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A Brief Review on Limestone Deposits in Korea, Vietnam and Applications 에너지공학 ISSN 1598-7981, 제29권 제3호(2020) Journal of Energy Engineering, Vol. 29, No. 3, pp.42~49(2020) https://doi.org/10.5855/ENERGY.2020.29.3.042 A Brief Review on Limestone Deposits in Korea, Vietnam and Applications of Limestone Yujung Kwaka․Lai Quang Tuana․Euntae Junga․Changsun Jangb․Chaewoon Ohc․Kyung Nam Shind† aCenter for Carbon Mineralization, Mineral Resources Division, Korea Institute of Geosciences and Mineral Resources, Daejeon, 34132, Korea. bDepartment of Transport and Sustainable Mobility, Global Green Growth Institute, Korea. cDivision of Policy Research, Green Technology Center, Seoul, 04554, Korea. dCenter for International Development Cooperation, Kyung-Hee University, Seoul, 02453, Korea (Received 5 August 2020, Revised 4 September 2020, Accepted 9 September 2020) Abstract Precipitated Calcium Carbonate (PCC) can be utilized in energy-effective paper production. Limestone is a raw material for synthesizing PCC. Since the PCC production yield depends on the physicochemical properties of the limestone, a basic investigation of the raw limestone is required. This study provides a brief review of the origin of limestone, limestone distribution characteristics, and limestone deposits in Korea and Vietnam. Most limestones in Korea were formed in the Paleozoic era. On the other hand, limestones in Vietnam have various ages from the Precambrian to the Triassic. Limestone is the most largely produced mineral in Korea, but Vietnam has 5 times more amount of limestone reserves than Korea. Key words : Review, limestone deposits, Korea, Vietnam, Applications 1. Introduction rial. For example, using aragonite PCC as a filler for recycled paper has not only improved whiteness, Recently, researches on the synthesis of precipi- strength, and lifespan, but also reduced industrial tated calcium carbonate (PCC) are actively focused byproducts such as wastewater. In addition, the re- in order to prevent the deepening of global warming fining-drying time is short, so the energy use can be and to recycle depleting resources(Wardhani et al., cut down(Kim et al., 2009). 2018; Zevenhoven et al., 2019; Habte et al., 2020; The PCC synthesis process consists of calcining Abeywardena et al., 2020; Grimes et al., 2020; Adny- limestone, hydration of quicklime, and carbonation ani et al., 2020). PCC is a polymorphs of CaCO3 of slaked lime. To perform this process more effi- including hexagonal calcite, orthorhombic aragonite, ciently, the aragonite yield is important. According and hexagonal vaterite. In addition, crystal size and to KS E 3077(Korean Standard Test) ‘Testing meth- shape have great impacts on their application. od for hydraulic activity of limestone used to pre- In this context, aragonite would be considerably cipitated calcium carbonate’, hydration activity is de- more significant than the others listed above. Arago- fined as the difference between the initial temper- nite is a needle-like material with a large aspect ratio. ature and the temperature 30 seconds after starting Furthermore, their particle size distribution and shape the reaction. can be experimentally controled during synthesis Previous studies have demonstrated that the higher (Park et al., 2004). These characteristics have made the hydration activity of quicklime, the higher the aragonite to be preferred as an industrial raw mate- yield of aragonite-type PCC(Kim et al., 2007; You et al, 2017). Also, Yang et al. (2014b) pointed that im- †To whom corresponding should be addressed. purities within a limestone makes the hydration acti- Tel : +82-02-961-9671 E-mail : [email protected] vity lower and that different crystallographic charac- A Brief Review on Limestone Deposits in Korea, Vietnam and Applications of Limestone 43 Table 1. Major carbonate phase in geologic periods. Era Period Dominant Carbonate Mineral 0 Ma Quaternary Aragonite + High-Mg Calcite (Aragonite Sea) 2.58 Cenozoic Neogene 23.03 Paleogene Low-Mg Calcite 66.0 Cretaceous (Calcite Sea) ∼145.0 Mesozoic Jurassic 201.3 Triassic 251.9 Permian Aragonite + High-Mg Calcite (Aragonite Sea) 298.9 Pennsylvanian Carboni 323.2 ferous Mississippian 358.9 Paleozoic Devonian 419.2 Silurian Low-Mg Calcite (Calcite Sea) 443.8 Ordovician 485.4 Cambrian teristics of limestones with similar CaO content re- As can be seen from the above equation, the for- sult in distinct hydration activity. You et al. (2017) mation of carbonate minerals is greatly affected by and Yang et al. (2014a) showed that the geologi- carbon dioxide. When carbon dioxide is dissolved in cally older limestone has the lower hydration activ- water, reactions such as Eq.(2)~(4) occur, releasing ity in their samples. Since the hydration activity de- hydrogen ions. Therefore, when the partial pressure pends on the parameters such as impurity content, of carbon dioxide in seawater is high(i.e. pH is crystallinity, age, etc. of a limestone, a basic inves- low), dissolution of CaCO3 occurs, but when the tigation of limestone must be preceded before syn- partial pressure of carbon dioxide is low, the gen- thesizing aragonite PCC. This study introduces a eration rate of H+ ions decreases (i.e. the pH of sea- brief concept of limestone formation and compares water increases), resulting in precipitation of CaCO3. the associated natural limestone resources in Korea Therefore, when the temperature of seawater in- and Vietnam. creases and the pressure decreases, the partial pres- sure of CO2 decreases, and eventually CaCO3 is 2. The origin of limestone precipitated because of the low solubility of carbo- nate minerals. Limestone is a sedimentary rock mainly composed CO2+H2O↔H2CO3 (2) of calcium carbonate, and contains SiO2, Al2O3, Fe2O3 as impurities. Limestone is formed by chemical pre- ↔ + - cipitation or biochemical precipitation. Biochemical H2CO3 H +HCO3 (3) limestone forms from the accumulation of marine HCO -↔H++CO 2- (4) organisms such as shells and corals. Chemical lime- 3 3 stone is formed by a reaction shown in Eq.(1). Ions in sea water also influence the precipitation 2+ - of calcite and aragonite. As seawater salinity in- H2O+CO2+CaCO3 ↔ Ca +2HCO3 (1) creases (i.e. ionic strength increases), the solubility Journal of Energy Engineering, Vol. 29, No. 3 (2020) 44 Yujung Kwak․Lai Quang Tuan․Euntae Jung․Changsun Jang․Chaewoon Oh․Kyung Nam Shin Table 2. Paleozoic Stratigraphy in South Korea. Mesozoic Triassic Donggo Formation Gohan Formation Dosagok Formation Permian Hambaeksan Formation Pyeongan Supergroup Jangseong Formation Bamchi Formation Geumcheon Formation Carboniferous Manhang Formation Devonian Imjin System Silurian Hoedongri Formation Paleozoic Duwibong Formation Jigunsan Formation Ordovician Makgol Formation Dumugol Formation Joseon Supergroup Dongjeom Formation Hwajeol Formation Daegi Formation Cambrian Myobong Formation Myeonsan Formation of carbonate minerals increases, and the precipitation 3. The Korean limestones becomes difficult. In addition, Mg2+ ions in seawater 2+ prevent precipitation of calcite. This is because Mg 3.1. Distribution characteristics ions are well adsorbed on the surface of calcite and According to the geological map of Korea, dis- prefer to be substituted in the crystal structure, so 2 the stability of the crystal decreases and eventually tribution area of limestone is about 1,899 km , but if increase the solubility of calcite. On the other hand, including the limestone area covered by the allu- aragonite is relatively less affected by Mg2+ ions. vium, it accounts for 18% of Korea territory(Park et When the content of Mg2+ ions in seawater increa- al., 2017). Limestones in Korea are mainly dis- ses, aragonite precipitation is more preferred than tributed in the early Paleozoic era, the Joseon Super- calcite. Therefore, the types of carbonate rocks group. In the Joseon Supergroup, clastic sedimentary formed through geological history are different. Dur- rocks are embedded in carbonate rocks deposited in ing the period of rapid seafloor spreading, Mg2+ ions shallow sea environments. The Joseon Supergroup is are adsorbed to the hot seafloor basalt, resulting in divided into the Yeongwol, Taebaek, Yongtan, Py- precipitation of calcite with low magnesium(S Boggs, eongchang, and Mungyeong Group according to lith- 1995). The major carbonate mineral phases accord- ology and geographical distribution. Among these, ing to the geological age are shown in Table 1. the Yeongwol Group is subdivided into the Sam- bangsan, Machari, Wagok, Mungok and Yeongheung Formations, and the Taebaek Group is subdivided into the Myeonsan, Myobong, Daegi, Sesong, Hwajeol, Dongjeom, Dumugol, Makgol, Jigunsan and Duwi- bong Formations(Jang et al., 2018). The stratigraphy 에너지공학 제29권 제3호 2020 A Brief Review on Limestone Deposits in Korea, Vietnam and Applications of Limestone 45 of the Paleozoic era in Korea is summerized in ided into Jecheon-Danyang districts, Samcheok-Tae- Table 2(The Geological Society of Korea, 1999). baek-Jeongseon districts, and Andong-Uljin districts. Limestone ores are classified into five categories ac- The Taebaek Group corresponds to Cambro-Ordo- cording to the state of production, composition, crys- vician. A limestone layer is located in the upper tallinity, and organization: (1) Crystalline limestone Myobong Formation. In the Daegi Formation, milky type, (2) Micro-crystalline calcite type, (3) Micro-crys- white, dark gray, and pink massive limestone, dolo- talline marble type, (4) Coarse-crystalline marble mite limestone and stratified limestone are the main type, (5) Mega-crystalline calcite type. Limestone in
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