• Korean Journal of Chemical Engineering
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• v.35 no.11
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• pp.2232-2240
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• 2018

We applied methanesulfonic acid (MSA) as a green catalyst to produce levulinic acid (LA) from monomeric sugars. To optimize reaction factors and assess the effect of reciprocal interactions, a statistical experimental design was applied. Optimized result of 40.7% LA yield was obtained under the following conditions: 60 g/L galactose, 0.4 M MSA at $188^{\circ}C$ for 26.7 min. On the other hand, 66.1% LA yield was achieved under 60 g/L fructose and 0.4 M MSA at $188^{\circ}C$ for 36 min conditions. For the effect of combined severity factor on the LA yield from galactose, the LA yield showed a peaked pattern, which was linearly increased until a CSF 3.2 and then diminished with a high CSF. Moreover, it was closely fitted to a non-linear Gaussian peak pattern with a high regression value of 0.989. These results suggest that MSA and galactose, derived from marine red macro-algae, can potentially be applied for the conversion into platform chemicals.

• Economic and Environmental Geology
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• v.28 no.4
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• pp.337-350
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• 1995

The Hwacheon-ri mineralized area is located within the Cretaceous Gyeongsang Basin of the Korean peninsula. The mineralized area includes the Hwacheon, Daeweon, Kuryong and Cheongryong mines. Each of these mines occurs along copper-bearing hydrothermal quartz veins that crosscut late Cretaceous volcanic rocks, although some disseminated ores in host rocks also exist locally. Mineralization can be separated into three distinct stages (I, II, and III) which developed along preexisting fracture zones. Stage I is ore-bearing, whereas stages II and III are barren. The main phase of ore mineralization, stage I, can be classified into three substages (Ia, Ib and Ic) based on ore mineral assemblages and textures. Substage Ia is characterized by pyrite-arsenopyrite-molybdenite-pyrrhotite assemblage and is most common at the Hwacheon deposit. Substage Ib is represented by main precipitation of Cu, Zn, and Pb minerals. Substage Ic is characteristic of hematite occurrence and is shown only at the Kuryong and Cheongryong deposits. Some differences in the ore mineralization at each mine in the area suggest that the evolution of hydrothermal fluids in the area varied in space (both vertically and horizontally) with respect to igneous rocks relating the ore mineralization. Fluid inclusion data show that stage I ore mineralization mainly occurred at temperatures between ${\approx}350^{\circ}$ and ${\approx}200^{\circ}C$ from fluids with salinities between 9.2 and 0.5 wt.% eq. NaCl. In the waning period of substage Ia, the high temperature and salinity fluid gave way to progressively cooler, more dilute fluids of later substage Ib and Ic (down to $200^{\circ}C$, 0 wt.% NaCl). There is a systematic decrease in the calculated ${\delta}^{18}O_{H2O}$ values with paragenetic time in the Hwacheon-ri hydrothermal system from values of ${\approx}2.7$‰ for substage Ia, through ${\approx}-2.8$‰ for substage Ib, to ${\approx}-9.9$‰ for substage Ic. The ${\delta}D$ values of fluid inclusion water also decrease with decreasing temperature (except for the Daeweon deposit) from -62‰ (substage Ia) to -80‰ (substage Ic and stage III). These trends are interpreted to indicate the progressive cooler, more oxidizing unexchanged meteoric water inundation of an initial hydrothermal system which is composed of highly exchanged meteoric water. Equilibrium thermodynamic interpretation of the mineral assemblages with the variation in amounts of chalcopyrite through the paragenetic time, and the evolution of the Hwacheon-ri hydrothermal fluids indicate that the solubility of copper chloride complexes in the hydrothermal system was mainly controlled by the variation of temperature and $fo_2$ conditions.

• Economic and Environmental Geology
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• v.35 no.3
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• pp.203-210
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• 2002

In order to elucidate the growth mechanism of sulfide chimney formed as a result of seafloor hydrothermal mineralization, we carried out the mineralogical and fluid inclusion studies on the inactive, sulfide- and silica-rich chimney which has been recovered from a hydrothermal field in the Cleft segment of the Juan de Fuca Ridge. According to previous studies, many active and inactive vents are present in the Cleft segment. The sulfide- and silica-rich chimney is composed of amorphous silica, pyrite, sphalerite and wurtzite with minor amounts of chalcopyrite and marcasite. The interior part of the chimney is highly porous and represents a flow channel. Open spaces within chimneys are typically coated with colloform layers of amorphous silica. The FeS content of Zn-sulfides varies widely from 13.9 to 34.3 mole% with Fe-rich core and Fe-poor rims. This variation possibly reflects the change of physicochemical characteristics of hydrothermal fluids. Chemical and mineralogical compositions of the each growth zone are also varied, possibly due to a thermal gradient. Based on the microthermometric measurements of liquid-rich, two-phase inclusions in amorphous silica that was precipitated in the late stage of mineralization, minimum trapping temperatures are estimated to be about 1140 to 145$^{\circ}$C with the salinities between 3.2 and 4.8 wt.% NaCI equiv. Although the actual fluid temperatures of the vent are not available, this study suggests that the lowtemperature conditions were predominant during the mineralization in the hydrothermal field at Cleft segment. Comparing with the previously reported chimney types, the morphology, colloform texture, bulk chemistry, and a characteristic mineral assemblage (pyrite + marcasite + wurtzite + amorphous silica) of this chimney indicate that the chimney have been formed from a relatively low-temperature (<250$^{\circ}$C) hydrothermal fluid that was changed by sluggish fluid flow and conductive cooling.

• Journal of the Korean Recycled Construction Resources Institute
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• v.6 no.4
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• pp.103-111
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• 2012

One of the basic physical properties of the hardened cement paste, the rigidity, is deteriorated during concrete matrix forming, depending on the replacement rate of the crushed stone powder, and due to drying shrinkage. Therefore, the concrete containing crushed stone powder has been limitedly used as non-structural construction material. To improve these disadvantages, a hydrothermal reaction employing method can be considered. High-temperature and high-pressure water is involved in the hydrothermal reaction in the mixing with specific materials. The rigidity improving mechanism is related to the synthesis of calcium silicate. The calcium silicate is produced through reaction between calcium compounds and the silicic acid. Various kinds of calcium silicate can be produced depending on the CaO/$SiO_2$ mole ratio, the temperature of the hydrothermal synthesis, the pressure, and the reaction time. The product of the synthesis mechanism, tobermorite crystal, plays a pivotal role for the rigidity reinforcement. The crushed stone powder, analyzed in this study, contains 50 to 60% of $SiO_2$ and 10 to 20% $Al_2O_3$. The composite rate is appropriate to create the tobermorite crystal through formation of hardened cement matrix under the hydrothermal synthetic conditions and with the CaO in the cement. Moreover, further reinforcement was promoted using the property of material under the identical density through promoting the formation of tobermorite crystal.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.23 no.5
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• pp.241-245
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• 2013

Granular bamboo-derived active carbons (AC) were impregnated (or coated) with $TiO_2$ nano crystalline powders. The photocatalytic activity of the $TiO_2$-impregnated active carbons ($TiO_2$/AC) were determined on the basis of the degradation rate of methylene-blue aqueous solution under UV irradiation. The active compounds of $TiO_2$ were impregnated onto the AC under moderate hydrothermal conditions (${\leq}200^{\circ}C$, pH 11). The mean size of $TiO_2$ particles calculated from BET surface area were found to be as 50 nm. The $TiO_2$ precipitates were coated on the cavities or pores on the surfaces of highly activated carbons. Since the hydrothermal process led to a lowering of the on-set temperature of the anatase-to-rutile transition of $TiO_2$ as low as $200^{\circ}C$, $TiO_2$ crystallites of a pure anatase or a mixed form with rutile were successfully coated on the AC depending on the synthesis temperatures.

• Economic and Environmental Geology
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• v.32 no.5
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• pp.445-454
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• 1999

The Sanjeon Au-Ag deposit consists of three subparallel hydrothermal quartz-calcite veins which filled fault-related fractures (generally $N20^{\circ}$ to 35"W-trending and $70^{\circ}$ to $80^{\circ}$ SW-dipping) within quartz porphyry. The vein mineralization shows an apparent variation of mineral assemblages with paragenetic time: (1) early, white quartz + pyrite + arsenopyrite + brown sphalerite, (2) middle, white (vein) to clear quartz (vug) + base-metal sulfides + electrum + argentite, (3) late, calcite + pyrite + native silver. Mineralogic and fluid inclusion data indicate that gold-silver minerals were deposited at temperatures from 2l $0^{\circ}$ to $250^{\circ}$ with salinities of 4 to 5 wt. % equiv. NaCl and log fS2 values from -14.0 to -12.2 atm. The linear relationship between homogenization temperature and salinity data indicates that gold-silver deposition was a result of meteoric water mixing. Ore mineralization occurred at pressure conditions of about 70 bars, which corresponds to the mineralization depths of about 260 m to 700 m. There is a remarkable decrease of the calculated 1)180 values of water from 1.3 to -9.7%0 in hydrothermal fluid with increasing paragenetic time. This indicates a progressive increase of meteoric water influx in the hydrothermal system at the Sanjeon deposit. Oxygen-hydrogen, sulfur, and carbon isotope values of hydrothermal fluids indicate that the ore mineralization was formed largely from meteoric waters with the contribution of sulfur and carbon from a deep igneous source.

• Journal of the Mineralogical Society of Korea
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• v.31 no.2
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• pp.87-101
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• 2018

The Manjang deposit developed in the Hwajeonri formation of the Okcheon metamorphic belt consists of the Central and Main orebodies of Cu-bearing hydrothermal vein type and the Western orebody of Fe-skarn type. This study focuses on the Cu mineralization of the Central and Main orebodies to compare with the genetic environments of the Western orebody previously studied. The Central orebody produced pyrrhotite and chalcopyrite as major ore minerals with vein texture, while the Main orebody contains pyrite, arsenopyrite, and chalcopyrite as major ore minerals with vein, massive, and brecciated texture. Sphalerite, galena, magnetite, ilmenite, rutile, cassiterite, wolframite, and stannite are also accompanied. Local occurrence of skarn is dominated by grossular and hedenbergite, reflecting the reduced condition of the skarnization. Geothermometries of sphalerite-stannite in the Central orebody and arsenopyrite-pyrite in the Main orebody indicate the formation temperature of $204-263^{\circ}C$ and $383-415^{\circ}C$, respectively. Sulfur fugacity of $10^{-6}-10^{-7}atm$. in the Main orebody decreased toward the Central orebody. Sulfur isotope compositions of sulfide minerals from the Central and Main orebodies are 4.6-7.9‰ and 4.3-7.0‰, respectively, reflecting magmatic origin with slight influence by host rock. Considering ore mineralogy, texture as well as physicochemical conditions, the Main and Central orebodies of hydrothermal Cu mineralization reflect the characteristics of proximal and distal type ore mineralization, respectively, related to hidden igneous rocks, and they were generated under different hydrothermal systems from the Fe-skarn Western orebody.

• Journal of the Mineralogical Society of Korea
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• v.20 no.4
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• pp.267-275
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• 2007

Melting slag generated from municipal-incinerator ash contains lots of impurities which have adverse effects on zeolite synthesis. These impurities are detrimental to zeolite synthesis, and the yield and purity of zeolite was decreased. And thus its performance is lowered. In melting slag, there are lots of components such as $Fe_2O_3$, FeO and CaO. To remove these impurities, we treated the melting slag with hydrochloric acid at initial pH 1, 3, 5, and 7. After the treatment, the $SiO_2,\;Fe_2O_3,\;and\;TiO_2$ ratios increased, but the $Al_2O_3,\;FeO,\;CaO,\;Na_2O$ and MgO ratios decreased. We reacted these treated slag in a NaOH solution under hydrothermal conditions at $80^{\circ}C$. The hydrothermal products from the slag and the slag treated at pH 7 and pH 5 were determined to be tobermorite, whereas those at pH 3 and pH 1, Na-P1 and Na-X zoelite respectively. CaO was found to inhibit the synthesis of zeolite.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.29 no.5
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• pp.203-207
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• 2019

Calcium phosphates such as hydroxyapatite (HAp), tricalcium phosphate (${\beta}$-TCP), and biphasic calcium phosphate (BCP, HAp/${\beta}$-TCP) have been prepared via hydrothermal treatment. The synthesis was conducted by reacting ($Ca(OH)_2$) aqueous solution with phosphoric acid ($H_3PO_4$) under different hydrothermal synthesis conditions (temperatures up to $150^{\circ}C$ and pH lower than 12). The effects of initial precursor Ca/P ratio (1.30, 1.50 and 1.67) and post heat treatment on the phase evolution behavior of the powders and sintered ceramics were investigated. The phases of resulting powders and sintered ceramics were controllable by adjusting the initial Ca/P ratio. A single HAp phase without any noticeable second phase was obtained for the initial Ca/P ratio of 1.67 in the overall heat treatment range. Pure ${\beta}$-TCP and biphasic calcium phosphate (HAp/${\beta}$-TCP) were synthesized from precursor solutions having Ca/P molar ratios of 1.30 and 1.50, respectively, after having been heat treated at $900^{\circ}C$ or higher. Dense ceramics with translucency were obtained at considerably lower sintering temperatures.

• Economic and Environmental Geology
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• v.32 no.5
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• pp.435-444
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• 1999

The antimony deposits of the Hyundong mine, located in the northeastern part of the Sobaegsan massif, occur as hydrothermal quartz+carbonate veins and stockworks which fill the fault fractures developed in Precambrian metamOlphic rocks (mainly, granitic gneiss). Hydrothermal alteration occurs commonly in the vicinity of mineralized veins and is characterized by sericitization and silicification. A K-Ar age of alteration sericite is 139.2$\pm$ 4.4 Ma, implying the early Cretaceous age of mineralization, possibly in association with intrusion of nearby acidic dikes (mainly, quartz porphyry). The hydrothermal mineralization occurred in five mineralization stages. These are: (I) stage I, characterized by deposition of chalcedonic quartz; (2) stage II, deposition of quartz with base-metal sulfides and stibnite; (3) stage III, deposition of quartz and carbonates (calcite, dolomite, ankerite, rhodochrosite) with various antimony-bearing minerals such as stibnite, polybasite, berthierite, native antimony, gudmundite and ullmannite; (4) stage IV, deposition of calcite with stibnite; and (5) stage V, deposition of barren calcite. Antimony occurs mostly as stibnite within stages II to IV veins, which has various habits including disseminated, veinlets and euhedral coarse crystals. Fluid inclusion studies indicate that hydrothermal mineralization at Hyundong occurred from the fluids with temperature and salinity of $330^{\circ}$C to 120 and 5.3 wI. % equiv. NaCI. The temperature and salinity of ore fluids systematically decreased with elapsed time in the course of mineralization, possibly due to the influx of larger amounts of meteoric groundwater. The deposition of antimony-bearing minerals occurred at low temperatures «$250^{\circ}$C), mainly due to the cooling and dilution of fluids. Based on the evidence of fluid boiling during the early stage II mineralization, the mineralization occurred under low pressure conditions (about 80 bars, corresponding to depths of about 350 m under hydrostatic pressure regime). Thermodynamic considerations of ore . mineral assemblages indicate that antimony deposition also occurred as the results of decreases in temperature and sulfur fugacity of hydrothermal fluids. Calculated sulfur isotope composition of ore fluids ($\delta^{34}S_{\Sigma s}$=5.4 to 7.8$\textperthousand$) indicates an igneous source of sulfur.