• Journal of Korean Society of Environmental Engineers
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• v.38 no.11
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• pp.603-610
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• 2016

This work studies the synthesis of birnessite (${\delta}-MnO_2$), a catalyst of oxidative-coupling reactions, from the powder of spent alkaline manganese batteries (SABP, <8 mesh) and evaluate its reactivity for 1-naphthol (1-NP) removals. Manganese oxides using commercial reagents ($MnSO_4$, $MnCl_2$) and the acid birnessite (A-Bir) by McKenzie method were also synthesized, and their crystallinity and reactivity for 1-NP were compared with one another. 96% Mn and 98% Zn were extracted from SABP by acid leaching at the condition of solid/liquid (S/L) ratio 1:10 in $1.0M\;H_2SO_4+10.5%\;H_2O_2$ at $60^{\circ}C$. From the acid leaching solution, 69% (at pH 8) and 94.3% (pH>13) of Mn were separated by hydroxide precipitation. Optimal OH/Mn mixing ratio (mol/mol) for the manganese oxide (MO) synthesis by alkaline (NaOH) hydrothermal techniques was 6.0. Under this condition, the best 1-NP removal efficiency was observed and XRD analysis confirmed that the MOs are corresponding to birnessite. Kinetic constants (k, at pH 6) for the 1-NP removals of the birnessites obtained from Mn recovered at pH 8 (${Mn^{2+}}_{(aq)}$) and pH>13 ($Mn(OH)_{2(s)}$) are 0.112 and $0.106min^{-1}$, respectively, which are similar to that from $MnSO_4$ reagent ($0.117min^{-1}$). The results indicated that the birnessite prepared from the SABP as a raw material could be used as an oxidative-coupling catalyst for removals of trace phenolic compounds in soil and water, and propose the recycle scheme of SAB for the birnessite synthesis.

• Resources Recycling
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• v.9 no.1
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• pp.63-69
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• 2000

Ferromanganese dust is an oxide substance of Mn. If imprities are removed and oxidation degree is controlled, the dust can be recycled for soft ferrite materials. The ferromanganese dust contained about 7 kinds of impurities, expecially about 9000 ppm of $SiO_2$ contents of the ferromanganese dust from 9000 ppm to under 500 ppm by fritting method. The $SiO_2$ in ferromanganese dust can be converted into water soluble compounds by alkali fritting and removed by water leaching. KOH and NaOH were used. The most effective conditions to get rid of $SiO_2$ from the dust are that the weight ratio of alkali to ferromanganese dust is 1.75 and fritting is run at $550^{\circ}C$ for 1 hour.

• Journal of Soil and Groundwater Environment
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• v.13 no.3
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• pp.52-58
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• 2008

Mn-impregnated activated carbon (Mn-AC) prepared at different conditions was applied in the treatment of synthetic wastewater containing both organic and inorganic contaminants. Phenol and As(III) was used as the representative organic and inorganic contaminants, respectively. After evaluation of the physicochemical characteristic and stability of Mn-AC, oxidation of As(III) as well as adsorption of phenol by activated carbon(AC) and Mn-AC were investigated in a batch reactor. To investigate the stability of Mn-AC, dissolution of Mn from each Mn-AC was measured pH ranging from 2 to 4. Although Mn-AC was unstable at a strong acidic condition, the dissoluted Mn was below 3 ppm at pH 4. XRD analysis of Mn-AC indicated that the mineral type of the impregnated manganese was $Mn_2O_3$. From the simultaneous treatment of As(III) and phenol by AC and Mn-AC, As(III) oxidation by Mn-AC was greater than that by AC at lower pH, while the reverse order was observed at higher pH. After impregnation of Mn onto AC, 13% decrease of the surface area was observed, causing 8% reduction of phenol removal. Considering removal properties of As(III) and phenol, Mn-AC could be applied in the simultaneous treatment of wastewater contaminated with multi-contaminants.

• Proceedings of the KAIS Fall Conference
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• 2009.05a
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• pp.902-905
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• 2009

축사 또는 쓰레기장에서 에서 발생되는 있는 물질인 암모니아, 아민, 메탄, 탄화수소류 등에 대한 처리를 위한 촉매 개발을 수행하였다. 암모니아를 금속산화물형태의 촉매를 사용하여 산화하였을 경우 $N_2$, NO, $NO_2$, $N_2O$가 일정 비율로 생성되게 된다. 이때의 NO, $NO_2$는 악취는 발생하지 않으나 유독성 가스이므로 이에 대한 선택성이 낮은 촉매를 선별하고 온도에 따른 활성능을 시험하여 최적의 촉매조성을 도출하였다. 다양한 산화가를 지닌 망간을 대상으로 각종 조촉매의 혼합에 따른 실험을 수행하여 최적 조성을 도출 하였다. 촉매 선별작업에서는 충전층을 사용하고, 선별된 촉매에 대하여 모노리스에 코팅하여 사용할 수 있는 모노리스형태의 반응기를 장착하여 모노리스 형태 촉매의 반응성 및 피독특성을 실험하였다.

• Economic and Environmental Geology
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• v.41 no.3
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• pp.327-334
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• 2008

Understanding the chemical characteristics of sediments and the nutrient diffusion from sediments to the water body is important in the management of surface water quality. Changes in chemical properties and nutrient concentration of a submerged soil were monitored for 6 months using a microcosm with the thickness of 30cm for upland soil and 15cm of water thickness above the soil. The soil color changed from yellowish red to grey and an oxygenated layer was formed on the soil surface after 5 week flooding. The redox potential and the pH of the pore water in the microcosm decreased during the flooding. The nitrate concentration of the surface water was continuously increased up to $8\;mg\;l^{-1}$ but its phosphate concentration decreased from $2\;mg\;l^{-1}$ to $0.1\;mg\;l^{-1}$ during flooding. However, the concentrations of $NH_4^+$, $PO_4^{3-}$, Fe and Mn in the pore water were increased by the flooding during this period. The increased $NO_3^-$ in the surface water was due to the migration of $NH_4^+$ formed in the soil column and the oxidation to $NO_3^-$ in the surface water. The increased phosphate concentration in the pore water was due to the reductive dissolution of Fe-oxide and Mn-oxide, which scavenged phosphate from the soil solution. The oxygenated layer played a role blocking the migration of phosphate from the pore water to the water body.

• Journal of the Korean Society of Propulsion Engineers
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• v.12 no.5
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• pp.26-34
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• 2008

The performance of several catalysts to decompose the high test peroxide (HTP) was described in this paper. Manganese oxide, Platinum and Iridium were coated on the gamma alumina. The catalyst activity as active materials was measured at the flask reactor. The response time of various catalysts was also measured with a 50 Newton class thruster. $Ir/Al_2O_3$ that showed the best activity in the flask reactor and response time at the thruster, failed the reaction when continuous mode test was carried out with the thruster. $Pt/Al_2O_3$ and $MnO_2/Al_2O_3$ can be substitutes to decompose the HTP. In addition, for larger thruster, $MnO_2/Al_2O_3$ can be a good catalyst because its cost is below 5 % of $Pt/Al_2O_3$.

• Proceedings of the Korean Society of Propulsion Engineers Conference
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• 2008.11a
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• pp.371-374
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• 2008

The performance of several catalysts to decompose the high test peroxide (HTP) was described in this paper. Manganese oxide, Platinum and Iridium were coated on the gamma alumina. The response time of various catalysts was measured with a 50 Newton class thruster. Ir/$Al_2O_3$ that showed the fastest response time at the thruster, failed the reaction when continuous mode test was carried out with the thruster. Pt/$Al_2O_3$ and MnO_2/Al_2O_3$ can be substitutes to decompose the HTP. In addition, for larger thruster, MnO_2/Al_2O_3$ can be a good catalyst because its cost is below 5 % of Pt/$Al_2O_3$.

• Journal of Korean Society of Environmental Engineers
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• v.35 no.8
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• pp.564-570
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• 2013

Domestic treatment facilities for acid mine drainage (AMD) mostly used a passive treatment process. But some passive treatment facility discharged high manganese concentrations because it is required high pH (>9) for abiotic oxidation of Mn(II) to Mn(IV). This study was focused on the feasibility of biological manganese treatment using the manganese-oxidizing bacteria (Pseudomonas sp. MN5) from AMD and economical application method of it. To investigate the various conditions of water quality the most part of the experiments were based on batch test. And result of it showed that maximum manganese oxidation rate were $10.4mg/L{\cdot}h$ at the pH7. We also performed small column tests in which MOB were attached to the functional polyurethane (FPU) media containing alkaline chemicals. Manganese concentration decreased 42 mg/L to below 6 mg/L. But anaerobic condition formed by excessive bacterial respiration in column resulted in increasing effluent manganese concentration.

• Applied Chemistry for Engineering
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• v.18 no.4
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• pp.350-355
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• 2007

The effect of moisture in flue gas on SCR reaction of NMO (Natural Manganese Ore) was studied. The experiments were performed over NMO with NO, $NH_3$ at independent condition or simultaneous condition. $NH_3$ can be oxidized at low temperature by the lattice oxygen in NMO catalyst. The concentration of NO and $NO_2$ by $NH_3$ oxidation with moisture is higher above $300^{\circ}C$ than that without moisture. Moisture would competitively adsorb with NO and $NH_3$ on NMO catalyst. It caused poor NOx conversion to compete against $H_2O$. Besides the NOx conversion efficiency was reduced at below $250^{\circ}C$ because of the dipped $H_2O$ competitively adsorbed $NH_3$. The reactivity of NMO varied with the calcination temperature and the optimum calcination temperature was $400^{\circ}C$ regardless $H_2O$.

• Economic and Environmental Geology
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• v.19 no.2
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• pp.109-122
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• 1986

Mn-Pb-Zn-Ag deposits of the Janggun mine are hosted in the Cambro-Ordovician Janggun limestone mostly along the contacts of the Jurassic Chunyang granite. The deposits are represented by several ore pipes and steeply dipping lenticular bodies consisting of lower Pb-Zn-Ag sulfide ores and upper manganese carbonate and oxide ores. The former consists mainly of arsenic, antimony, silver, manganese, and tin-bearing sulfides, whereas the latter are characterized by hypogene rhodochrosite, and superficial manganese oxides including todorokite, nsutite, pyrolusite, cryptomelane, birnesite and janggunite. Origin of the upper manganese ore deposits has been a controversial subject among geologists for this mine: hydrothermal metasomatic vs. syngenetic sedimentary origin. Syngenetic advocators have proposed a new sedimentary rock, rhodochrostone, which is composed mainly of rhodochrosite in mineralogy. In the present study, carbon, oxygen and sulfur isotopic compositions were analayzed obtaining results as follows: Rhodochrosite minerals, (Mn, Ca, Mg, Fe) $CO_3$, from hydrothermal veins, massive sulfide ores and replacement ores in dolomitic limestone range in isotopic value from -4.2 to -6.3‰ in ${\delta}^{13}C$(PDB) and +7.6 to +12.9‰ in ${\delta}^{18}O$(SMOW) with a mean value of -5.3‰ in ${\delta}^{13}C$ and +10.7‰ in ${\delta}^{18}O$. The rhodochrosite bearing limestone and dolomitic limestone show average isotopic values of -1.5‰ in ${\delta}^{13}C$ and +17.5‰ in ${\delta}^{18}O$, which differ from those of the rhodochrosite mentioned above. This implies that the carbon and oxygen in ore fluids and host limestone were not derived from an identical source. ${\delta}^{34}S$ values of sulfide minerals exhibit a narrow range, +2.0 to +5.0‰ and isotopic temperature appeared to be about $288{\sim}343^{\circ}C$. Calculated initial isotopic values of rhodochrosite minerals, ${\delta}^{18}O_{H_2O}=+6.6$ to +10.6‰ and ${\delta}^{13}C_{CO_2}=-4.0$ to -5.1 ‰, strongly suggest that carbonate waters should be deep seated in origin. Isotopic data of manganese oxide ores derived from hypogene rhodochrosites suggest that the oxygen of the limestone host rock rather than those of meteoric waters contribute to form manganese oxide ores above the water table.