• Journal of Korean Society of Environmental Engineers
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• v.32 no.9
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• pp.879-886
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• 2010

This study investigated the removal characteristics of highly concentrated $NH_4$-N and $PO_4$-P by struvite crystallization using converter slag as a seed crystal. The optimal pH range for removal and recovery of $NH_4$-N and $PO_4$-P by struvite crystallization was measured to be 8.0~8.75, in which total removal efficiencies for $NH_4$-N and $PO_4$-P by struvite precipitation and crystallization were 34.3~61.0% and 91.0~96.2%, respectively. The maximum removal efficiencies for $NH_4$-N and $PO_4$-P by struvite crystallization were 29.4% at pH 8.5 and 65.1% at pH 8.0, respectively. The removal efficiency of $NH_4$-N by struvite crystallization decreased with increasing calcium ion concentration. The analysis results of SEM, EDS and XRD exhibited that $NH_4$-N and $PO_4$-P in meta-stable region of struvite crystallization could be eliminated through formation of magnesium ammonia phosphate (MAP) and hydroxyapatite (HAp) on seed crystals by struvite precipitation and crystallization.

• 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.

• Asian-Australasian Journal of Animal Sciences
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• v.24 no.12
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• pp.1699-1705
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• 2011

Magnesium ammonium phosphate (MAP) was recovered from swine wastewater and the feasibility of reutilizing it as a slowly-releasing fertilizer was evaluated. Maize growth was investigated with normal and high application rates of MAP and a fused super phosphate (FSP) fertilizer. A total of 5 treatments ($T_0$ = control, $T_1$ = MAP based on 30 kg P $ha^{-1}$, $T_2$ = FSP based on 30 kg P $ha^{-1}$+urea equivalent to nitrogen of MAP applied in $T_1$, $T_3$ = MAP based on 40 kg P $ha^{-1}$, $T_4$ = FSP based on 40 kg P $ha^{-1}$+urea equivalent to nitrogen of MAP applied in $T_3$) were arranged with 3 replications. In the case of height and circumference, significant differences were found between controls and treated maize plants (p<0.01). However, no statistical differences were found between MAP- and FSP-urea treated maize. Leaf area and green biomass yield were significantly (p<0.01) higher in the treated group than control. Leaf area was also found significantly higher (p<0.01) in the higher MAP- treated group (2,374 $cm^2$ $plant^{-1}$) than other treatments. $N_2O$ emission was found to be lower in MAP treated soil than that from FSP-urea treated soil, which might be due to the slow releasing pattern of MAP. It could be assumed from the results that MAP would be an eco-friendly sustainable fertilizer source for crop production.

• Journal of Animal Science and Technology
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• v.51 no.4
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• pp.337-342
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• 2009

The feasibility of reutilization of magnesium ammonium phosphate (MAP) or struvite slurry recovered from the process through microwave irradiation was studied in this experiment. For this purpose, 4 different operations were performed with or without Mg source addition and different levels of MAP recycled in a batch reactor. Dissolution rate of MAP, ${NH_4}^+$ elimination pattern and physicochemical changes of MAP during microwave irradiation were also studied. The result showed that only 33% orthophosphate ($PO_4-P$) and 27% $NH_4-N$ removal occurred without adding any external Mg source (run A), whereas 87% $PO_4-P$ and 40% $NH_4-N$ removed when 1.0 M ratio of $MgCl_2$ (run B) was added based on $PO_4-P$ in influent. Although the addition of 1.0 molar ratio of microwave irradiated MAP (Run C) removed lower $PO_4-P$ and $NH_4-N$ than 1.0 M $MgCl_2$ (run B), $PO_4-P$ removal was double when compared with no Mg addition (run A). Addition of half MAP and half $MgCl_2$ (run D) showed the similar removal efficiency (88% $PO_4-P$ and 35% $NH_4-N$) with sole $MgCl_2$ addition (run B). Based on these results, the reutilization of MAP irradiated by microwave would be a feasible way to enhance the removal efficiencies of N and P, as well as curtail the Mg chemical usage. Track study showed that $NH_4-N$ gradually increased at initial stage of microwave irradiation of MAP, and then started eliminating from liquor as temperature increased over $45^{\circ}C$. Dissolution rate of ${PO_4}^{-3}$ during microwave irradiation was proportional to the initial MAP concentration, having $0.0091x^{0.6373}$ mg/sec. It was found from the scanning electron microscope (SEM) study that physical structure of MAP crystal started breaking down into small cube granules within very short time by electromagnetic vibration force during microwave irradiation and then gradually melted down into solution.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.4
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• pp.599-607
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• 2000

In this research, ${NH_4}^+-N$ and ${PO_4}^{3-}-P$ in wastewater were removed by crystallization. Nitrogen and phosphate have been regarded as key nutrients in the eutrophication of rivers and lakes. Struvite, $MgNH_4PO_4{\cdot}6H_2O$, is insoluble in alkaline solutions. Fertilizer industry wastewater contains organic and nitrogen concentration of 330 mg/L and 550 mg/L, respectively. Nitrogen in this wastewater cannot be treated by conventional biological treatment without physicochemical pretreatment, because nitrogen concentration is relatively high compared to organic concentration. Magnesium ions used in this study were from bittern and commercial magnesium salts of $MgCl_2$ and $Mg(OH)_2$. Bittern obtained as a by-product of seasalt manufacture contains $8,000mg\;Ca^{2+}/L$ and $32,000mg\;Mg^{2+}/L$. Optimum initial pH was 10.5~11.0 and the reaction was complete or done in 2 min. Nitrogen removal efficiency using bittern, $MgCl_2 $ and $Mg(OH)_2$ (as source of $Mg^{2+}$) was 71 %, 81% and 83%. respectively. Phosphate removal efficiency was 99%, 98% and 93%, respectively. Therefore, bittern, $MgCl_2$ and $Mg(OH)_2$ can be efficiently used as $Mg^{2+}$ source for crystallization of nitrogen and phosphate. However, bittern is economically favorable $Mg^{2+}$ source for removing nitrogen and phosphate in wastewater.

• Journal of Animal Science and Technology
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• v.45 no.4
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• pp.641-648
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• 2003

In a batch mode treatment process, which electrolyzes the wastewater after derivation of N-P crystal formation and recovery, the characteristics of pollutant removal induced with the changes of loading rate and hydraulic retention time were studied. $MgCl_2$ was used as Mg source for the formation of struvite and the molar ratio of $MgCl_2$ to $PO_4^{3-}$ in influent was 1.3. When analyzing the average treatment efficiencies and removal characteristics obtained from four separate operations (Run I, II, III, IV), removal efficiencies of PO43- was not function of its loading rate. Under a condition of sufficient aeration and Mg source provided, over 88% of $PO_4^{3-}$ was eliminated by the formation of MAP without any pH adjustment, in spite of loading rate variation. An optimum-loading rate of NH4-N to achieve high removal efficiency was approximately $100g/m^3/d$. Below that loading rate, the removal of NH4-N was proportional to the loading rate into the system, and hence stable and high removal efficiency, over 90%, was achieved. However, when the loading rate increased over that rate, removal efficiency began to drop and fluctuate. Removal efficiency of TOCs was dependant upon the hydraulic retention time ($r^2$=0.97), not upon the loading rate. Stable and high color removal (94%) was obtained with 2 days of HRT in electrolysis reactor.

• Journal of Korean Society of Water and Wastewater
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• v.21 no.3
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• pp.273-278
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• 2007

Modern society has moved from a phosphorus recycling loop, where animal manure and human wastes were spread on farming land to recycle nutrients, to a once-through system, where phosphates are extracted from mined, non-renewable phosphate rock and end up either in landfill(sewage sludge, incinerator ash) or in surface waters. In this research, crystallization of nitrogen and phosphate with natural sources of $Mg^{2+}$ in synthetic water was tested. The operational parameters of pH, mixing time, and the magnesium molar ratio were investigated to find optimal conditions of the MAP precipitation using synthetic wastewater. The removal efficiency of phosphate increased with pH up to 11. By MAP precipitaiton of the synthetic waste water, 94% of the phosphate were eliminated at pH 11. It was found that at least 10 minutes mixing time was required and 20 minutes mixing time was recommended for efficient phosphate removal. High efficiency removal of phosphate was possible when the magnesium molar ratio was 1.0~2.0. The comparative study of different magnesium sources showed that coagulants (PAC) was the more efficient sources than only magnesium. The result showed that 97% of phosphate removal. In conclusion, coagulants (PAC) induced crystallization of struvite and hydroxyapatite was shown to be a technically viable process that could prove cost effective for removing phosphate in wastewater.

• Journal of Animal Science and Technology
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• v.51 no.3
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• pp.249-254
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• 2009

The effect of Mg supplement on the composting of swine manure and the formation of $MgNH_4PO_46H_2O$ (MAP) crystal during composting were examined. Mg source was added at a rate of 1.2 molar ratios to soluble phosphate ($PO_4$) level in swine manure. The temperature profiles and final compost qualities revealed that the Mg source addition didn't retard the decomposition of organic matters. As the added Mg reacted with $NH_4$ and $PO_4$ in manure, creating MAP crystal, the $NH_4$ level was reduced, and this was resulted in low nitrogen lose during the composting. The phosphate level was also decreased with the addition of Mg source, and hence the ratio of orthophosphate to total phosphate (OP/TP) in the final compost was lowered. Therefore, it was assured that supplement of Mg source into the composting materials could enhance the quality of compost by preserving nourishment and converting it into a slowly releasing fertilizer. X-Ray diffraction examination of the final compost showed that a distinct MAP crystal was formed during the composting, and the crystal mainly existed with the compost particle size less than 2.8 mm and over 2/3 of nourishment of the final compost was found in those particles.

• Proceedings of the KAIS Fall Conference
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• 2007.11a
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• pp.305-307
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• 2007

Struvite(MAP) 및 hydroxyapatite(HAP) 결정화로 질소 및 인을 제거하기 위한 최적조건을 평가하기 위한 실험을 실시하였으며, $Mg^{2+}$, $NH_4^+$, $PO_4^{3-}$ 및 $Ca^{2+}$용액을 이용하여 인공폐수를 조제하였으며 각 이온의 몰비 조건을 1:1:1에서 실험을 수행하였다. $Ca^{2+}$ 및 $PO_4^{3-}$를 이용한 HAP 결정화는 알칼리조건의 pH 범위에서는 pH에 큰영향을 받지 않고 HAP가 형성되었으며, MAP 및 HAP 동시 결정화를 위한 실험에서는 pH가 증가하면서 $NH_4^+$, $PO_4^{3-}$ 제거효율은 감소하며 $Ca^{2+}$ 및 $Mg^{2+}$는 모든 pH에서 99% 이상 제거되었다. 폐수중에 $Ca^{2+}$이 포함되어 있다면 pH 9.5에서 $Mg^{2+}:NH_4^+:PO_4^{3-}:Ca^{2+}$는 1.2:1.0:1.2:2.0의 몰비로 존재했을 때 MAP 및 HAP 생성 최적조건인 것으로 나타났다. 그러나 pH가 10이상이 되면 부반응으로 인해 각종 무정형 결정체가 생성되므로 MAP 생성을 위해서는 pH 9.5로 운영을 하는 것이 가장 바람직하다.

• Journal of Animal Science and Technology
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• v.51 no.1
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• pp.75-80
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• 2009

Composition changes of swine manure and the effects on MAP ($MgNH_4PO_46H_2O$) crystallization by microwave irradiation were examined. The concentration of ${PO_4}^{3-}$ was increased within a fixed period of time and then decreased, but $NH_4$-N was reduced continuously during microwave irradiation. Concentration of ${PO_4}^{3-}$ was started to reduce just from the point of foam formation during microwave irradiation, and the temperature at that time was always $49^{\circ}C$ irrespectively to microwave irradiation rate. Inorganic carbon was reduced with microwave irradiation, but soluble organic carbon (TOCs) was increased proportionally. Crystallization rate under conditions of non-microwave irradiation, irradiation up to $93^{\circ}C$ and $48^{\circ}C$ was 87.8%, 87.3% and 98.5%, respectively, showing 10% enhancement when irradiated up to $48^{\circ}C$. However, removal efficiency of ammonia nitrogen was proportional to the microwave irradiation rate or duration, obtaining 2.5%, 4.5% and 10.2%, respectively. Based on these results, it would be a useful strategy to irradiate microwave up to $49^{\circ}C$ to enhance MAP crystallization rate by changing the ionic pattern of nutrients in the manure. Meanwhile, provision of enough microwave irradiation rate might be needed to achieve high $NH_4$-N removal.