Ammonium phosphate as promised hydrogen storage material

Barakat, N.A.M.,Ahmed, E.,Abdelkareem, M.A.,Farrag, T.E.,Al-Meer, S.,Al-Deyab, S.,Elsaid, K.,Nassar, M.M. Pergamon Press ; Elsevier Science Ltd 2015 International journal of hydrogen energy Vol.40 No.32

Most of the reported hydrogen storage materials are either expensive or based on synthetically complicated compounds. Ammonium phosphates are cheap and available product; it is being used as fertilizer. These compounds could be utilized as hydrogen storage materials. Stoichiometrically, mono-, di- and tri-ammonium phosphate can lead to evolve 3.875, 7.867 and 11.903 hydrogen equivalent, respectively. Using Pt/C (20 wt %) leads to produce 17.28, 11.35 and 10.15% from the equivalent hydrogen in the mono-, di- and tri-ammonium phosphate, respectively. Analyzing the obtained gases by GC confirms evolution of pure hydrogen. Moreover, ion chromatography detects and ions in the liquid which indicates hydrolysis of the ammonium phosphate. Ni/C and Co/C NPs can be exploited as catalysts; Ni/C containing 20 wt% metal reveals comparable results to Pt/C. Overall, this study opens promising avenue to develop new catalysts to enhance the hydrolysis of ammonium phosphate to produce hydrogen. Comparing to the reported hydrogen storage materials, ammonium phosphates possess comparable hydrogen content 97.28, 118.3 and 115.72 kg/m<SUP>3</SUP> for mono-, di- and tri-ammonium phosphate, respectively which is very close to the MgH<SUB>2</SUB> (115.5 kg/m<SUP>3</SUP>) and not so far from ammonia borane (148.2 kg/m<SUP>3</SUP>). However, in contrast to these compounds, hydrogen can be released from the introduced storage materials by hydrolysis only using the proper catalyst. Furthermore, the hydrolysis process results in producing different acids; nitrous, nitric and phosphoric acid which should be considered in the reactor construction precautions.

MAP 결정화 적용을 위한 잉여슬러지의 인 및 암모니아의 거동 특성

오경수,김장호,박기태,박대원,김형수 대한상하수도학회 2021 상하수도학회지 Vol.35 No.1

Phosphorus is a vital resource for sustaining agriculture and nutrition, but a limited non-renewable resource. This paper aimed to derive the behavioral characteristics of phosphate, ammonia and metals of waste activated sludge (WAS) by process of activated sludge for application of magnesium ammonium phosphate (MAP) crystallization system. WAS used in the experiment was obtained in each activated sludge process, such as A2O, MLE (Modified Ludzack Ettinger), and oxidation ditch. WAS was analyzed for the behavior of phosphate ammonia and metallic materials according to pH and microwave conditions. As a result of evaluating the phosphate, nitrogen, and metal material behavior of each WAS according to the microwave and pH conditions, the release path of the polyphosphate contained in the cells into the phosphate form by analyzing the phosphorus release rate of the excess sludge of various microbial community structures was confirmed. These results are believed to be able to estimate the origin of the released phosphate. In addition, the evaluation of the behavior of phosphate, nitrogen, and metal substances according to microwave heating and pH for each activated sludge process was carried out in a batch test, and the amount of phosphate released was in the order of A2O, MLE, and oxidation dich processes. These results confirmed that phosphate emission was closely related to the dominance of polyphosphate-accumulating microorganisms, whereas in the case of ammonia, it was found that the composition of extracellular polymers and the characteristics of influent water were more affected than the dominance of specific microorganisms. The amount of metal released had a direct effect on the reaction pH condition, and the amount of metal ions released from the WAS released under alkaline conditions formed a metal compound with phosphate and ammonia, resulting in less release.

Immobilization of ammonium and phosphate in aqueous solution by zeolites synthesized from fly ashes with different compositions

Xiaodong Ji,Mulan Zhang,Yujie Wang,Yichu Song,Yaoyao Ke,Yunqi Wang 한국공업화학회 2015 Journal of Industrial and Engineering Chemistry Vol.22 No.-

Immobilization of ammonium and phosphate by zeolites synthesized from low-calcium (LC-Z) and highcalcium (HC-Z) fly ashes is studied. LC-Z has higher ammonium immobilization capacity while HC-Z has better performance in phosphate uptake. As part of Ca2+ released from HC-Z compete with ammonium the exchangeable sites in LC-Z, LC-Z can affect phosphate immobilization of HC-Z, and HC-Z also lowers ammonium uptake of LC-Z. Separate dosing of LC-Z and HC-Z, i.e., first LC-Z and then HC-Z, is proved better than mixed dosing at simultaneous immobilization of ammonium and phosphate. The effect parameters for phosphate and ammonium immobilization of LTH-Z are investigated.

H12MDI를 이용한 수분산 폴리우레탄 수지의 합성 및 ammonium dihydrogen phosphate에 의한 물성변화에 관한 연구

이주엽,남상성 한국유화학회 2014 한국응용과학기술학회지 Vol.31 No.1

본 연구에서는 H12MDI(4,4'-methylene dicyclohexyl diisocyanate)를 이용한 수분산 폴리우레탄 수지를 합성한 다음 방염제로 활용이 되고 있는 2-인산암모늄(ammonium dihydrogen phosphate) 수용액을 수분산 우레탄 수지에 적하량을 점차 증가시켜 변화하는 물성을 피혁(leather)에 표면 코팅처리된 상태 및 열풍 건조시킨 필름의 물성을 측정 분석하였다. 내용제성 측정 결과 높은 내용제성 물성을 지닌 폴리우레탄 수지에 2-인산암모늄의 함량에 따른 물성적 변화는 크게 없었으며 모두 높은 물성치를 나타내었다. 인장 강도 측정치에서는 폴리우레탄 단독 필름의 측정치가 3.114 kgf/㎟로 가장 높은 수치를 나타내었으며, 2-인산암모늄의 합량이 제일 높은 DPU-AD3가 가장 낮은 인장력 2.510 kgf/㎟을 나타내었다. 또한 내마모도 측정에서는 DPU가 제일 높은 50.50 ㎎.loss로 우수한 물성변화를 나타내었고, 연실율의 경우역시 우레탄 단독 코팅인 DPU가 602 %로 가장 높은 수치를 나타내었다. DSC측정결과 2-인산암모늄의 함유가 높은 DPU-AD3이 Tm 값이 384℃로 고온에서 가장 안정한 수치를 나타내었다. For this research, prepared ammonium dihydrogen phosphate aqueous solution and polyurethane dispersion. Use these resin, this article has been analyzed about change of mechanical properties by increasing amount of ammonium dihydrogen phosphate aqueous solution in polyurethan resin on coated leather and dried film. According to measure data for solvent resistance, DPU(polyurethane dispersion) resin and DPU-AD1, D2, D3(samples of polyurethaneresin with ammonium dihydrogen phosphate aqueous solution) had good property. As known in the results, increase of ammonium dihydrogen phosphate constant did not influence to big change of polyurethane resin properties. As test of tensile strength, DPU had highest tensile characteristic(3.114 kgf/㎟) and DPU-AD3 had lowest tensile characteristic(2.510 kgf/㎟). As same as tensile characteristic, abrasion test determined DPU(50.5 ㎎.loss) had highest properties. In elongation case, DPU had best properties(602 %) in this experiment.

제올라이트와 슬래그계 물질을 이용한 암모늄, 카드뮴, 인산염의 동시 제거능 평가

김용우(Yong-Woo Kim),우희수(Hee-Soo Woo),박희수(Hee-Soo Park),이광헌(Gwanghun Lee),오명학(Myounghak Oh),박준범(Junboum Park) 한국토목섬유학회 2011 한국지반신소재학회 학술발표회 Vol.2011 No.4

The reactive vertical drain could be applied to man-made island constructed by dredged materials and waste landfill. However, these materials could be considered as main reason of multiple contamination such as ammonium, cadmium and phosphate. Therefore, the reactive vertical drain containing various materials is necessary to remediate many kinds of contamination mentioned above simultaneously. In this study, a series of batch test which consists of two process is performed. Zeolite, basic oxygen furnace slag and blast furnace slag are used as reactive materials. Ammonium, cadmium and phosphate are targeted for removal. As a result, zeolite-basic oxygen furnace slag or blast furnace slag sequence batch test shows the best efficiency for multiple contamination removal.

A Comparative Study on the Use of Seawater and Sea Salt in Nutrient Elimination

김우항,Cainglet, Annaliza Pabrua,Kim, Woo-Hang 해양환경안전학회 2016 海洋環境安全學會誌 Vol.22 No.7

An excess in the nutrients such as nitrogen and phosphate leads to a phenomenon called eutrophication. In order to avoid this, numerous methods have been used to remove excess nutrients in the water. In this study, the use of a chemical method was assessed through the formation of magnesium ammonium phosphate. The difference in the removal efficiency of seawater and sea salt solution as primary sources of $Mg^{2+}$ ions and $Ca^{2+}$ ions for the formation of magnesium ammonium phosphate (MAP) and hydroxyapatite (HAP) respectively, were observed, taking into account the changes in pH and concentration. The results showed that seawater removed about 90 % phosphate and less than 50 % ammonia in sewage water condition, whereas the sea salt solution removed almost 90 % phosphate and 70 % ammonia in solution at pH 9 and 10 mM concentration of sea salt which further increases as the optimum ${Mg/PO_4}^{3-}$, ${NH_4}^+$ ratio reaches 2. The difference in the removal efficiency of seawater and sea salt was due to the fact that the set-ups were prepared in different conditions. This study suggests that both seawater and sea salt can be used to remove nutrients from the water. The relatively higher removal of phosphate can be explained by the formation of HAP from free $Ca^{2+}$ ions initially present in seawater and sea salt solution. 부영양화를 일으키는 대표적인 영양물질인 질소와 인을 제거하기 위하여 많은 연구들이 진행되어오고 있다. 본 연구에서는 질소와 인을 제거하기 위하여 해수 및 해수염에 존재하는 마그네슘과 칼슘을 사용하여 스트루바이트와 수산화인회석을 만들어 침전을 시켰다. 실험의 목적은 해수와 해수염을 사용하여 pH와 농도의 변화에 따른 영양염의 제거율을 비교평가 하였다. 하수의 실험조건에서 해수를 사용한 결과 인의 제거율은 90 %, 질소의 제거율은 50 %로 나타났다. 또한 pH 9, 질소와 인의 농도 10 mM, ${Mg/PO_4}^{3-}$, ${NH_4}^+$의 비율 2의 조건에서 해수염을 사용하여 실험한 결과 질소의 제거율은 90 %, 인의 제거율은 70 %로 나타났다. 상대적으로 인의 제거율이 높은 이유는 해수를 사용한 경우 질소와 인의 몰 농도의 차이에서 비롯되었으며, 해수염을 사용한 경우 해수에 포함된 칼슘이 인과 반응하여 수산화인회석으로 침전 제거되었다고 할 수 있다. 수중의 질소와 인을 제거를 위하여 해수와 해수염을 사용한 결과 높은 제거율을 나타내었다.

침전반응들에 의한 잉크 폐액에서 Ca<SUP>2+</SUP>와 Mg<SUP>2+</SUP>제거에 관한 연구

이승석(Seung-Seok Lee) 한국환경관리학회 2013 環境管理學會誌 Vol.19 No.3

유효 염료 5~10%, Ca<SUP>2+</SUP> 이온 40~150 ppm 그리고 Mg<SUP>2+</SUP> 이온 10~50 ppm을 함유한 잉크 폐액들을 재사용하기 위하여 잉크 품질을 저하시키는 Ca<SUP>2+</SUP> 와 Mg<SUP>2+</SUP> 이온들을 제거하고자 다음과 같은 3가지 범주의 실험을 수행하였다. 1)옥살산암모늄과 인산암모늄을 사용한 이온화합물에 의한 침전. 2)EDTA-2Na와 EDTA-4Na를 사용한 킬레이트 반응. 3)피트산과 이소프로필아민을 사용한 산과 염기에 의한 제거 반응. 반응은 70℃에서 한 시간 동안 진행하였고 침전된 화합물 제거 후 ICP를 이용하여 액상 내 잔류 이온 농도를 분석하였다. 실험 결과 옥살산암모늄과 인산암모늄을 사용한 침전반응과과 이소프로필 아민이 폐액 내 Ca<SUP>2+</SUP>와 Mg<SUP>2+</SUP> 이온들 제거에 우수한 성능을 나타내었다. 특히 옥살산암모늄은 99.2% 이상의 Ca<SUP>2+</SUP> 제거 효율을 나타내었고 이소프로필아민은 최고 93%의 Mg<SUP>2+</SUP> 제거 효율을 나타내어 이러한 결과를 바탕으로 염료 함유 폐액의 재사용 가능성을 제시하고자 한다. Following precipitation reactions are carried out to remove Ca<SUP>2+</SUP> and Mg<SUP>2+</SUP> ions from waste ink liquids which contain 5~10% available dyes, 40~150ppm of Ca<SUP>2+</SUP> and 10~50ppm of Mg<SUP>2+</SUP> ion. 1)Precipitation reactions by ionic compounds using ammonium oxalate and ammonium phosphate. 2)Chelating reactions using EDTA-2Na and EDTA-4Na. 3)Precipitation reactions using phytic acid and isopropylamine. Waste ink liquids can be reused if Ca<SUP>2+</SUP> and Mg<SUP>2+</SUP> ions which cause deterioration of ink quality are removed. All reactions are performed at 70℃ for 1 hour and precipitates are filtered by glass fiber filter and residual ions are analyzed by ICP. The experimental results show that precipitation reactions using ammonium oxalate, ammonium phosphate and isopropylamine showed relative good removal efficiency. Among the various reagents, the most effective Ca<SUP>2+</SUP> removing agent is ammonium oxalate which removed over than 99.2% of Ca<SUP>2+</SUP> ions. In the case of Mg<SUP>2+</SUP> ions, the most effective removing agent is isopropylamine which removed up to 93%.

Ultrasonic Pre-treatment for Enhanced Phosphorus Resource Recovery from Livestock Manure through MAP Synthesis

Min-Sung Yu,Daegi Kim,Kyung Jin Min,Kwanyong Lee,Ki Young Park 한국폐기물자원순환학회 2015 한국폐기물자원순환학회 학술대회 Vol.2015 No.05

In this study, enhancement of phosphorus and nitrogen recovery efficiency from livestock manure through Magnesium Ammonium Phosphate (MAP) crystallization method has been suggested as an alternative to solve the problems of the existing phosphorus resource recovery method. It can become a useful fertilizer. This study focused on improvement of phosphorus resource recovery by changing energy density of ultrasonic dose for MAP crystallization. Solubilization rate (as phosphate/phosphorus) of phosphorus in livestock manure was measured by ultrasonic treatment. The energy density range of 100-50,000 of ultrasonic dose was determined. Optimal ultrasonic energy density was 1,000 dose as 64.5% of phosphate ratio. However, when the higher than 1,000 dose of ultrasonic energy density did not more improve phosphate solubilization ratio. Consequently, when use ultrasonic treatment at 1,000 dose of energy density, the phosphorus could recover approximately 65% from livestock manure by MAP crystallization. Moreover, this MAP becomes more valuable due to its nature as a slow-release fertilizer.

Ultrasonic Pre-treatment for Enhanced Phosphorus Resource Recovery from Livestock Manure through MAP Synthesis

( Min-sung Yu ),( Kyung Jin Min ),( Daegi Kim ),( Kwanyong Lee ),( Ki Young Park ) 한국폐기물자원순환학회(구 한국폐기물학회) 2015 한국폐기물자원순환학회 춘계학술발표논문집 Vol.2015 No.-

In this study, enhancement of phosphorus and nitrogen recovery efficiency from livestock manure through Magnesium Ammonium Phosphate (MAP) crystallization method has been suggested as an alternative to solve the problems of the existing phosphorus resource recovery method. It can become a useful fertilizer. This study focused on improvement of phosphorus resource recovery by changing energy density of ultrasonic dose for MAP crystallization. Solubilization rate (as phosphate/phosphorus) of phosphorus in livestock manure was measured by ultrasonic treatment. The energy density range of 100-50,000 of ultrasonic dose was determined. Optimal ultrasonic energy density was 1,000 dose as 64.5% of phosphate ratio. However, when the higher than 1,000 dose of ultrasonic energy density did not more improve phosphate solubilization ratio. Consequently, when use ultrasonic treatment at 1,000 dose of energy density, the phosphorus could recover approximately 65% from livestock manure by MAP crystallization. Moreover, this MAP becomes more valuable due to its nature as a slow-release fertilizer.

혐기성 회분식 배양에서 양돈폐수의 NH_4-Nitrogen이 혐기성 미생물에 미치는 영향

김연옥 한국산업미생물학회 1998 한국미생물·생명공학회지 Vol.26 No.2

본 연구에서는 양돈폐수의 생물학적 처리의 난점 중 하나인 NH_4-N이 혐기성 미생물에 미치는 영향을 조사하기 위해 폐수를 여러가지 비율로 희석하여 혐기성 회분식 배양을 시도하였으며 COD 제거율과 NH_4-N의 농도를 측정 비교하였다. 또한 MgO를 첨가하여 폐수내의 NH_4-N를 MgNH_4PO_4·6H_2O의 결정체로 형성시킨 후 침전 제거하고 같은 조건에서 배양하였다. 3개월 이상 원폐수에서 적응된 master culture는 75%의 폐수와 25%의 희석수에서 빠른 COD 제거율을 보였으며, MAP법으로 NH4-H를 60%제거한 폐수에서는 200시간 후 80%이상의 COD 제거율을 보였다. 같은 조건에서 NH_4-N를 함유하고 있는 폐수는 50%정도의 COD 제거율을 보여, MAP법으로 NH_4-N를 제거한 폐수의 협기성소화가 월등함을 알 수 있다. 특히 중효한 결과는 NH_4-N 농도가 협기성 미생물에 미치는 영향보다는 C:N의 비율이 2 이하 일때 치명적인 영향을 줌을 규명하였으며 MAP법에 의해 형성된 struvit는 혐기성 미생물에 독성 영향을 주지않음을 알수 있었다. This study presents the influence of ammonium-nitrogen on microorganisms in swine wastewater. For the anaerobic batch fermentation, two different methods were used. One is the dilution of wastewater with water. The other method is the elimination of ammonium-nitrogen from the wastewater. By addition of MgO into wastewater, non-soluble crystall was formed under alkaline condition as MgNH_4PO_46H_2O (MAP). The master culture was adapted in swine wastewater for more than 3 months, in water-dilution method, the dilution of wastewater with 25% water gave us the best result in efficiency of COD removal. Two hundred hours later MAP-treated wastewater showed the efficiency of the COD removal more than 80%. Under same condition obtained none MAP-treated wastewater about 50%. MAP treatment carried out the very effective anaerobic digestion with swine wastewater. The important result in this study is that the low ratio of C:N influenced on anaerobic microorganisms more than high concentration of ammonium nitrogen in swine wastewater. The struvite for the crystallforming has no toxic effect on methanogenic bacteria.