp.740-746
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• 2009

In the present study, the drowning-out crystallization of L(+)-calcium lactate was investigated in order to develop the crystallization separation process. The crystallization of the calcium lactate was induced by injecting the alcoholic anti-solvent into the aqueous solution of calcium lactate and the control of the calcium lactate crystal size during the crystallization was primarily investigated under the consideration of the anti-solvent species, anti-solvent composition and agitation speed as the key operating factors. Alcohols of methanol, ethanol, n-propanol and i-propanol were used as the anti-solvent for the drowning-out crystallization. Prior to the crystallization experiment, the solubility of calcium lactate in the water-alcohol mixture was measured along with the variation of the alcohol species and composition, which was necessary to estimate the supersaturation level of the crystallization. By the drowning-out crystallization, the calcium lactate crystals of the fabric shape were obtained. Using the ethanol as the antisolvent, the fabric crystals close to the needle shape were produced. However, the hairy crystals were obtained by using the propanol as the anti-solvent. Due to such morphological features, the crystals was highly apt to form the aggregates. The aggregation of the crystals was intensified as increasing the alcohol fraction in the water-alcohol mixture. Meanwhile, the agitation caused the breakage of crystals, resulting in the decrease of the crystal size. Therefore, the crystal size in the crystallization was predominantly determined by the competition between the crystal aggregation and breakage.

• Journal of Korean Society on Water Environment
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• v.25 no.6
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• pp.916-921
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• 2009

This study was aimed to both enhance the fluoride removal and to reduce the phosphorus removal in treating semiconductor wastewater using $Ca(OH)_2$ at low pH so as to facilitate struvite crystallization reaction. The struvite crystallization could be introduced after fluoride removal by retaining the phosphorus source. As the results, the method applied in this study achieved high fluoride removal efficiency (about 91%) with retardation of phosphorus removal at pH 4, compared to conventional methods where the removal of fluoride and phosphorus were done at pH 11. Therefore, the fluoride removal at low pH would contribute to the enhancement of nitrogen and phosphorus removals in a consecutive struvite crystallization reactor. Treatment of semiconductor wastewater at low pH using $Ca(OH)_2$ also had lower (about 20%) water content of precipitated sludge compared to conventional method. As the molar ratio of Ca to F increased the removal efficiencies of fluoride and phosphorus increased. Although the amount of seed dosage didn't affect the removal of fluoride and phosphorus, its increase reduced the water content of precipitated matter. Finally, considering consecutive struvite reaction, the optimum condition for the removal of fluoride and phosphorus was as follow: pH: 4, the molar ratio of Ca:F: 1:1.

• Journal of Korean Society of Water and Wastewater
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• v.21 no.6
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• pp.745-753
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• 2007

By struvite and hydroxyapatite crystallization, was high concentration of nitrogen and phosphorus in wastewater simultaneously. Particularly, removal of nitrogen and phosphate for crystallization have been applied to landfill leachates and animal wastewater. The purpose of this study is to decide the optimum struvite crystallization factors, sequence of $Mg^{2+}$ addition, pH control and the molar ratio of $Mg^{2+}$ over $PO_4^{3-}$. In conclusion, dosage of the magnesium followed by pH control formed magnesium hydroxide, so pH was decreased. Therefore, pH adjustment should followed by after magnesium dosage and then pH should be adjusted to 11. Over pH 10, it was not good for struvite crystallization efficiency by side reaction. Following of the $Mg^{2+}$ and the $PO_4^{3-}$ are dosed excessively, the removal efficiency of the $NH_4^+$ increased. A molar ratio of $Mg^{2+}:NH_4^+:PO_4^{3-}$, 1.3:1:1.3 was the most on effective for $NH_4^+$ removal at pH 9.5. But for the perfect removal $NH_4^+$, it is thought to be that molar ratio should be 2:1:2.