• 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.

• Korean Journal of Mineralogy and Petrology
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• v.34 no.3
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• pp.169-176
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• 2021

This study aimed to fundamentally understand structural changes of zeolite under pressure and in the presence of different pressure-transmitting media (PTM) for application studies such as immobilization of heavy metal cation or CO₂ storage using pressure. High-pressure X-ray powder diffraction study was conducted on the zeolite-W (K_6.4Al_6.5Si_25.8O₆₄× 15.3H₂O, K-MER) to understand linear compressibility and the bulk moduli in different PTM conditions. Zeolite-w is a synthetic material having the same framework as natural zeolite merlinoite ((K, Ca_0.5, Ba_0.5, Na)₁₀ Al₁₀Si₂₂O₆₄× 22H₂O). The space group of the sample was identified as I4/mmm belonging to the tetragonal crystal system. Water, carbon dioxide, and silicone-oil were used as pressure-transmitting media. The mixture of sample and each PTM was mounted in a diamond anvil cell (DAC) and then pressurized up to 3 GPa with an increment of ca. 0.5 GPa. Pressure-induced changes of powder diffraction patterns were measured using a synchrotron X-ray light source. Lattice constants, and bulk moduli were calculated using the Le-Bail method and the Birch-Murnaghan equation. In all PTM conditions, linear compressibility of c-axis (𝛽^c) was 0.006(1) GPa^-1 or 0.007(1) GPa^-1. On the other hand, the linear compressibility of a(b)-axis (𝛽^a) was 0.013(1) GPa^-1 in silicone-oil run, which is twice more compressible than the a(b)-axis in water and carbon dioxide runs, 𝛽^a = 0.006(1) GPa^-1. The bulk moduli were measured as 50(3) GPa, 52(3) GPa, and 29(2) GPa in water, carbon dioxide, and silicone-oil run, respectively. The orthorhombicities of ac-plane in the water, and carbon dioxide runs were comparatively constant, near 0.350~0.353, whereas the value decreased abruptly in the silicone-oil run following formula, y = -0.005(1)x + 0.351(1) by non-penetrating pressure fluid condition.