• Journal of the Mineralogical Society of Korea
• /
• v.23 no.4
• /
• pp.377-393
• /
• 2010

Pumiceous tuffs occurring in the Beomgockri Group are examined applied-mineralogical characteristics and their controling factors to evaluate their potentials as the adsorption-functional mineral resources. The pumiceous tuffs are diagenetically altered to low-grade zeolitcs and bentonites in the Janggi area. Compositional specialty due to the presence of pumice fragments induces the altered tuffs to exhibit the characteristic adsorption property combined with cation exchange capacity, specific surface area, and acidic pH. Unusual lower pH in the adsorption-functional mineral substances is turned out to be originated from the presence of H-smectite having $H^+$ in the interlayer site of the sheet structure. On account of disordered crystallinity resulting from the exchanged $H^+$ in the interlayer site, the smectite commonly forms crenulated edges in the planar crystal form and exhibits characteristic X-ray diffraction patterns showing comparatively lower intensities of basal spacings including (001) peak than conventional Ca-smectite. Based on the interpretation of paragenetic relations and precursor of the H-smectite, a genetic model of the peculiar clay mineral was proposed. The smectite formation may be facilitated resulting from the precipitation of opal-CT at decreasing pH condition caused by the release of H+ during diagenetic alteration of pumice fragments. Because of the acidic smectite, the low-grade mineral resources from the Beomgockri Group may be applicable to the adsorption industry as the raw materials of acid clays and bed-soil.

• Applied Chemistry for Engineering
• /
• v.9 no.5
• /
• pp.639-647
• /
• 1998

Al-containing titanium silicalite-1 ([Al]-TS-1) catalyst was prepared hydrothermally, and the effects of synthesis parameters such as silica/alumina sources, $SiO_2/TiO_2$ ratio, and aging treatment were investigated. The structure, crystal size, and shape were examined by XRD and SEM, and the extent of titanium incorporation into the zeolite framework was examined using UV-vis DRS spectroscopy. For [Al]-TS-1 catalyst preparation, aging of ca. 24h was essential, and the faster crystallization rates were achieved with Cab-O-Sil than with Ludox or TEOS as a silica source. In addition, the higher crystallinity and faster crystallization rate were obtained using sodium aluminate as an aluminum source. 2-butanol oxidation using $H_2O_2$ as an oxidant was carried out to confirm the redox property of the [Al]-TS-1. Acid sites catalyzed toluene alkylation study indicated that lattice titanium species in [Al]-TS-1 weakened the acid strength, and the para-ethyltoluene selectivity was enhanced as a results.

• Korean Chemical Engineering Research
• /
• v.57 no.5
• /
• pp.611-619
• /
• 2019

This study was carried out to investigate fuel decomposition characteristics and coke formation according to types of endothermic fuels and methods of catalyst molding. Methylcyclohexane (MCH), n-dodecane, and exo-tetrahydrodipentadiene (exo-THDCP) were used as the endothermic fuels. As a catalyst, USY720 supported with platinum was used. It was manufactured by only using pressure to disk-type, or pelletized with a binder and a silica solution. The characteristics of the catalysts according to the molding method were analyzed by X-ray diffraction analysis, scanning electron microscopy, nitrogen adsorption-desorption isotherm, and ammonia temperature programmed desorption analysis. The reaction was carried out under conditions of high temperature and high pressure ($500^{\circ}C$, 50 bar) in which the fuel could exist in a supercritical state. The product was analyzed by gas chromatograph/mass spectrometer and the coke produced by the catalyst was analyzed by thermogravimetric analyzer. After the reaction, the composition of the products varied greatly depending on the structure of the fuel. In addition, the crystallinity and surface properties of the catalysts were not changed by the method of catalyst molding, but the changes of the acid sites and the pore characteristics were observed, which resulted in changes in the amount and composition of products and coke.

• Resources Recycling
• /
• v.32 no.6
• /
• pp.45-53
• /
• 2023

This study discussed the trend and future strategy of adsorption technology R&D to effectively recover ammonia emitted from the livestock fields. A proper ammonia adsorbent should incorporate acidic or hydrogen bonding functional groups on the surface, as well as a high specific surface area and a good surface structure appropriate for ammonia adsorption. Activated carbon and minerals such as zeolite have widely been used as ammonia adsorbents, but their adsorption effects are generally low, so any improvement through surface modification should be necessary. For example, incorporation of metal chloride included in a porous adsorbent can promote ammonia adsorption effectiveness. Recently, new types of adsorbents such as MOFs (Metal-Organic Frameworks) and POPs (Porous Organic Polymers) have been developed and utilized. They have shown very high ammonia adsorption capacity because of adjustable and high specific surface area and porosity. In addition, Prussian Blue exhibited high ammonia adsorption and desorption performance and selectivity. This looks relatively advantageous in relation to the recovery of ammonia from livestock waste discharge. In the future, further research should be made to evaluate ammonia adsorption/desorption efficiency and purity using various adsorbents under conditions suitable for livestock sites. Also, effective pre- and/or post-treatment processes should be integrated to maximize ammonia recovery.

• Korean Journal of Mineralogy and Petrology
• /
• v.35 no.3
• /
• pp.367-376
• /
• 2022

This study is a preliminary step to understand the reaction between various liquids and zeolite in the subduction zone environment. Stilbite, NaCa₄(Al₉Si₂₇)O₇₂·28(H₂O), was selected and high pressure study was conducted on compressional behavior by the pressure-transmitting medium (PTM). Water and NaHCO₃ solution that can exist in the subduction zone was used as PTM, and samples were pressurized from ambient to a maximum of 2.5 GPa. Below 1.0 GPa, both experiments show a low linear compressibility in the range of 0.001 to 0.004 GPa^-1 and a high bulk modulus of 220(1) GPa. This is presumably because the structure of the stilbite becomes very dense due to insertion of water molecules or cations into the channel. On the other hand, at 1.0 GPa or higher, the trends of the two experiments are different. In the water run, the linear compressibility of the c-axis is increased to 0.006(1) GPa^-1. In the NaHCO₃ run, the linear compressibility of the b- and c-axis is increased to 0.006(1) GPa^-1. The bulk modulus after 1.0 GPa shows values of 40(1) and 52(7) GPa in water and NaHCO₃ run, respectively, confirming that stilbite becomes more compressible than that before 1.0 GPa. It is caused by the migration of cations and water molecules inside the channel, as the water molecules in the PTM start to freeze and stop to insert toward the channel at 1.0 GPa or more. In the NaHCO₃ run, it is assumed that the distribution of extra-framework species inside the structure is changed by substitution of the Na⁺ cation. It can be expected from tendency of the relative intensity ratio of the (001) and (020) peaks which show a different from that of the water run.

• Korean Journal of Mineralogy and Petrology
• /
• v.36 no.4
• /
• pp.313-321
• /
• 2023

Numerous studies have investigated the adsorptive sequestration of radioactive cesium in the natural environment. Among these studies, adsorption onto minerals and high-temperature treatment stand out as highly effective, as demonstrated by the use of zeolite. In this study, cesium was ion-exchanged with birnessite and subsequently underwent high-temperature treatment up to 1100℃ to investigate both mineral phase transformation and the leaching characteristics of cesium. Birnessite has a layered structure consisting of MnO₆ octahedrons that share edges, demonstrating excellent cation adsorption capacity. The high-temperature treatment of cesium-ion-exchanged birnessite resulted in changes in the mineral phase, progressing from cryptomelane, bixbyite, birnessite to hausmannite as the temperature increased. This differs from the phase transformation observed in the tunneled manganese oxide mineral todorokite ion-exchanged with cesium, which shows phase transformation only to birnessite and hausmannite. The leaching of cesium from cesium-ion-exchanged birnessite was estimated by varying the reaction time using both distilled water and a 1 M NaCl solution. The leaching quantity changed according to the treatment temperature, reaction time, and type of reaction solution. Specifically, the cesium leaching was higher in the sample reacted with 1 M NaCl compared to the sample with distilled water and also increased with longer reaction time. For the samples reacted with distilled water, the cesium leaching initially increased and then decreased, while in the NaCl solution, the leaching decreased, increased again, and finally nearly stopped like the sample in the distilled water for the sample treated at 1100℃. These changes in leaching are closely associated with the mineral phases formed at different temperatures. The phase transformation to cryptomelane and birnessite enhanced cesium leaching, whereas bixbyite and hausmannite hindered leaching. Notably, hausmannite, the most stable phase occurring at the highest temperature, demonstrated the greatest ability to inhibit cesium leaching. This results strongly suggest that high-temperature treatment of cesium-ion-exchanged birnessite effectively immobilizes and sequesters cesium.

• Journal of the Korean Chemical Society
• /
• v.37 no.2
• /
• pp.191-198
• /
• 1993

The crystal structures of $Cd_{6-}A$ evacuated at $2{\times}10^{-6}$ torr and $750^{\circ}C$ (a = 12.204(1) $\AA$) and dehydrated $Cd_{6-}A$ reacted with 0.1 torr of Cs vapor at $250^{\circ}C$ for 12 hours (a = 12.279(1) $\AA$) have been determined by single crystal X-ray diffraction techniques in the cubic space group Pm3m at $21(1)^{\circ}C.$ Their structures were refined to final error indices, $R_1=$ 0.081 and $R_2=$ 0.091 with 151 reflections and $R_1=$ 0.095 and $R_2=$ 0.089 with 82 reflections, respectively, for which I > $3\sigma(I).$ In vacuum dehydrated $Cd_{6-}A$, six $Cd^{2+}$ ions occupy threefold-axis positions near 6-ring, recessed 0.460(3) $\AA$ into the sodalite cavity from the (111) plane at O(3) : Cd-O(3) = 2.18(2) $\AA$ and O(3)-Cd-O(3) = $115.7(4)^{\circ}.$ Upon treating it with 0.1 torr of Cs vapor at $250^{\circ}C$, all 6 $Cd^{2+}$ ions in dehydrated $Cd_{6-}A$ are reduced by Cs vapor and Cs species are found at 4 crystallographic sites : 3.0 $Cs^+$ ions lie at the centers of the 8-rings at sites of $D_{4h}$ symmetry; ca. 9.0 Cs+ ions lie on the threefold axes of unit cell, ca. 7 in the large cavity and ca. 2 in the sodalite cavity; ca. 0.5 $Cs^+$ ion is found near a 4-ring. In this structure, ca. 12.5 Cs species are found per unit cell, more than the twelve $Cs^+$ ions needed to balance the anionic charge of zeolite framework, indicating that sorption of Cs0 has occurred. The occupancies observed are simply explained by two unit cell arrangements, $Cs_{12}-A$ and $Cs_{13}-A$. About 50% of unit cells may have two $Cs^+$ ions in sodalite unit near opposite 6-rings, six in the large cavity near 6-ring and one in the large cavity near a 4-ring. The remaining 50% of unit cells may have two Cs species in the sodalite unit which are closely associated with two out of 8 $Cs^+$ ions in the large cavity to form linear $(Cs_4)^{3+}$ clusters. These clusters lie on threefold axes and extend through the centers of sodalite units. In all unit cells, three $Cs^+$ ions fill equipoints of symmetry $D_{4h}$ at the centers of 8-rings.