• Korean Chemical Engineering Research
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• v.62 no.2
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• pp.181-190
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• 2024

Here, we develop a centrifugal microfluidic reactor with simple, fast, and high-throughput manner for the generation of magnetic Janus micro-adsorbents (MAs). By using the multi-micronozzle consisting of two separate aligned needles and centrifugal tubes, we have synthesized highly monodispersed Prussian blue- and magnetic nanoparticle-laden micro-adsorbents (PB-MNP-MAs). The enhanced cesium (Cs⁺) adsorption was demonstrated by conducting the adsorption isotherm and kinetics experiment which can be contributed to the porous nature of the Ca-alginate networks with a high surface area of embedded PB nanoparticles, resulting to perform rapid adsorption activity within 10 min. After Cs⁺ adsorption process, the as-synthesized PB-MNP-MAs were successfully harvested by introducing the external magnetic fields. Therefore, we believe that our findings can be provided new direction towards the development of advanced functional adsorbents in biological and environmental fields.

• Clean Technology
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• v.25 no.1
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• pp.91-97
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• 2019

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.

• Applied Chemistry for Engineering
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• v.21 no.1
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• pp.63-70
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• 2010

Transition metal based spent catalysts (Ni-Mo and Co-Mo), which were scrapped from the petrochemical industry, were reused for the removal processes of volatile organic compounds (VOCs). Especially the optimum regeneration procedures were determined using the removal efficiency of VOCs. In this work, the spent Ni-Mo and spent Co-Mo catalysts were pretreated with different physic-chemical treatment procedure: 1) acid aqueous solution, 2) alkali solution, 3) chemical agent and 4) steam. The various characterization methods of spent and its regenerated catalysts were performed using nitrogen adsorption, X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with an energy dispersive spectrometry (EDS). It was found that all spent catalysts were found to be potentially applicable catalysts for catalytic oxidation of benzene. The experimental results also indicated that among the employed physico-chemical pretreatment methods, the oxalic acid aqueous (0.1 N, $C_2H_2O_4$) pretreatment appeared to be the most efficient in increasing the catalytic activity, although the catalytic activity of spent Ni-Mo and spent Co-Mo catalysts in the oxidation of benzene were greatly dependent on the pretreatment conditions. The pretreated spent catalysts at optimum condition could be also applied for removing other aromatic compounds (Toluene/Xylene).

• Korean Journal of Environmental Agriculture
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• v.12 no.3
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• pp.209-218
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• 1993

The behaviour of insectcide ethoprophos (O-ethyl S,S-propyl phosphorodithioate) in soil was investigated. In a laboratory study, the degradation of ethoprophos in soil followed first-order reaction kinetics. The half-life of the insecticide in the soil incubated with 10, 18 and $25^{\circ}C$ was 12.4, 5.5 and 2.5 days, respectively. Arrhenius activation energy was 73.8 KJ/mole. The half-life was 46.4, 17.6 and 6.9 day in the soil with 7, 14 and 19% of soil water content, respectively. The moisture dependence B value in empirical equation was 1.67. The adsorption isotherm for ethoprophos in the soil agreed with freundlich equation. The adsorption distribution coefficient (Kd) was 0.27. In a field study prepared in autumn with undisturbed soil column in a mini-lysimeter system, ethoprophos residues were largely distributed in the top $0{\sim}2cm$ soil layer and moved down to the top 6cm soil layer. Persistence of ethoprophos in field soil was correlated with variation in weather pattern during the period of experiments. The half-life of ethoprophos treated at March and October was about 17 and 5 days, respectively. The ethoprophos woil was degraded up to 90% at 37day after the both treatment. In persistence and mobility of ethoprophos in field soil, the observed data were reasonably corresponded with predicted data by some computer model of pesticide behaviour.

• Applied Chemistry for Engineering
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• v.21 no.6
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• pp.648-652
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• 2010

Catalytic activities of the partial oxidation of methane (POM) to hydrogen were investigated over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK in a fixed bed flow reactor (FBFR) under atmosphere, and the catalysts were characterized by BET, XPS, XRD. The BET surface areas, pore volume and pore width of Horvath-Kawaze, micro pore area and volume of t-plot of Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were $284m^2/g$, $0.233cm^3/g$, 3.9 nm, $30m^2/g$, $0.015cm^3/g$ and $396m^2/g$, $0.324cm^3/g$, 3.7nm, $119m^2/g$, $0.055cm^3/g$, repectively. The nitrogen adsorption isotherms were type IV with hysteresis. XPS showed that Si 2p and O 1s core electronlevels of Ti-SPK and Zr-SPK substituted Ti and Zr shifted to slightly lower binding energies than SPK. The oxidation states of Pd on the surface of catalysts were $Pd^0$ and $Pd^{+2}$. XRD patterns showed that crystal structures of fresh catalyst changed amorphous into crystal phase after reaction. The conversion and selectivity of POM to hydrogen over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were 77, 84% and 78, 72%, respectively, at 973 K, $CH_4/O_2$ = 2, GHSV = $8.4{\times}10^4mL/g_{cat}{\cdot}h$ and were kept constant even after 3 days in stream. These results confirm superior activity, thermal stability, and physicochemical properties of catalyst in POM to hydrogen.

• Clean Technology
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• v.26 no.1
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• pp.7-12
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• 2020

Ti-SBA-15 catalysts doped with lanthanide ions (Ln/Ti-SBA-15) were successfully synthesized using conventional hydrothermal method. In addition, they were characterized by XRD, FT-IR, DRS, BET, and PL. The activity of these materials on the photocatalytic decomposition of methylene blue under ultraviolet light irradiation was also examined. Ti-SBA-15 catalysts doped with various lanthanide ions maintained their mesoporous structure. The pore size and pore volume of Ln/Ti-SBA-15 materials decreased but their surface area increased upon the doping of lanthanide ion. Ln/Ti-SBA-15 materials exhibited the type IV nitrogen isotherm with desorption hysteresis loop type H2, which was characteristic of mesoporous materials. The size of hysteresis increased in the doping of lanthanide ions on Ti-SBA-15 material. There was no absorption in the visible region (> 400 nm) regardless of the doping of lanthanide ions to TiO₂ particles, while the broad bands at 220 nm appeared at the Ln/Ti-SBA-15 samples, indicating the framework incorporation of titanium into SBA-15. 1 mol% Pr/ Ti-SBA-15 catalysts showed the highest photocatalytic activity on the decomposition of methylene blue but the Ti-SBA-15 catalysts doped with Eu, Er, and Nd ions showed lower activity compared to pure Ti-SBA-15 catalyst. The PL peaks appeared at about 410 nm at all catalysts while the excitonic PL signal was proportional to the photocatalytic activity for the decomposition of methylene blue.

• Applied Chemistry for Engineering
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• v.19 no.5
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• pp.574-581
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• 2008

The optimum regeneration conditions for the regeneration of three way spent catalysts (TWCs), which were taken from automobiles with different driving conditions, were investigated to evaluate the suitability as alternative catalysts for removing VOCs. The spent catalysts were washed with five different acids ($HNO_3$, $H_2SO_4$, $C_2H_2O_4$, $C_6H_8O_7$, and $H_3PO_4$) to remove contaminants and examine the optimum conditions for recovering the catalytic activity. The physicochemical properties of spent and its regenerated TWCs were evaluated by using nitrogen adsorption-desorption isotherms, XRD, and ICP. The relative atomic ratios of contaminants and platinum group metals (PGMs) of the spent TWCs were greatly dependent on the placed positions. The main contaminants formed were lubricant oil additives and metallic components. Also, the regeneration treatment increased the PGMs ratio, BET surface area, and average pore diameter of TWCs. The catalytic activity results indicated that the spent TWCs have the possibility for removing VOCs. Moreover, the employed acid treatments greatly enhanced the catalytic activity of the spent TWCs. Especially, nitric and oxalic acids provided the most improvement in the catalytic behavior. The catalytic activities of the regenerated TWCs were significantly influenced by the containing platinum ratios rather than the removal ratios of contaminants and the changes in the structural properties offered by the acid treatments.

• Korean Chemical Engineering Research
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• v.46 no.3
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• pp.581-584
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• 2008

The catalyst carriers of the mesoporous layer compounds were prepared to carry out the partial oxidation of methane(POM) to hydrogen. The catalytic activities of POM to hydrogen were investigated over Ru(3)/SPK and Ru(3)/SPM catalyst in a fixed bed flow reactor under atmosphere. In addition, the catalysts and carriers were characterized by BET, TEM, TPR. The BET surface areas of the silica-pillared $H^+-kenyaite$(SPK) and the silica-pillared $H^+-magadite$(SPM) were $760m^2/g$ and $810m^2/g$, repectively, and the average pore sizes were 3.0 nm and 2.6 nm, repectively. The nitrogen adsorption isotherms were type IV with developed hysteresis. The TEM showed that the mesoporous layer compounds were formed well. The Ru(3)/SPK and the Ru(3)/SPM catalyst were obtained high hydrogen yields(90%, 87%), and were kept constant high hydrogen yields even about 60 hours at 973 K, $CH_4/O_2=2$, $1.25{\times}10^{-5}g-Cat.hr/ml$. The TPR peaks of Ru(3)/SPK and the Ru(3)/SPM catalyst showed the similar reducibilities around 453 K and 413 K. It could be suggested that SPK and SPM had the physicochemical properties as oxidation catalyst carries from these analysis data.

• Journal of Korean Society of Environmental Engineers
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• v.39 no.3
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• pp.112-117
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• 2017

Ion exchange fiber, PADD was synthesized by the reaction between PAN based acrylic fiber and DETA with $AlCl_3{\cdot}6H_2O$, and was analyzed by FT-IR and SEM to investigate its characteristics. The experimental results of Cr(VI) removal by PADD were better fitted with Langmuir adsorption isotherm, and the maximum uptake value ($Q_{max}$) was calculated to be 6.93 mmol/g. The kinetic data can be well described by Lagergen pseudo-second order rate model. The Cr(VI) adsorption capacity of PADD was 4.11 mmol/g at pH 2, which shows the effect of pH changes on the removal of Cr(VI). The adsorption selectivity of Cr(VI) was higher than phosphate and As(V). Total ion exchange capacity of PADD was 4.70 mmol/g, which was measured by acid-base back titration.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.11
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• pp.1146-1152
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• 2005

Graft copolymers were synthesized from methylcellulose(MC) and acrylic acid(AA) with active carboxyl groups in the presence of potassium persulfate($K_2S_2O_8$) initiator to enhance adsorption capacity of toxic heavy metal such as $Pb^{2+}$ and $Cu^{2+}$ from wastewater. The resulting grafted copolymers(MC-g-AA/PAA) were mixture of the graft copolymers from MC and AA(MC-g-AA) and polyacrylic acid homopolymers(PAA). The degree of palling was increased with rising concentration of monomer and initiator under the reaction conditions at $60^{\circ}C$, 3 hrs. The water insoluble property of MC-g-AA showed more than 19.7% degree of grafting. So that it could be an adsorbent of heavy metals. Adsorption characteristics of the MC-g-AA were evaluated depending on the degree of grading, pH of wastewater, adsorption time, dosage of MC-g-AA and concentration of heavy metals in the different conditions. Degree of grafting, and initial concentration of heavy metal ions increased, the adsorption amount of $Pb^{2+}$ and $Cu^{2+}$ increased, but added MC-g-AA increased, the adsorption amount per unit weight of $Pb^{2+}$ and $Cu^{2+}$ decreased. The MC-g-AA showed the high $Pb^{2+}$ and $Cu^{2+}$ adsorption amount in the range pH $4{\sim}6$. Also all of $Pb^{2+}$ and $Cu^{2+}$ ions reached in adsorption equilibrium in neighborhood 4 hours. The adsorption of heavy metals described by Freundlich isotherm, it was determined the value of l/n of $Pb^{2+}$ and $Cu^{2+}$ that 0.4294 and 0.3453, respectively.