• Journal of the Mineralogical Society of Korea
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• v.20 no.3
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• pp.223-229
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• 2007

The mechanism of hydrothermally synthesizing Na-A zeolite from siliceous mudstone at a $Na_2O/SiO_2$ ratio of 0.6, a $SiO_2/Al_2O_3$ 2.0 and a $H_2O/Na_2O$ 119 has been observed by IR, DTA, XRD and SEM. This mudstone is a tertiary periodic sedimentary rock and widely spreads around the Pohang area. In the early hydrothermal synthesis at $80^{\circ}C$ in an autoclave, sodium silicate and sodium aluminate were found to be preferentially reacted to generate Na-A type zeolite. Gibbsite and bayerite were also formed due to the presence of extra aluminum oxide in the feedstock. As reaction time in-creased up to 50 h, residual sodium aluminatewas reacted with siliceous mudstone, causing the Na-A zeolite crystal to grow and the hydroxylsodalite to generate. Therefore, in the $14{\sim}50\;h$ synthetic time, Na-A zeolite and hydroxylsodalite were formed. Also, if reaction time passed over 50 h, a part of the Na-A zeolite was finally redissolved and reacted with hydroxylsodalite to synthesize Na-P zeolite, generating porous surface of Na-A zeolite and disappearing hydroxylsodalite.

• Journal of the Mineralogical Society of Korea
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• v.20 no.4
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• pp.247-253
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• 2007

The effect of heat treatment and acid leaching of siliceous mudstone on the purity of silica precursors, such as sodium silicate and silicic acid, was studied. As well as the temperatures for the heat treatment of siliceous mudstone, the concentrations of hydrochloric acid and sulfuric acid were varied to achieve the highest content of silicon in the precursors while minimizing energy and chemical consumption. It was found that the optimum conditions were achieved at the heat treatment temperature of $600^{\circ}C$ and hydrochloric acid of 1.56 M. The relative concentrations of silicon in the synthesized sodium silicate and silicic acid were as high as 99.2 and 99.5%, respectively.

• Proceedings of the Petrological Society of Korea Conference
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• 2009.05a
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• pp.120-123
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• 2009

• Journal of the Mineralogical Society of Korea
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• v.20 no.3
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• pp.155-163
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• 2007

A novel route to the synthesis of tetramethoxysilane and other silicon alkoxides is described using siliceous mudstone as the raw material. The reaction of amorphous silica with triethanol-amine is enhanced by using an alkali metal hydroxide catalyst to form a range of triethanol-amnine-substituted silatrane species. These can undergo alkoxide exchange in acidic alcohols to form alkoxysilatranes, tetraalkoxysilanes, hexaalkoxydisiloxanes and higher siloxanes. Products were identified by FT-IR spectroscopy, XRD, SEM, 1H and 13C NMR spectroscopy, or gas chromatography.

• Journal of the Mineralogical Society of Korea
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• v.17 no.1
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• pp.49-59
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• 2004

Organic smectite was hydrothermally synthesized by treating the opal-rich siliceous mudstone from the Pohang area with TMAOH solutions and 1:1 solutions of TMAOH+NaOH at $80^{\circ}C$ and concentrations ranging 10∼15%. Smectite was solely formed without accompanying any mineral products in case of TMAOH, whereas NaP and hydroxysodalite was synthesized together with smectite under the blending solution of TMAOH+NaOH. The synthesized smectite is identified as an organic smectite intercalating $TMA^{+}$ within its interlayer site, specifically corresponding to monmorillonite species, through mineralogical characterization by XRD, DTA, and IR analyses. The experimental results indicate that main precursor of the synthesized smectite is undoubtedly opal-CT, and the original sedimentary smectite included as considerable amounts in the mudstone seems to play a major role as Al-sources necessary far the smectite formation. Original inert components such as quartz and mica do not affect mostly to the synthesis reaction, and thus, are resultantly found as impurities in the synthetic products. These experimental results may imply that a new effective method for the low-temperature (less than $100^{\circ}C$) hydrothermal synthesis of organic smectite will be established if some Al-sources adequate for this synthetic system are available.

• Journal of the Mineralogical Society of Korea
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• v.21 no.4
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• pp.341-347
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• 2008

The feasibility of commercializing the hydrothermal synthesis of Na-A type zeolite from siliceous mudstone has been conducted using a 50-liter bench-scale autoclave and the application of the zeolite as an environmental remediation agent. Siliceous mudstone, which is widely distributed around the Pohang area, was adopted as a precursor. The siliceous mudstone is favorable for the synthesis of zeolite because it contains 70.7% $SiO_2$ and 10.0% $Al_2O_3$, which are major ingredient of zeolite formation. The synthesis of zeolite was carried out under the following conditions that had been obtained from the previous laboratory-scale tests: 10hr reaction time, $80^{\circ}C$ reaction temperature, $Na_2O/SiO_2$ ratio = 0.6, $SiO_2/Al_2O_3$ ratio = 2.0 and $H_2O/Na_2O$ ratio= 98.6. The crystallinity and morphology of the zeolite formed were similar to those obtained from the laboratory-scale tests. The recovery and cation exchange ion capacity were 95% and 215 cmol/kg, respectively, which are slightly higher than those obtained in laboratory scale tests. To examine the feasibility of the zeolite as an environmental remediation agent, experiments for heavy metal adsorption to zeolite were conducted. Its removal efficiencies of heavy metals in simulated waste solutions decreased in the following sequences: Pb > Cd > Cu = Zn > Mn. In a solution of 1500 mg/L total impurity metals, the removal efficiencies for these impurity metals were near completion (> 99%) except for Mn whose efficiency was 98%. Therefore, the synthetic Na-A type zeolite was proven to be a strong absorbent effective for removing heavy metals.

• Journal of the Mineralogical Society of Korea
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• v.13 no.4
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• pp.171-185
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• 2000

Siliceous mudstones are embedded on a large scale in the Tertiary formations of Pohang area. Some useful zeolites such as NsP, (Na, TMA)P, analcime and hydroxysodalite were synthesized from the siliceous mudstones by treating with the variety of solution, i.e ., NaOH, NaOH+NaCl, NaOH, NaOH+$NaAlO_2$and NaOH+TMAOH at the low-temperature hydrothermal system ranging 60~12$0^{\circ}C$. Major precursor of zeolites is found as opal-CT in the zeolite-forming reaction. Smectite, which is included in considerable amounts in the mudstone, appears to play a major role of Al-source in the zeolite synthesis. In comparison, chalcedonic quartz and mica are rather insoluble in alkaline solution, and thus, these are observed as major impurities in the reaction products. An addition of $NaAlO_2$to NaOH solution is effective for eliminating these impurities in the reaction procedure, through these are partly dissolved when elevating the reaction temperature, concentration, and time. Phase change from NaP to hydroxysodalite takes place at the NaOH concentrations of 3.0~4.0 M, and the reaction is not sensitive to the temperature shift. NaP is more stable at lower NaOH concentration and higher activity of $Na_{+}$ whereas analcime is sensitive to the temperature change and stable at higher than $100^{\circ}C$ and 2.0~4.0 M in NaOH concentration. For the pure NaP synthesis without any other products, the treatment of mudstones with 1:1 solution of NaOH and $NaAlO _2$ turns out to be quite effective. NaP was successfully synthesized together with analcime at $100^{\circ}C$ as well as lower concentrations of NaOH+NaCl solution. In addition, the organic type, (Na, TMA)P was formed together with smectite in the 1:1 solution of NaOH and TMAOH.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.1
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• pp.51-64
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• 2022

For effective preservation of the rocks, which bearing plant fossils at Gumkwangdong Formation, Pohang, the properties of rock and treatment of chemicals were examined in an artificial weathering test. The rocks are diatomaceous siliceous mudstone, which contain a small amount of smectite and has developed laminated layers. The rocks react with water, the d₀₀₁ spacing of smectite was increased. On the one hand, the physical properties of the rock samples, such as surface hardness, improved after the application of ethyl silicate-based stone strengthener. On the other hand, the spacing of interlayer of swelling clay minerals decreased and spacing of laminae layer increased. When the ethyl silicate-based stone strengthener was applied after pretreatment with a swelling inhibitor, interlayer and spacing of laminae changes were similar to those when only the stone strengthener was treated. The effect of the swelling inhibitor was almost negligible. When the rocks that have been conserved with chemicals react with water, spacing of laminae has widened much, whereas when the rocks was in contact with moisture only, there was little change. In addition, if it is placed in the outdoor after conservation treatment, although it occurs slightly slower than the untreated rock, the separation of the lamination layer and the pulverization of the rock occur within a very short time. Consolidation is required to improve the physical properties of fossil rock, but when exposed to rain and undergoing freeze-thaw process, the effect is lost very quickly. Therefore, regardless of the chemical treatment, it is a priority to prevent direct rainfall contact with the rock.

• The Korean Journal of Petroleum Geology
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• v.2 no.2 s.3
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• pp.91-99
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• 1994

In the Heunghae area, genetic relationships among sedimentary facies, lithology, stratigraphy and diagenetic mineral facies of the Yeonil Group, are discussed. Conglomerate and sandstone of lower to middle parts of the Yeonil Group contain considerable amounts of volcaniclastic sediments, which were derived from the Tertiary volcanics exposed in the western margins of the sedimentary basin. A new stratigraphic division of the Yeonil Group into the Chunbuk and Pohang Formations is proposed on the basis of sedimentary facies, lithologic characteristics including volcaniclastic feature, and the presence of a key bed of siliceous mudstone overlying the Chunbuk Formation. Diagenetic mineral facies largely depend on the lithology and composition of sediments. Heulandite, smectite, calcite, and opal-CT are commonly found as diagenetic minerals in the Yeonil Group. Among these authigenic minerals, heulandite occurs as the coarse- grained main cement in conglomerates and sandstones of the Chunbuk Formation. Formation of the zeolite cement is favored by partial volcaniclastic lithology of the Chunbuk Formation. Smectite composition and diagenetic mineral facies such as heulandite and opal-CT may reflect that the Yeoil Group has undergone a shallow rial temperature ranging $40{\~}60^{\circ}C$.