Oxidative desulfurization (ODS) has received much attention in recent years because refractory sulfur compounds such as dibenzothiophenes can be oxidized selectively to their corresponding sulfoxides and sulfones, and these products can be removed by extraction and adsorption. In this work, The oxidative desulfurization of marine diesel fuel was performed in a batch reactor with hydrogen peroxide ($H_2O_2$) in the presence of various supported heteropoly acid catalysts. The catalysts were characterized by XRD, XRF, XPS and nitrogen adsorption isotherm techniques. Based on the sulfur removal efficiency of promising silica supported heteropoly acid catalysts, the ranking of catalytic activity was: $30\;H_3PW_{12}/SiO_2$ > $30\;H_3PMo_{12}/SiO_2$ > $30\;H_4SiW_{12}/SiO_2$, which appears to be related with their intrinsic acid strength. The $30\;H_3PW_{12}/SiO_2$ catalyst showed the highest initial sulfur removal efficiency of about 66% under reaction conditions of $30^{\circ}C$, $0.025g\;mL^{-1}$ (cat./oil), 1 h reaction time. However, through the recycle test of the $H_3PW_{12}/SiO_2$ catalyst, significant deactivation was observed, which was attributed to the elution of the active component $H_3PW_{12}$. By introducing cesium cation ($Cs^+$) into the $H_3PW_{12}/SiO_2$ catalyst, the stability of the catalyst was improved with changing the solubility, and the $Cs^+$ ion exchanged catalyst could be recycled for at least five times without severe elution.
KIM, JAEMIN;CHOI, BYOUNG-JU;LEE, SANG-HO;BYUN, DO-SEONG;KANG, BOONSOON
The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
/
v.24
no.2
/
pp.351-373
/
2019
The cold eddies around the Ulleung Basin in the East Sea were identified from satellite altimeter sea level data using the Winding-Angle method from 1993 to 2015. Among the cold eddies, the Dokdo Cold Eddies (DCEs), which were formed at the first meandering trough of the East Korea Warm Current (EKWC) and were pinched off to the southwest from the eastward flow, were classified and their migration patterns were analyzed. The vertical structures of water temperature, salinity, and flow velocity near the DCE center were also examined using numerical simulation and observation data provided by the Hybrid Coordinate Ocean Model and the National Institute of Fisheries Science, respectively. A total of 112 DCEs were generated for 23 years. Of these, 39 DCEs migrated westward and arrived off the east coast of Korea. The average travel distance was 250.9 km, the average lifespan was 93 days, and the average travel speed was 3.5 cm/s. The other 73 DCEs had moved to the east or had hovered around the generated location until they disappeared. At 50-100 m depth under the DCE, water temperature and salinity (T < $5^{\circ}C$, S < 34.1) were lower than those of ambient water and isotherms made a dome shape. Current faster than 10 cm/s circulates counterclockwise from the surface to 300 m depth at 38 km away from the center of DCE. After the EKWC separates from the coast, it flows eastward and starts to meander near Ulleungdo. The first trough of the meander in the east of Ulleungdo is pushed deep into the southwest and forms a cold eddy (DCE), which is shed from the meander in the south of Ulleungdo. While a DCE moves westward, it circumvents the Ulleung Warm Eddy (UWE) clockwise and follows U shape path toward the east coast of Korea. When the DCE arrives near the coast, the EKWC separates from the coast at the south of DCE and circumvents the DCE. As the DCE near the coast weakens and extinguishes about 30 days later after the arrival, the EKWC flows northward along the coast recovering its original path. The DCE steadily transports heat and salt from the north to the south, which helps to form a cold water region in the southwest of the Ulleung Basin and brings positive vorticity to change the separation latitude and path of the EKWC. Some of the DCEs moving to the west were merged into a coastal cold eddy to form a wide cold water region in the west of Ulleung Basin and to create a elongated anticlockwise circulation, which separated the UWE in the north from the EKWC in the south.
Kim, Daehyuk;Shin, Hong-Ryeol;Choi, Min-bum;Choi, Young-Jin;Choi, Byoung-Ju;Seo, Gwang-Ho;Kwon, Seok-Jae;Kang, Boonsoon
Journal of Korean Society of Coastal and Ocean Engineers
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v.32
no.6
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pp.587-601
/
2020
The ocean circulation was simulated in the East Sea and Ulleungdo-Dokdo region using ROMS (Regional Ocean Modeling System) model. By adopting the East Sea 3 km model and the HYCOM 9 km data, Ulleungdo 1 km model and Ulleungdo-Dokdo 300 m model were constructed with one-way grid nesting method. During the model development, a correction method was proposed for the distortion of the open boundary data which may be caused by the bathymetry data difference between the mother and child models and the interpolation/extrapolation method. Using this model, a super-high resolution ocean circulation with a horizontal resolution of 300 m near the Ulleungdo and Dokdo region was simulated for year 2018. In spite of applying the same conditions except for the initial and boundary data, the numerical models result indicated significantly different characteristics in the study area. Therefore, these results were compared and verified by using the surface current data estimated by satellites altimeter data and temperature data from NIFS (National Institute of Fisheries Science). They suggest that in general, the improvement of the one-way grid nesting with the HYCOM data on RMSE, Mean Bias, Pattern correlation and Vector correlation is greater in 300 m model than in the 1 km model. However, the nesting results of using East Sea 3 km model showed that simulations of the 1 km model were better than 300 m model. The models better resolved distinct ridge/trough structures of isotherms in the vertical sections of water temperature when using the higher horizontal resolution. Furthermore, Karman vortex street was simulated in Ulleungdo-Dokdo 300 m model due to the terrain effect of th islands that was not shown in the Ulleungdo 1 km model.
Choi, Kung-Won;Park, Seong-Sook;Kang, Chan-Ung;Lee, Joon Hak;Kim, Sun Joon
Economic and Environmental Geology
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v.54
no.6
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pp.689-698
/
2021
Since the mine reclamation scheme was implemented from 2007 in Korea, various remediation programs have been decontaminated the pollution associated with mining and 254 mines were managed to reclamation from 2011 to 2015. However, as the total amount of contaminated mine drainage has been increased due to the discovery of potential hazards and contaminated zone, more efficient and economical treatment technology is required. Therefore, in this study, the adsorption properties of arsenic was evaluated according to the adsorbents which were derived from water treatment sludge(Alum based adsorbent, ABA-500) and granular ferric hydroxide(GFH), already commercialized. The alum sludge and GFH adsorbents consisted of aluminum, silica materials and amorphous iron hydroxide, respectively. The point of zero charge of ABA-500 and GFH were 5.27 and 6.72, respectively. The result of the analysis of BET revealed that the specific surface area of GFH(257 m2·g-1) was larger than ABA-500(126~136 m2·g-1) and all the adsorbents were mesoporous materials inferred from N2 adsorption-desorption isotherm. The adsorption capacity of adsorbents was compared with the batch experiments that were performed at different reaction times, pH, temperature and initial concentrations of arsenic. As a result of kinetic study, it was confirmed that arsenic was adsorbed rapidly in the order of GFH, ABA-500(granule) and ABA-500(3mm). The adsorption kinetics were fitted to the pseudo-second-order kinetic model for all three adsorbents. The amount of adsorbed arsenic was increased with low pH and high temperature regardless of adsorbents. When the adsorbents reacted at different initial concentrations of arsenic in an hour, ABA-500(granule) and GFH could remove the arsenic below the standard of drinking water if the concentration was below 0.2 mg·g-1 and 1 mg·g-1, respectively. The results suggested that the ABA-500(granule), a low-cost adsorbent, had the potential to field application at low contaminated mine drainage.
The mobility and transport of radioactive cesium are crucial factors to consider for the safety assessment of high-level radioactive waste disposal sites in granite. The retardation of radionuclides in the fractured crystalline rock is mainly controlled by the hydrochemical condition of groundwater and surface reactions with minerals present in the fractures. This paper reports the experimental results of cesium sorption to the Wonju Granite, a typical Mesozoic granite in Korea, performed in an anaerobic chamber that mimics the anoxic environment of a deep disposal site. We measured the rates and amounts of cesium (133Cs) removed by crushed granite samples in different electrolyte (NaCl, KCl, and CaCl2) solutions and a synthetic groundwater solution, with variations in the initial cesium concentration (10-5, 5×10-6, 10-6, 5×10-7 M). The cesium sorption kinetic and isotherm data were successfully simulated by the pseudo-second-order kinetic model (r2= 0.99) and the Freundlich isotherm model (r2= 0.99), respectively. The sorption distribution coefficient of granite increased almost linearly with increasing biotite content in granite samples, indicating that biotite is an effective cesium scavenger. The cesium removal was minimal in KCl solution compared to that in NaCl or CaCl2 solution, regardless of the ionic strength and initial cesium concentration that we examined, showing that K+ is the most competitive ion against cesium in sorption to granite. Because it is the main source mineral of K+ in fracture fluids, biotite may also hinder the sorption of cesium, which warrants further research.
Copper is one of the non-ferrous metals used in the electrical/electronic manufacturing industries due to its superior properties particularly the high conductivity and less resistivity. The effluent generated from the surface finishing process of these industries contains higher copper content which gets discharged in to water bodies directly or indirectly. This causes severe environmental pollution and also results in loss of an important valuable metal. To overcome this issue, continuous R & D activities are going on across the globe in adsorption area with the purpose of finding an efficient, low cost and ecofriendly adsorbent. In view of the above, present investigation was made to compare the performance of a plant root (Datura root powder) as a bio-adsorbent to that of the synthetic one (Tulsion T-42) for copper adsorption from such effluent. Experiments were carried out in batch studies to optimize parameters such as adsorbent dose, contact time, pH, feed concentration, etc. Results of the batch experiments indicate that 0.2 g of Datura root powder and 0.1 g of Tulsion T-42 showed 95% copper adsorption from an initial feed/solution of 100 ppm Cu at pH 4 in contact time of 15 and 30 min, respectively. Adsorption data for both the adsorbents were fitted well to the Freundlich isotherm. Experimental results were also validated with the kinetic model, which showed that the adsorption of copper followed pseudo-second order rate expression for the both adsorbents. Overall result demonstrates that the bio-adsorbent tested has a potential applicability for metal recovery from the waste solutions/effluents of metal finishing units. In view of the requirements of commercial viability and minimal environmental damage there from, Datura root powder being an effective material for metal uptake, may prove to be a feasible adsorbent for copper recovery after the necessary scale-up studies.
Two sets of thermal reaction experiment for chlorinated hydrocarbons were performed using an isothermal tubular-flow reactor in order to investigate thermal decomposition, including product distribution of chlorinated hydrocarbons. The effects of $H_2$ or Ar as the reaction atmosphere on the thermal decomposition and product distribution for dichloromethane($CH_2Cl_2$) was examined. The experimental results showed that higher conversion of $CH_2Cl_2$ was obtained under $H_2$ atmosphere than under Ar atmosphere. This phenomenon indicates that reactive-gas $H_2$ reaction atmosphere was found to accelerate $CH_2Cl_2$ decomposition. The $H_2$ plays a key role in acceleration of $CH_2Cl_2$ decomposition and formation of dechlorinated light hydrocarbons, while reducing PAH and soot formation through hydrodechlorination process. It was also observed that $CH_3Cl,\;CH_4,\;C_2H_6,\;C_2H_4$ and HCl in $CH_2Cl_2/H_2$ reaction system were the major products with some minor products including chloroethylenes. The $CH_2Cl_2$/Ar reaction system gives poor carbon material balance above reaction temperature of $750^{\circ}C$. Chloroethylenes and soot were found to be the major products and small amounts of $CH_3Cl$ and $C_2H_2$ were formed above $750^{\circ}C$ in $CH_2Cl_2$/Ar. The thermal decomposition reactions of chloroform($CHCl_3$) with argon reaction atmosphere in the absence or the presence of $CH_4$ were carried out using the same tubular flow reactor. The slower $CH_3Cl$ decay occurred when $CH_4$ was added to $CH_3Cl$/Ar reaction system. This is because :$CCl_2$ diradicals that had been produced from $CHCl_3$ unimolecular dissociation reacted with $CH_4$. It appears that the added $CH_4$ worked as the :$CCl_2$ scavenger in the $CHCl_3$ decomposition process. The product distributions for $CHCl_3$ pyrolysis under argon bath gas were distinctly different for the two cases: one with $CH_4$ and the other without $CH_4$. The important pyrolytic reaction pathways to describe the important features of reagent decay and intermediate product distributions, based upon thermochemistry and kinetic principles, were proposed in this study.
Bayarsaikhan Battsetseg;Hu Sik Kim;Hyeon Uk Choo;Jong Sam Park;Woo Taik Lim
Korean Journal of Mineralogy and Petrology
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v.36
no.2
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pp.117-124
/
2023
X-ray diffraction analysis, X-ray fluorescence analysis, thermal differential and thermos gravimetric analysis, cation exchange capacity analysis, and Cesium (Cs), Strontium (Sr) adsorption experiments were performed to investigate the physical and chemical properties of natural zeolite from Guryongpo in Korea. As a result of X-ray diffraction analysis, minerals such as mordenite, heulandite, clinoptilolite, and illite are contained, and as a result of X-ray fluorescence analysis, elements such as SiO2, Al2O3, CaO, K2O, MgO, Fe2O3 and Na2O are contained, and the cation exchange capacity was 148.6 meq/100 g. As a result of thermal differential and thermos gravimetric analysis, it was confirmed that the thermal stability was excellent up to 600 ℃. As a result of the adsorption equilibrium experiment over time, the equilibrium was reached within 30 min. for Cesium (Cs) and within 8 hr. for Strontium (Sr), and the adsorption rates of Cesium (Cs) and Strontium (Sr) were 80% and 18%, respectively. As a result of the single-component isothermal adsorption experiment, in conformed to the Langmuir model, and the maximum Cesium (Cs) adsorption amount was 131.5 mg/g, which was high, while the Strontium (Sr) maximum adsorption amount was 29.5 mg/g, which was low. In the case of the natural zeolite used in this study, the content of minerals including 8-rings such as clinoptilolite, heulandite, and mordenite is high, showing high selectivity for Cesium (Cs).
Zeolite template carbon (ZTC) was synthesized as an adsorbent to remove low-concentration CH4 from the atmosphere. The synthesis of ZTC was performed using CH4 and C2H2 as carbon precursors and their impact on adsorption was investigated. ZTC was also synthesized using Y zeolite ion-exchanged with CaCl2 and LiCl as templates to investigate the effect of using metals in ion exchange. The comparison of the carbon precursors revealed that C2H2 had a higher carbon yield than CH4. The synthesized ZTC exhibited developed micropores due to carbon deposition deep inside the micropores of the zeolite template. The kinetic diameter of C2H2 (0.33 nm) is smaller than that of CH4 (0.38 nm), which allowed for its deposition. The study compared metal precursors used for ion exchange and confirmed that the CaCl2-based ZTC developed more micropores compared to the LiCl-based ZTC. The ion-exchanged Ca inhibited pore blocking by the carbon precursor, allowing it to enter the pores. The ability of synthesized ZTC to adsorb N2 and CH4 at 298 K was investigated. The results showed that CH4 had a higher overall adsorption amount than N2. The sample synthesized using C2H2 and CaY exhibited the highest N2 and CH4 adsorption capacity. However, the sample synthesized with CH4 had the highest CH4/N2 gas uptake ratio, which is a crucial factor in designing an adsorption process. The observed difference was likely caused by the underdevelopment of ultrafine pores that are associated with N2 adsorption. This resulted in a reduction of N2 adsorption, leading to an increase in CH4/N2 separation.
Arsenic has recently become of the most serious environmental concerns, and the worldwide regulation of arsenic fur drinking water has been reinforced. Arsenic contaminated groundwater and soil have been frequently revealed as well, and arsenic contamination and its treatment and measures have been domestically raised as one of the most important environmental issues. Arsenic behavior in geo-environment is principally affected by oxides and clay minerals, and particularly iron (oxy)hydroxides have been well known to be most effective in controlling arsenic. Among a number of iron (oxy)hydroxides, for this reason, 2-line ferrihydrite was selected in this study to investigate its effect on arsenic behavior. Adsorption of 2-line ferrihydrite was characterized and compared between As(III) and As(V) which are known to be the most ubiquitous species among arsenic forms in natural environment. Two-line ferrihydrite synthesized in the lab as the adsorbent of arsenic had $10\sim200$ nm for diameter, $247m^{2}/g$ for specific surface area, and 8.2 for pH of zero charge, and those representative properties of 2-line ferrihydrite appeared to be greatly suitable to be used as adsorbent of arsenic. The experimental results on equilibrium adsorption indicate that As(III) showed much stronger adsorption affinity onto 2-line ferrihydrite than As(V). In addition, the maximum adsorptions of As(III) and As(V) were observed at pH 7.0 and 2.0, respectively. In particular, the adsorption of As(III) did not show any difference between pH conditions, except for pH 12.2. On the contrary, the As(V) adsorption was remarkably decreased with increase in pH. The results obtained from the detailed experiments investigating pH effect on arsenic adsorption show that As(III) adsorption increased up to pH 8.0 and dramatically decreased above pH 9.2. In case of As(V), its adsorption steadily decreased with increase in pH. The reason the adsorption characteristics became totally different depending on arsenic species is attributed to the fact that chemical speciation of arsenic and surface charge of 2-line ferrihydrite are significantly affected by pH, and it is speculated that those composite phenomena cause the difference in adsorption between As(III) and As(V). From the view point of adsorption kinetics, adsorption of arsenic species onto 2-line ferrihydrite was investigated to be mostly completed within the duration of 2 hours. Among the kinetic models proposed so for, power function and elovich model were evaluated to be the most suitable ones which can simulate adsorption kinetics of two kinds of arsenic species onto 2-line ferrihydrite.
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