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Characterization of Synthesized Carbonate and Sulfate Green Rusts: Formation Mechanisms and Physicochemical Properties (합성된 탄산염 및 황산염 그린 러스트의 형성 메커니즘과 이화학적 특성 규명)

  • Lee, Seon Yong;Choi, Su-Yeon;Chang, Bongsu;Lee, Young Jae
    • Korean Journal of Mineralogy and Petrology
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    • v.35 no.2
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    • pp.111-123
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    • 2022
  • Carbonate green rust (CGR) and sulfate green rust (SGR) commonly occur in nature. In this study, CGR and SGR were synthesized through co-precipitation, and their formation mechanisms and physicochemical properties were investigated. X-ray diffraction (XRD) and Rietveld refinement showed both CGR and SGR with layered double hydroxide structure were successfully synthesized without any secondary phases under each synthetic condition. Refined structural parameters (unit cell) for two green rusts were a (=b) = 3.17 Å and c = 22.52 Å for CGR and a (=b) = 5.50 Å and c = 10.97 Å for SGR with the crystallite size 57.8 nm in diameter from (003) reflection and 40.1 nm from (001) reflections, respectively. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) results showed that both CGR and SGR had typical hexagonal plate-like crystal morphologies but their chemical composition is different in the content of C and S. In addition, Fourier transform infrared (FT-IR) spectroscopy analysis revealed that carbonate (CO32-) and sulfate (SO42-) molecules were occupied as interlayer anions of CGR and SGR, respectively. These SEM/EDS and FT-IR results were in good agreement with XRD results. Changes in the solution chemistry (i.e., pH, Eh and residual iron concentrations (Fe(II):Fe(III)) of the mixed solution) were observed as a function of the injection time of hydroxyl ion (OH-) into the iron solution. Three different stages were observed in the formation of both CGR and SGR; precursor, intermediator, and green rust in the formation of both CGR and SGR. This study provides co-precipitation methods for CGR and SGR in a way of the stable synthesis. In addition, our findings for the formation mechanisms of the two green rusts and their physicochemical properties will provide crucial information with researches and industrials in utilizing green rust.

A Study on Infiltration Process and Physicochemical Influence in the Unsaturated and the Saturated Zone of the Bottom Ashes from Thermal Power Plant (화력발전소 배출 바닥재의 불포화대와 포화대 침투과정과 물리화학적 영향에 대한 연구)

  • Park, Byeong-Hak;Joun, Won-Tak;Ha, Seoung-Wook;Kim, Yongcheol;Choi, Hanna
    • Economic and Environmental Geology
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    • v.55 no.1
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    • pp.97-109
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    • 2022
  • This study focused on the physicochemical effects of bottom ash dissolved precipitation on the soil and groundwater environment. The iced column and percolation experiments showed that most of the bottom ash particles were drained as the ash-dissolved solution, while the charcoal powder was filtered through the soil. Ion species of Al, As, Cu, Cd, Cr, Pb, Fe, Mn, Ca, K, Si, F, NO3, SO4 were analyzed from the eluates collected during the 24 h column test. In the charcoal powder eluates, a high concentration of K was detected at the beginning of the reaction, but it decreased with time. The concentrations of Al and Ca were observed to increase with time, although they existed in trace amount. In the bottom ash eluates, the concentrations of Ca and SO4 decreased by 30 mg·L-1 and 67 mg·L-1, respectively, over 24 h. It is regarded that the infiltration patterns of the bottom ash and biochar in the unsaturated zone were different owing to their particle sizes and solvent properties. It is expected that a significant amount of the bottom ash will mix with the precipitation and percolate below the water table, especially in the case of thin and highly permeable unsaturated zone. The biochar was filtered through the unsaturated zone. The biochar did not dissolve in the groundwater, although it reached the saturation zone. For these reasons, it is considered that the direct contamination by the bottom ash and biochar are unlikely to occur.

Technical and Economical Assessment of Adsorption and Reverse Osmosis for Removal of Ammonia from Groundwater of Kathmandu, Nepal (네팔 카트만두 지하수에서 암모늄 제거를 위한 이온 교환 및 역삼투의 기술 및 경제 평가)

  • Kunwar, Pallavi;Ahn, Jaewuk;Baek, Youngbin;Yoon, Jeyong
    • Journal of Appropriate Technology
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    • v.6 no.2
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    • pp.174-182
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    • 2020
  • The permissible limit of ammonia concentration in drinking water recommended by the World Health Organization (WHO) is 1.5 mg/L. However, in the case of groundwater in Kathmandu, Nepal, the concentration of ammonia fluctuates dramatically from 0 to 120 mg/L at different locations and groundwater depths (Chapagain et al., 2010). Such a high concentration of ammonia causes aesthetic problems in drinking water, such as bad taste and odor; hence, prior treatment is required. In Kathmandu, half of the population utilizes groundwater, which is also employed for drinking water, but owing to a lack of knowledge of household water filters, residents of Kathmandu tend to depend greatly on commercially available jar water than on the installation of a proper household filtration method. Thus, in our study, we employed adsorption and reverse osmosis (RO) as two of the most viable decentralized/household treatment options to address the issue of high contamination of ammonia in drinking water. We evaluated their performances from technical and the economic perspectives using synthetically prepared groundwater at varying ammonia concentrations (50 mg/L and 15 mg/L). Consequently, it was found that adsorption via ion exchange (IE) resin was a comparatively better ammonia removal technology than RO, with 100% ammonia removal even after regeneration; the removal by RO was limited to up to 90%. Furthermore, our study suggests that IE is the most suitable ammonia removal technology for places with lower water consumption (< 50 L/day), whereas RO seemed to be a cost-effective technology for places with higher water consumption, where the daily water demand exceeds 50 L/day. Lastly, these assessments suggest that installing a suitable household treatment system would be more efficient and sustainable from both technical and economic points of view than purchasing commercially bottled water.

A Study on Synthesis of Ca and Mg Compounds from Dolomite with Salt Additional React (MgCl2·6H2O) (염 첨가 반응(MgCl2·6H2O)을 이용하여 백운석으로부터 Ca 화합물과 Mg 화합물 합성에 관한 연구)

  • Hwang, Dae Ju;Yu, Young Hwan;Cho, Kye Hong;Lee, Jong Dae
    • Korean Chemical Engineering Research
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    • v.59 no.3
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    • pp.399-409
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    • 2021
  • In order to utilize dolomite as a calcium/magnesium compound material, it was prepared highly reactive calcined dolomite(CaO·MgO) using a microwave kiln (950 ℃, 60 min). The experiment was performed according to the standard of the hydration test (ASTM C 110) and hydration reactivity was analyzed as medium reactivity (max 74.1 ℃, 5 min). Experiments were performed with calcined dolomite and salt (MgCl2·6H2O) (a) 1:1, (b) 1:1.5, and (c) 1:2 wt% based on the hydration reaction of calcined dolomite. The result of X-ray diffraction analysis confirmed that MgO of calcined dolomite increased to Mg(OH)2 as the salt addition ratio increased. After the separating reaction, calcium was stirred at 80 ℃, 24 hr that produced CaCl2 of white crystal. XRD results, it was confirmed calcium chloride hydrate (CaCl2·(H2O)x) and CaO of calcined dolomite and salt additional reaction was separated into CaCl2. And it was synthesized with Ca(OH)2 99 wt% by NaOH adding reaction to the CaCl2 solution, and the synthesized Ca(OH)2 was manufactured CaO through the heat treatment process. In order to prepare calcium carbonate, CaCO3 was synthesized by adding Na2CO3 to CaCl2 solution, and the shape was analyzed in cubic form with a purity of 99 wt%.

Dehydration of Lactic Acid to Bio-acrylic Acid over NaY Zeolites: Effect of Calcium Promotion and KOH Treatment (NaY 제올라이트 촉매 상에서 젖산 탈수반응을 통한 바이오아크릴산 생산: Ca 함침 및 KOH 처리 영향)

  • Jichan, Kim;Sumin, Seo;Jungho, Jae
    • Clean Technology
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    • v.28 no.4
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    • pp.269-277
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    • 2022
  • With the recent development of the biological enzymatic reaction industry, lactic acid (LA) can be mass-produced from biomass sources. In particular, a catalytic process that converts LA into acrylic acid (AA) is receiving much attention because AA is used widely in the petrochemical industry as a monomer for superabsorbent polymers (SAP) and as an adhesive for displays. In the LA conversion process, NaY zeolites have been previously shown to be a high-activity catalyst, which improves AA selectivity and long-term stability. However, NaY zeolites suffer from fast deactivation due to severe coking. Therefore, the aim of this study is to modify the acid-base properties of the NaY zeolite to address this shortcoming. First, base promoters, Ca ions, were introduced to the NaY zeolites to tune their acidity and basicity via ion exchange (IE) and incipient wetness impregnation (IWI). The IWI method showed superior catalyst selectivity and stability compared to the IE method, maintaining a high AA yield of approximately 40% during the 16 h reaction. Based on the NH3- and CO2-TPD results, the calcium salts that impregnated into the NaY zeolites were proposed to exit as an oxide form mainly at the exterior surface of NaY and act as additional base sites to promote the dehydration of LA to AA. The NaY zeolites were further treated with KOH before calcium impregnation to reduce the total acidity and improve the dispersion of calcium through the mesopores formed by KOH-induced desilication. However, this KOH treatment did not lead to enhanced AA selectivity. Finally, calcium loading was increased from 1wt% to 5wt% to maximize the amount of base sites. The increased basicity improved the AA selectivity substantially to 65% at 100% conversion while maintaining high activity during a 24 h reaction. Our results suggest that controlling the basicity of the catalyst is key to obtaining high AA selectivity and high catalyst stability.

Seasonal color change of the oxyhydrous precipitates in the Taebaek coal mine drainage, south Korea, and implications for mineralogical and geochemical controls

  • Kim, J. J.;C. O. Choo;Kim, S. J.;K. Tazaki
    • Proceedings of the Mineralogical Society of Korea Conference
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    • 2001.06a
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    • pp.38-39
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    • 2001
  • The seasonal changes in pH, Fe, Al and SO$_4$$\^$2-/ contents of acid drainage released from coal mine dumps play a major role in precipitation of metal hydroxides in the Taebaek coal field area, southeastern Korea. Precipitates in the creeks underwent a cycle of the color change showing white, reddish brown and brownish yellow, which depends on geochemical factors of the creek waters. White precipitates consist of Al-sulfate (basaluminite and hydrobasaluminite) and reddish brown ones are composed of ferrihydrite and brownish yellow ones are of schwertmannite. Goethite coprecipitates with ferrihydrite and schwertmannite. Ferrihydrite formed at higher values than pH 5.3 and schwertmannite precipitated below pH 4.3, and goethite formed at the intermediate pH range between the two minerals. With the pH being increased from acid to intermediate regions, Fe is present both as schwertmannite and goethite. From the present observation, the most favorable pH that basauluminte can precipitate is in the range of pH 4.45-5.95. SEM examination of precipitates at stream bottom shows that they basically consist of agglomerates of spheroid and rod-shape bacteria. Bacteria species are remarkably different among bottom precipitates and, to a less extent, there are slightly different chemical compositions even within the same bacteria. The speciation and calculation of the mineral saturation index were made using MINTEQA2. In waters associated with yellowish brown precipitates mainly composed of schwertmannite, So$_4$ species is mostly free So$_4$$\^$2-/ ion with less AlSo$_4$$\^$+/, CaSo$\sub$(aq)/, and MgSo$\sub$4(aq)/. Ferrous iron is present mostly as free Fe$\^$2+/, and FeSo$\sub$4(aq)/ and ferric iron exists predominantly as Fe(OH)$_2$$\^$+/, with less FeSo$\sub$4(aq)/, Fe(OH)$_2$$\^$-/, FeSo$_4$$\^$-/ and Fe$\^$3+/, respectively Al exists as free Al$\^$3+/, AlOH$_2$$\^$-/, (AlSo$_4$)$\^$+/, and Al(So$_4$)$\^$2-/. Fe is generally saturated with respect to hematite, magnetite, and goethite, with nearly saturation with lepidocrocite. Aluminum and sulfate are supersaturated with respect to predominant alunite and less jubanite, and they approach a saturation state with respect to diaspore, gibbsite, boehmite and gypsum. In the case of waters associated with whitish precipitates mainly composed of basaluminite, Al is present as predominant Al$\^$3+/ and Al(SO$_4$)$\^$+/, with less Al(OH)$\^$2+/, Al(OH)$_2$$\^$+/ and Al(SO$_4$)$\^$2-/. According to calculation for the mineral saturation, aluminum and sulfate are greatly supersaturated with respect to basaluminite and alunite. Diaspore is flirty well supersaturated while jubanite, gibbsite, and boehmite are already supersaturated, and gypsum approaches its saturation state. The observation that the only mineral phase we can easily detect in the whitish precipitate is basaluminite suggests that growth rate of alunite is much slower than that of basaluminite. Neutralization of acid mine drainage due to the dilution caused by the dilution effect due to mixing of unpolluted waters prevails over the buffering effect by the dissolution of carbonate or aluminosilicates. The main factors to affect color change are variations in aqueous geochemistry, which are controlled by dilution effect due to rainfall, water mixng from adjacent creeks, and the extent to which water-rock interaction takes place with seasons. pH, Fe, Al and SO$_4$ contents of the creek water are the most important factors leading to color changes in the precipitates. A geochemical cycle showing color variations in the precipitates provides the potential control on acid mine drainage and can be applied as a reclamation tool in a temperate region with four seasons.

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LC-MS/MS analysis and anti-inflammatory effects of crude extract from Coptidis Rhizoma (황련 추출물의 LC-MS/MS 분석 및 항염증 효과)

  • Min-Jung, Kim;Ye-Jin, Yang;Kwang-Youn, Kim;Hun Hwan, Kim;Jae Dong, Son;Ju-Hye, Yang;Dong bin, Lee;Woo Hyun, Kim;Hu-Jang, Lee;Seon Been, Bak;Kwang-Il, Park
    • Herbal Formula Science
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    • v.31 no.1
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    • pp.1-10
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    • 2023
  • Objectives : The main aim of this study was to examine the LC-MS/MS used to identify phenolic compounds of CRE(Coptidis Rhizoma 70% EtOH Extract). Also, we investigated antioxidative activities and Anti-inflammatory activities. Methods : LC-MS/MS Analysis HPLC and LC-MS/MS were performed on a 1260 series HPLC system (Agilent Technologies, Inc., California, USA) and 3200 QTrap tandem mass system (Sciex LLC) operated in positive ion mode (spray voltage set at -4.5 kV). The solvent used was DW and Acetonitrile containing 0.1% formic acid, a gradient system was used at a flow rate of 0.5 mL/min for analysis, and a Prontosil C18 column (length, 250 mm; inner diameter, 4.6 mm; particle size, 5 ㎛; Phenomenex Co., Ltd., California, USA, Biochoff Chromatography) was used. The solvent conditions used in the mobile phases were 0-10 min at 10-15% B, 10-20 min at 20% B, 20-30 min at 25%, 30-40 min at 40%, 40-50 min at 70%, 50-60 min at 95%, and 60-70 min at 95%. The analysis was performed at a wavelength of 284 nm and a temperature of 35℃. The cell viability was measured using a 3-(4,5-dimethyethiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity. We examined the effects of CRE on the lipopolysaccharide (LPS)-induced production of nitric oxide (NO) in a RAW 264.7 cells Results : The chemical analysis CRE by Liquid chromatography-tandem mass spectrometry (LC-MS/MS) confirmed that Rosmarinic acid, Ferrulic acid, 3-O-feruloylquinic acid, and 5-O-feruloylquinic acid as phenolic components. DPPH radical scavenging activity was the inhibitory activity of CRE showed at 200 ㎍/mL a statistically significant level. MTT assay demonstrated that the CRE did not have a cytotoxic effect in RAW 264.7 and LPS-induced RAW264.7 cells. Also, CRE reduced NO production in RAW 264.7 cells stimulated with LPS. Conclusions : Based on these findings, The chemical analysis 4 major components CRE such as Rosmarinic acid, Ferrulic acid, 3-O-feruloylquinic acid, and 5-O-feruloylquinic acid. Moreover, we confirmed that CRE has effects antioxidant and anti-inflammatory. The results demonstrate that CRE can be used as an antioxidant and a powerful chemopreventive ingredient against inflammatory diseases.

SHRIMP Zircon U-Pb Age and Geochemistry of Igneous Rocks in the Ssangyong and Yongchu Valleys and Mungyeong Saejae Geosites, Mungyeong Geopark (문경지질공원 쌍룡계곡, 용추계곡, 문경새재 지질명소 화성암류의 SHRIMP 저어콘 U-Pb 연령과 지구화학)

  • Wonseok Cheong;Yoonsup Kim;Giun Han;Taehwan Kim
    • Korean Journal of Mineralogy and Petrology
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    • v.36 no.1
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    • pp.73-94
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    • 2023
  • We carried out the sensitive high resolution ion microprobe (SHRIMP) zircon U-Pb age dating and whole-rock geochemical analysis of granitoids and felsic porphyries in the Ssangyong Valley, Yongchu Valley, and Mungyeong Saejae geosites in the Mungyeong Geopark. The igneous rocks crop out in the western, northwestern and central parts of the Mungyeong city area, respectively, and intruded (meta)sedimentary successions of the Ogcheon Metamorphic Belt, Cambro-Ordovician Mungyeong Group and Jurrasic Daedong Group. The U-Pb isotopic compositions of zircon from two felsic porphyries and one granite samples in the Ssanyeong Valley yielded the Cretaceous intrusion ages of 93.9±3.3 Ma (tσ), 95.1±4.0 Ma (tσ) and 94.4±2.0 Ma (tσ), respectively. On the other hand, a felsic dike sample and a granite in the Yongchu Valley and a porphyritic granite in the Mungyeong Saejae had intrusion ages of 90.2±2.0 Ma (tσ), 91.0±3.0 Ma (tσ) and 88.6±1.5 Ma (tσ), respectively. Based on the average standard error calculated in combination with results of previous studies in this area (Lee et al., 2010; Yi et al., 2014; Aum et al., 2019), the geochronological results show that spatial variation in intrusion age of ~5 Myr between the Ssangyong (94.5±0.2 Ma) and Yongchu Valleys (89.7±0.4 Ma) is apparent. The geochemical compositions of major and trace elements in the samples showed an affinity of typical post-orogenic granite, indicating their petrogenesis during the late stage of Early Cretaceous magmatic activity possibly in association with subduction events of the Izanagi Plate.

Study on Skin pH Improvement Effect through Regulation of Na+/H+ Exchanger 1 (NHE1) Expression of Prunella vulgaris Extract and Its Active Compound, Caffeic Acid (꿀풀 추출물과 그 활성 화합물인 카페인산의 Na+/H+ exchanger 1 (NHE1) 발현 조절을 통한 피부 pH 개선 효과에 대한 연구)

  • No-June Park;Sim-Kyu Bong;Sang-A Park;Gi Hyun Park;Young Chul Ko;Hae Won Kim;Su-Nam Kim
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.49 no.1
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    • pp.87-96
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    • 2023
  • This study was conducted to discover substances that regulate skin surface acidification using human epidermal keratinocyte cell lines, and to investigate their effects on the moisturizing ability and skin barrier function of the stratum corneum. Prunella vulgaris (P. vulgaris) is an herb widely distributed in Northwest Africa and North America that has been studied for its anti-apoptotic, antioxidant, and anti-inflammatory effects. However, research on the regulation of NHE1 expression and the restoration of skin barrier function has not been conducted. Analysis of P. vulgaris revealed the presence of rosmarinic acid and caffeic acid as active ingredients, which were tested for toxicity in human epidermal keratinocyte cell lines (HaCaT), and showed no toxic effects were observed at high concentarion (100 ㎍/mL or 100 µM). It is known that sodium-hydrogen ion exchange pumps (NHE1) decrease in expression in aging skin to maintain the acidic pH of the stratum corneum, and it is hypothesized that this decrease plays an important role in the impaired restoration of skin barrier function in aging skin. P. vulgaris extract and caffeic acid increased the expression of NHE1 in keratinocytes, increased the expression of natural moisturizing factor (NMF) precursor filaggrin and ceramide synthesis enzyme serine palmitoyl transferase (SPT). In addition, P. vulgaris and caffeic acid decreased the extracellular pH of keratinocytes, indicating a direct effect on skin pH regulation. Taken together, these results suggest that P. vulgaris and caffeic acid can regulate skin pH through NHE1 modulation, and may help to restore skin barrier function by increasing NMF and ceramide synthesis. These results show the possibility that honeysuckle and caffeic acid can have a positive effect on skin health, and can be the basis for the development of new skin protection products using them.

A Study on the Recovery of Lithium from Secondary Resources of Ceramic Glass Containing Li-Al-Si by Ca-based Salt Roasting and Water Leaching Process (Li-Al-Si 함유 유리세라믹 순환자원으로부터 Ca계열 염배소법 및 이에 따른 수침출 공정에 의한 리튬의 회수 연구)

  • Sung-Ho Joo;Dong Ju Shin;Dongseok Lee;Shun Myung Shin
    • Resources Recycling
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    • v.32 no.1
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    • pp.42-49
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    • 2023
  • The glass ceramic secondary resource containing Li-Al-Si is used in inductor, fireproof glass, and transparent cookware and accounts for 14% of the total consumption of Li, which is the second most widely used after Li-ion batteries. Therefore, new Li resources should be explored when the demand for Li is exploding, and extensive research on Li recovery is needed. Herein, we recovered Li from fireproof Li-Al-Si glass ceramic, which is a new secondary resource containing Li. The fireproof glass among all Li-Al-Si glass ceramics was used as raw material that contained 1.5% Li, 9.4% Al, and 28.9% Si. The process for recovering Li from the fireproof glass was divided into two parts: (1) calcium salt roasting and (2) water leaching. In calcium salt roasting, a sample of fireproof glass was crushed and ground below 325 mesh. The leaching efficiency was compared based on the presence or absence of heat treatment of the fireproof glass. Moreover, the leaching rates based on the input ratios of calcium salt, Li-Al-Si glass, and ceramics and the leaching process based on calcium salt roasting temperatures were compared. In water leaching, the leaching and recovery rates of Li based on different temperatures, times, solid-liquid ratios, and number of continuous leaching stages were compared. The results revealed that fireproof glass ceramics containing Li-Al-Si should be heat treated to change phase to beta-type spodumene. CaCO3 salt should be added at a ratio of 6:1 with glass ceramics containing Li-Al-Si, and then leached 4 times or more to achieve a recovery efficiency of Li over 98% from a solution containing 200 mg/L of Li.