• 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 of Water and Wastewater
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• v.22 no.6
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• pp.641-646
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• 2008

In this research, recovery of high quality organics from excess activated sludge and its potential as a external carbon sources for BNR process was studied. By simultaneous treatment of alkali and ozone, TSS concentration was reduced by 32%, and RBDCOD fraction was increased by 76.2%, and major constitute of produced organic were acetic acid and propionic acid. Also, nitrogen and phosphorus were greatly solubilized. However, because acid-hydrolyzable phosphorus(AHP) was major part of solubilized phosphorus, $NH_4{^+}-N$ and $PO_4{^3}-P$ concentration were insufficient for effective formation of crystal like as MAP(Magnesium Ammonium Phosphate) and hydroxyapatite. By placing BPR reactor before alkali-ozone treatment reactor, $PO_4{^3}-P$ concentration in pretreated sludge was increased by 1.8 times, and improved potential of phosphorus recovery by crystallization. In experiment of crystallization, hydroxyapatite formation was more easily applied than MAP. By hydroxyapatite formation, $SCOD/PO_4-P$ ratio was greatly increased from 32.7 at control to 141.9 at $Ca^{2+}/PO{_4}^{3-}-P$ mole ratio of 2.4. The results based on this study indicated that the proposed system configuration has potential to reduce the excess sludge production, to recover phosphorus in usable forms as well as utilize organics as a external carbon source in BNR process.

• Journal of the Korean Ceramic Society
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• v.36 no.10
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• pp.1087-1093
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• 1999

Bioglass which is one of the surface active bionmaterials has a good biocompatibility but a poor mechanical strength, In the present work therefore two types of fluoride-containing bioglasses were coated on an alumina to improve mechanical strength. Crystallization of the coating layer and the hydroxyapatite formation on the bioactive glass coatings in tris-buffer solution were studied. When bioactive glass coated alumina was heat-treated Na2CaSi3O8 crystal was formed on the layer at lower temperature while wollastonite(CaSIO3) was obtained at higher temperature. Hydroxyapatite forming rate on the coating layer with Na2CaSi3O8 crystal was delayed with SiO2 contents in glass composition. However the hydroxyapatite was developed in 20minutes regardless SiO2 contents when the coating layer crystallized into wollastonite. More amount of P3+ ions were leached out of the coating layer with wollastonite than that with Na2CaSi3O8 crystal while Na+ and Ca2+ ions were leached out more easily from the Na2CaSi3O8 crystal containing coating layer.

• Journal of Korean Society of Water and Wastewater
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• v.31 no.6
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• pp.577-586
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• 2017

One of the major sources causing eutrophication and algal blooms of lakes or streams is phosphorus which comes from point and nonpoint pollution sources. HAP (hydroxyapatite) crystallization using granular alkaline materials can achieve the decrease of phosphorus load from wastewater treatment plants and nonpoint pollution control facilities. In order to induce HAP crystal formation, continuous supply of calcium and hydroxyl ions is required. In this research, considering HAP crystallization, several types of lime-based granular alkaline materials were prepared, and the elution characteristics of calcium and hydroxyl ions of each were analyzed. Also, column tests were performed to verify phosphorus removal efficiencies of granular alkaline materials. Material_1 (gypsum+cement mixed material) achieved the highest pH values in the column tests consistently, also, Material_2 (gypsum+slag mixed material) and Material_3 (calcined limestone material) achieved over pH 9.0 for 240 hours (10 days) and proved the efficiencies of long-term ion supplier for HAP crystallization. In the column tests using Material_3, considerable pH increase and phosphorus removal were carried out according to each linear velocity and filtration depth. T-P removal efficiencies were 87.0, 84.0, 68.0% and those of PO4-P 100.0, 97.0, 80.0% for linear velocity of 1.0, 2.5, 5.0 m/hr respectively. Based on the column test results, the applicability of phosphorus removal processes for small-scale wastewater treatment plants and nonpoint pollution control facilities was found out.

• Journal of the Korean Ceramic Society
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• v.54 no.5
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• pp.395-399
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• 2017

The thermal properties and crystallization behavior of calcium phosphate glass fabricated using eggshell were examined. Nature eggshell has several impurities in the main component of $CaCO_3$. To manufacture calcium phosphate glass, washed eggshell was dissolved in aqua-regia while adding a solution of isopropyl alcohol, D. I. water and phosphoric acid. The calcined precursor was melted at $1000^{\circ}C$, and the glass ($T_g$ : $540^{\circ}C$) was crystallized at $620{\sim}640^{\circ}C$, which temperature range is relatively low compared to the crystallization temperature of other general types of calcium phosphate glass. The calcium phosphate glass using eggshell was successfully crystallized without any additional nucleating agents due to the multiple effects of impurities such as $Fe_2O_3$, $Al_2O_3$, SrO and $SiO_2$ in the eggshell. The main crystalline phase was ${\beta}-Ca(PO_3)_2$ and a biocompatible material, hydroxyapatite, was also observed. The crystallization process was completed under the condition of a holding time of only 1 h at the low temperature.

• Proceedings of the Korea Water Resources Association Conference
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• 2022.05a
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• pp.401-401
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• 2022

우리나라 대규모 하수처리장에 상용화되어있는 응집공정의 운영상 난점을 극복하고자 대체공정으로 고안된 인 결정여과공정(HCF, Hydroxyapatite Crystallization-Filtration process)의 pilot plant를 구축하고 부산슬러지의 자원화를 위해 그 특성을 검토하였다. 기존의 hydroxyapatite(HAP) 결정화공정 내 탈탄산(decarbonation) 단계를 생략하는 HCF공정의 경우에 고농도의 Ca²⁺ 주입과 처리수내 탄산염으로 인해 HAP을 포함하는 석회계 슬러지가 발생하는데, 이는 산성화된 토양의 개량제(중화제)로 널리 사용될 수 있다. 본 연구를 위해 경기도 I하수처리장 2차침전지 후단에 구축된 처리용량 27.1 - 135.6 m³/day HCF pilot plant의 전처리 조건은 pH 10.0 - 11.0, Ca²⁺ 농도 80 mg/L이었다. 결정여과조는 선속도 1.0 - 5.0 m/hr, 상향류로 운전되며, 여재는 2.0 - 3.0 mm의 석회석 모래를 충전하였다. 역세척은 중앙에 Air lifting pipe를 설치하여 역세척수가 처리수와 분리배출되도록 설계하였고, 침전시켜 역세척 슬러지를 회수하였다. 처리수의 평균 T-P, PO₄-P 및 SS는 각각 0.05, 0.04, 1.1 mg/L으로 모든 항목에서 방류수 수질기준 이하로 안정적으로 유출되었다. 회수된 HCF 슬러지는 SEM-EDX, XRD, FT-IR을 활용하여 그 특성을 분석하였다. SEM-EDX로 분석된 슬러지의 원자분율은 CaCO₃ 또는 HAP으로 추측되었다. 또한, XRD spectrum 분석결과, 슬러지의 주요 구성성분은 calcite, HAP, phosphoric acid(H₃PO₄) 및 brusite로 나타났다. FT-IR 분석결과, 슬러지는 대부분 인산염 및 탄산염의 무기물로 구성되어 있으며, 유입수의 인 농도가 높을수록 슬러지 내 HAP의 함량이 calcite보다 높은 것으로 나타났다. 고농도의 Ca²⁺을 주입하여 탈탄산단계를 생략한 HCF의 부산슬러지는 HAP 이외에도 CaCO₃와 칼슘-인 화합물로 구성되어 있는 것으로 나타났다. 하수 인 고도처리를 위한 HCF공정의 하수처리시설 인 고도처리 적용이 검증되었으며, 부산슬러지를 산성화된 토양의 개량제(중화제) 또는 비료로서의 재활용 및 자원화 가능성이 시사되었다.

• 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.

• Journal of Korean Society on Water Environment
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• v.25 no.4
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• pp.515-521
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• 2009

In this study, the applicability of $CaCO_3$ as a seed material for crystallization reaction was tested. $CaCO_3$ was ground to lesser than 425 mesh and was made to media mixed with binder. Batch experiment was to investigate the ${PO_4}^{3-}-P$ removal efficiency of different parameters such as $CaCO_3$ dosage and binder ratio, size, type and mass of media. In addition, the effect of phosphorus removal from wastewater was tested using a lab-scaled crystallization reactor. At the results of the batch test, phosphorus removals were improved with increasing $CaCO_3$ dosage and media mass but were decreased with increasing media size. Moreover, phosphorus removals were influenced by specific surface area but media type. The average T-P and ${PO_4}^{3-}-P$ removal efficiency in a lab-scaled crystallization reactor with $CaCO_3$ media for wastewater were shown to be 60.2% and 60.3% for 18 days of operation time.

• Journal of the Korean Ceramic Society
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• v.52 no.3
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• pp.204-208
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• 2015

Synthesis of hydroxyapatite (HA) was attempted through a room-temperature reaction of calcined eggshell with phosphoric acid. Ball-milled, calcined eggshell powder, which has a specific surface area of $31.6m^2/g$, was mixed with various concentrations of phosphoric acid at room temperature. The mixtures showed high reactivity and a vigorous exothermic reaction ; the reacted samples showed both $Ca(OH)_2$ and $CaHPO_4$ crystal phases. After heating at temperatures above $400^{\circ}C$, an HA crystal phase was observed in all samples. The calcined eggshell showed a pure CaO single phase, while the $Ca(OH)_2$ phase was only observed in the wet, ball-milled calcined powder. The degree of formation of the HA crystal phase increased as the phosphoric acid concentration and the heating temperature were increased. A mixture with 50 wt% phosphoric acid concentration showed a well-developed HA crystal phase after heat treatment at $800^{\circ}C$, while the formation of a more intensive amorphous phase was observed in the products of the room-temperature reaction.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.7 no.4
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• pp.709-714
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• 2006

The propose of this study was to investigate the feasibility of using waste lime core to remove phosphorus from wastewater in continuous flow reaction. The phosphorus was found to be removed from municipal wastewater by hydroxyapatite crystallization and precipation. Waste lime core size 1, 2 showed phosphorus removal rate of about 90% during early 11 hrs of run time. In addition, breakpoint time was decreased by increased inflow rate regardless of waste lime core size.