• Title/Summary/Keyword: 흡착과 탈착

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Arsenic Removal Mechanism of the Residual Slag Generated after the Mineral Carbonation Process in Aqueous System (광물탄산화 공정 이후 발생하는 잔사슬래그의 수계 내 비소 제거 기작)

  • Kim, Kyeongtae;Latief, Ilham Abdul;Kim, Danu;Kim, Seonhee;Lee, Minhee
    • Economic and Environmental Geology
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    • v.55 no.4
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    • pp.377-388
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    • 2022
  • Laboratory-scale experiments were performed to identify the As removal mechanism of the residual slag generated after the mineral carbonation process. The residual slags were manufactured from the steelmaking slag (blast oxygen furnace slag: BOF) through direct and indirect carbonation process. RDBOF (residual BOF after the direct carbonation) and RIBOF (residual BOF after the indirect carbonation) showed different physicochemical-structural characteristics compared with raw BOF such as chemical-mineralogical properties, the pH level of leachate and forming micropores on the surface of the slag. In batch experiment, 0.1 g of residual slag was added to 10 mL of As-solution (initial concentration: 203.6 mg/L) titrated at various pH levels. The RDBOF showed 99.3% of As removal efficiency at initial pH 1, while it sharply decreased with the increase of initial pH. As the initial pH of solution decreased, the dissolution of carbonate minerals covering the surface was accelerated, increasing the exposed area of Fe-oxide and promoting the adsorption of As-oxyanions on the RDBOF surface. Whereas, the As removal efficiency of RIBOF increased with the increase of initial pH levels, and it reached up to 70% at initial pH 10. Considering the PZC (point of zero charge) of the RIBOF (pH 4.5), it was hardly expected that the electrical adsorption of As-oxyanion on surface of the RIBOF at initial pH of 4-10. Nevertheless it was observed that As-oxyanion was linked to the Fe-oxide on the RIBOF surface by the cation bridge effect of divalent cations such as Ca2+, Mn2+, and Fe2+. The surface of RIBOF became stronger negatively charged, the cation bridge effect was more strictly enforced, and more As can be fixed on the RIBOF surface. However, the Ca-products start to precipitate on the surface at pH 10-11 or higher and they even prevent the surface adsorption of As-oxyanion by Fe-oxide. The TCLP test was performed to evaluate the stability of As fixed on the surface of the residual slag after the batch experiment. Results supported that RDBOF and RIBOF firmly fixed As over the wide pH levels, by considering their As desorption rate of less than 2%. From the results of this study, it was proved that both residual slags can be used as an eco-friendly and low-cost As remover with high As removal efficiency and high stability and they also overcome the pH increase in solution, which is the disadvantage of existing steelmaking slag as an As remover.

Geochemical Characteristics of Soil Solution from the Soil Near Mine Tailing Dumps and the Contamination Assessment in Duckum Mine (토양수의 자구화학특성에 따른 금속폐광산 광미야적장주변 토양오염평가: 덕음광산)

  • 이상훈;정주연
    • Economic and Environmental Geology
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    • v.37 no.1
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    • pp.61-72
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    • 2004
  • The soil samples were collected from the paddy field near the mine tailing dumps in the abandoned Duckum mine in Korea. In the laboratory, the soil solution was extracted from the soil using centrifuge, and analysed for the chemical composition. Physical and chemical soil properties were also analysed. Kaolinite is the main clay minerals in the paddy soil and the CEC value is therefore relatively low. Nearly all soil samples show enrichment in their trace elemental concentrations(Cd, Cu, Pb and Zn) compared with natural background level. Some soil samples exceed the soil remediation intervention values for Cd, Pb and Zn and target value for Cu, when compared with Dutch standard, whereas As, Ni and Cr are in normal range. Lead concentrations in some samples near the mine tailing dumps also exceed the standard for remediation act for agricultural area set by Korean soil conservation law. The trace elemental concentrations are higher in the paddy soil nearer the mine tailing dumps and lower for the samples from distance. Similar trend with distance is found for the soil solution chemistry but the decrease with distance from the mine tailing dumps are sharper than the changes in soil chemistry. Cadmium, Cu and Pb concentrations in the soil solution are very low, ranging from a tenth and hundredths to a maximum of several mg/l, whereas their concentrations in soils are highly enriched for natural background. Most of the trace elements are thought to be either removed by reduced iron sulphides or iron oxides, depending on the redox changes. Geochemical equilibrium modelling indicate the presence of solubility controlling solid phases for Cd and Pb, whereas Zn and Cu might have been controlled by adsorption/desorption processes. Although pollutants migration through solution phase are thought to be limited by adsorption onto various Fe, Mn solid phases, the pollutants exist as easily releasable fractions such as exchangeable site. In this case, the paddy soil would act as pollutant pool, which will supply to plants in situ. whenever the geochemical conditions favour.

Assessment Techniques of Heavy Metal Bioavailability in Soil - A critical Review (토양 중 중금속 생물유효도 평가방법 - 총설)

  • Kim, Kwon-Rae;Owens, Gary;Naidu, Ravi;Kim, Kye-Hoon
    • Korean Journal of Soil Science and Fertilizer
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    • v.40 no.4
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    • pp.311-325
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    • 2007
  • The concept of metal bioavailability, rather than total metal in soils, is increasingly becoming important for a thorough understanding of risk assessment and remediation. This is because bioavailable metals generally represented by the labile or soluble metal components existing as either free ions or soluble complexed ions are likely to be accessible to receptor organismsrather than heavy metals tightly bound on soil surface. Consequently, many researchers have investigated the bioavailability of metals in both soil and solution phases together with the key soil properties influencing bioavailability. In order to study bioavailability changes various techniques have been developed including chemical based extraction (weak salt solution extraction, chelate extraction, etc.) and speciation of metals using devices such as ion selective electrode (ISE) and diffusive gradient in the thin film (DGT). Changes in soil metal bioavailability typically occur through adsorption/desorption reactions of metal ions exchanged between soil solution and soil binding sites in response to changes in environment factors such as soil pH, organic matter (OM), dissolved organic carbon (DOC), low-molecular weight organic acids (LMWOAs), and index cations. Increasesin soil pH result in decreases in metal bioavailability through adsorption of metal ions on deprotonated binding sites. Organic matter may also decrease metal bioavailability by providing more negatively charged binding sites, and metal bioavailability can also be decreases as concentrations of DOC and LMWOAs increase as these both form strong chelate complexeswith metal ions in soil solution. The interaction of metal ions with these soil properties also varies depending on the soil and metal type.

A study on the calibration characteristics of organic fatty acids designated as new offensive odorants by cryogenic trapping-thermal desorption technique (유기지방산 신규악취물질에 대한 저온농축 열탈착방식 (Thermal desorber)의 검량특성 연구)

  • Ahn, Ji-Won;Kim, Ki-Hyun;Im, Moon-Soon;Ju, Do-Weon
    • Analytical Science and Technology
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    • v.22 no.6
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    • pp.488-497
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    • 2009
  • In this study, analytical methodology for several organic fatty acids (OFA: propionic acid (PA), butyric acid (BA), isovaleric acid (IA), and valeric acid (VA)) designated as new offensive odorants in Korea (as of year 2010) was investigated along with some odorous VOCs (styrene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, and isobutyl alcohol). For this purpose, working standards (WS) containing all of these 13 compounds were loaded into adsorption tube filled with Tenax TA, and analyzed by gas chromatography (GC) system thermal desorber interfaced with. The analytical sensitivities of organic fatty acids expressed in terms of detection limit (both in absolute mass (ng) and concentration (ppb)) were lower by 1.5-2 times than other compounds (PA: 0.24 ng (0.16 ppb), BA: 0.19 ng (0.11 ppb), IA: 0.15 ng (0.07 ppb), and VA: 0.28 ng (0.13 ppb)). The precision of BA, IA, and VA, if assessed in terms of relative standard error (RSE), maintained above 5%, while the precison of other compounds were below 5%. The reproducibility of analysis improved with the aid of internal standard calibration (PA: $1.1{\pm}0.4%$, BA: $10{\pm}0.46$, IA; $12{\pm}0.3%$, VA: $4{\pm}0.1%$), respectively. The results of this study showed that organic fatty acid can be analyzed using adsorption tube and thermal desorber in a more reliable way to replace alkali absorption method introduced in the odor prevention law of the Korea Ministry of Environment (KMOE).

Ammonia Decomposition over Ni Catalysts Supported on Zeolites for Clean Hydrogen Production (청정수소 생산을 위한 암모니아 분해 반응에서 Ni/Zeolite 촉매의 반응활성에 관한 연구)

  • Jiyu Kim;Kyoung Deok Kim;Unho Jung;Yongha Park;Ki Bong Lee;Kee Young Koo
    • Journal of the Korean Institute of Gas
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    • v.27 no.3
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    • pp.19-26
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    • 2023
  • Hydrogen, a clean energy source free of COx emissions, is poised to replace fossil fuels, with its usage on the rise. Despite its high energy content per unit mass, hydrogen faces limitations in storage and transportation due to its low storage density and challenges in long-term storage. In contrast, ammonia offers a high storage capacity per unit volume and is relatively easy to liquefy, making it an attractive option for storing and transporting large volumes of hydrogen. While NH3 decomposition is an endothermic reaction, achieving excellent low-temperature catalytic activity is essential for process efficiency and cost-effectiveness. The study examined the effects of different zeolite types (5A, NaY, ZSM5) on NH3 decomposition activity, considering differences in pore structure, cations, and Si/Al-ratio. Notably, the 5A zeolite facilitated the high dispersion of Ni across the surface, inside pores, and within the structure. Its low Si/Al ratio contributed to abundant acidity, enhancing ammonia adsorption. Additionally, the presence of Na and Ca cations in the support created medium basic sites that improved N2 desorption rates. As a result, among the prepared catalysts, the 15 wt%Ni/5A catalyst exhibited the highest NH3 conversion and a high H2 formation rate of 23.5 mmol/gcat·min (30,000 mL/gcat·h, 600 ℃). This performance was attributed to the strong metal-support interaction and the enhancement of N2 desorption rates through the presence of medium basic sites.

Application of Adsorption Sampling and Thermal Desorption with GC/MS Analysis for the Measurement of Low-Molecular Weight PAHs in Ambient Air (환경대기 중 저분자 PAHs 측정을 위한 흡착-열탈착-GC/MS 방법의 적용)

  • Seo, Seok-Jun;Seo, Young-Kyo;Hwang, Yoon-Jung;Jung, Dong-Hee;Baek, Sung-Ok
    • Journal of Korean Society for Atmospheric Environment
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    • v.30 no.4
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    • pp.362-377
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    • 2014
  • Polycyclic aromatic hydrocarbons (PAHs) have been of particular concern since they are present both in the vapor and particulate phases in ambient air. In this study, a simple method was applied to determine the vapor phase PAHs, and the performance of the new method was evaluated with a conventional method. The simple method was based on adsorption sampling and thermal desorption with GC/MS analysis, which is generally applied to the determination of volatile organic compounds (VOCs) in the air. A combination of Carbotrap (300 mg) and Carbotrap-C (100 mg) sorbents was used as the adsorbent. Target compounds included two rings PAHs such as naphthalene, acenaphthylene, and acenaphthene. Among them, naphthalene was listed as one of the main HAPs together with a number of VOCs in petroleum refining industries in the USA. For comparison purposes, a method based on adsorption sampling and solvent extraction with GC/MS analysis was adopted, which is in principle same as the NIOSH 5515 method. The performance of the adsorption sampling and thermal desorption method was evaluated with respect to repeatabilities, detection limits, linearities, and storage stabilities for target compounds. The analytical repeatabilities of standard samples are all within 20%. Lower detection limits was estimated to be less than 0.1 ppbv. In the results from comparison studies between two methods for real air samples. Although the correlation coefficients were more than 0.9, a systematic difference between the two groups was revealed by the paired t-test (${\alpha}$=0.05). Concentrations of two-rings PAHs determined by adsorption and thermal desorption method consistently higher than those by solvent extraction method. The difference was caused by not only the poor sampling efficiencies of XAD-2 for target PAHs and but also sample losses during the solvent extraction and concentration procedure. This implies that the levels of lower molecular PAHs tend to be underestimated when determined by a conventional PAH method utilizing XAD-2 (and/or PUF) sampling and solvent extraction method. The adsorption sampling and thermal desorption with GC analysis is very simple, rapid, and reliable for lower-molecular weight PAHs. In addition, the method can be used for the measurement of VOCs in the air simultaneously. Therefore, we recommend that the determination of naphthalene, the most volatile PAH, will be better when it is measured by a VOC method instead of a conventional PAH method from a viewpoint of accuracy.

Preparation of High-capacity Ceramic Catalytic Support from Gibbsite (깁사이트를 이용한 고기능 세라믹 촉매담체의 제조)

  • Park, Byung-Ki;Suh, Jeong-Kwon;Lee, Jung-Min;Suhr, Dong-Soo
    • Journal of the Korean Ceramic Society
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    • v.39 no.3
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    • pp.245-251
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    • 2002
  • We prepared γ-alumina beads using the amorphous alumina, obtained by fast calcination of gibbsite, and its were immersed in aqueous solution of the mixture of 21.87% nitric acid and 28.57% acetic acid. The beads thus were hydrothermaly treated at 200$^{\circ}$C for 3h, and were investigated changes of crystal, pore characteristics, $N_2$ adsorption and desorption isotherms, mechanical strengths and thermal resistance. Acicular platelet crystals of 0.1∼0.3${\mu}$m were transformed into acicular boehmite crystals of 1∼2${\mu}$m having the same crystal structure. Through this changes, we found that reversible phase transformation due to hydrothermal reaction took placed between boehmite and ${\gamma}$-alumina. In comparison to the ${\gamma}$-alumina bead before hydrothermal treatment, $N_2$ adsorption capacity was increased from 450㎖/g to 670㎖/g, and pore volume between 100${\AA}$ and 1000${\AA}$ was increased form 0.15㎖/g to 0.77㎖g, and mechanical strength was increased form 1.4MPa to 2.2MPa. Also, it showed the remarkable thermal resistance which sustained ${\theta}$-alumina crystal structure and pores between 100${\AA}$ and 1000${\AA}$ at 1000$^{\circ}$C in 40vol% steam.

The Cracking Reaction of Vacuum Gas Oil on Mordenite Modified by HF and Steaming (불화수소산과 스팀처리한 모더나이트상에서 진공가스유의 분해반응)

  • Lee, Kyong-Hwan;Ha, Baik-Hyon
    • Applied Chemistry for Engineering
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    • v.7 no.5
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    • pp.925-937
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    • 1996
  • Three types of mordenites treated by steaming($SM_{6.5}$), HF solution for $SM_{6.5}(FM_a)$ and HF solutlon+steaming for $SM_{6.5}(FM_b)$ were prepared and used as cracking catalysts of vacuum gas oil. These samples were analysed by XRF and XPS for average and surface Si/Al atomic ratio, XRD for unit cell constants, nitrogen adsorption/desorption for porosity, pyridine-IR for acidic properties. In comparison with three type samples, $SM_{6.5}$ had a lot of acid amount and showed micropore volume mostly(>85% to total volume). Dealuminated $FM_a$, compared with $SM_{6.5}$, was decreased a little in acid amount and improved for porosity. Also, $FM_b$ was decreased further in acid amount and developed in mesopore dramatically. The catalytic activity and the yield of gasoline, kerosine+diesel and branched aromatic over the modified mordenites which have developed mesopore were improved. This is due to limited access of diffusion of large molecules within pore of the modified mordenites.

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Analysis of volatile aroma compounds from vanilla perfume using headspace disk type monolithic material sorptive extraction (시료상층부 원판 형태 단일 다공성 물질을 이용한 바닐라 향수의 휘발성 아로마 성분 추출 분석)

  • Son, Hyun-Hwa;Lee, Dong-Sun
    • Analytical Science and Technology
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    • v.24 no.6
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    • pp.421-428
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    • 2011
  • In this study, headspace disk type monolithic material sorptive extraction (HS-MMSE) was developed, validated and applied to the analysis of volatile aroma compounds from vanilla perfume by gas chromatography -mass spectrometry (GC/MS). HS-MMSE uses monolithic material (MonoTrap) based on silica bonded with octadecyl silane (ODS) and activated carbon as a sorbent. Aroma compounds was adsorbed onto the MonoTrap in headspace and extracted by only 100 ${\mu}L$ of solvent. Total 12 volatile compounds from vanilla perfume were successfully analyzed using HS-MMSE. The influence of extractive parameters was investigated and optimized, using benzyl acetate, linalyl acetate, vanillin, ethyl vanillin as target compounds. Under the optimum condition, the limit of detection (S/N = 3) and the limit of quantification (S/N = 10) of proposed method for the target compounds were obtained within the range of 8.35~13.76 ng and 27.82~45.88 ng, respectively. The method showed good linearity with correlation coefficient more than 0.9888, satisfactory recovery and reproducibility. These results showed that HS-MMSE using disk type MonoTrap is a new promising technique for the analysis of volatile aroma compounds from vanilla perfume.

분무진공동결건조기 개발

  • Ryu, Gyeong-Ha;Ban, Byeong-Min;Kim, Jae-Hyeong;Son, Sang-Ho
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.258-258
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    • 2013
  • 최근 건조 제품의 양질화, 고급화 및 편의화가 요구되어 이를 충족시키기 위한 새로운 건조방법이 계속 개발 되어 왔다. 이러한 방법들 중에서 저온과 진공하에서 건조가 이루어지는 진공 동결 건조는 가장 완벽한 건조 방법으로 최근 실용화 되고 있다. 진공동결건조란 건조의 한 종류로 수분을 함유한 시료를 동결시킨 후 진공펌프를 이용하여 수증기압을 3중점 이하로 낮추어 얼음을 직접 증기로 만드는 승화의 원리에 의해서 얻어진다. 분무진공동결건조의 특징은 (1) 물리적구조의 보존성, (2) 화학적인 안정성, (3) 생물학적인 활동의 보존성, (4) 제품의 높은 복원성 및 재생성이다. 따라서 분무진공동결건조 기술은 크게 진공, 분무, 동결, 건조, 멸균 등과 같은 요소기술의 복합기술이라 할 수 있다. 분말을 제조하기 위해서 진공동결건조 후 분쇄하는 방법을 사용하나 본 방법에서는 정밀화학품 제조를 위해서 분무진공동결건조 방식을 사용한다. 이를 통하여 적당한 크기인 5~10 um의 입경 제조가 가능하고, 공기동력학적인 입경이 기존 방식에 비해 작아서 허파까지의 운반효율이 1.5~2배 우수하다. 화학, 의학 분야에서의 분무동결 건조는 주로 민감한 제품, 즉 생물학적 고유성의 손상 없이 물을 제거하는데 사용되어 영구적으로 저장 가능한 상태로 보관할 수 있으며 물의 첨가로 원상태로 복구할 수 있어서 매우 각광을 받고 있다. 의약용 냉동건조 제품은 항생물질, 박테리아, 혈청, 백신, 검사 약물, 단백질을 포함하는 생물공학 제품들, 세포, 섬유, 화학제품 등이 있으며 주로 vial 또는 ampule 상태로 건조가 이루어진다.본 연구에서는 원료를 $-194^{\circ}C$의 액체질소에 분무시켜 동결된 미립자를 형성한 후 진공 및 저온상태에서얼음의 승화(sublimation)에 기반한 1차 건조와 수증기 탈착(desorption)에 기초한 2차 건조 과정으로 구성된 분무진공동결건조기를 개발하였다. 분무동결 과정의 해석을 통해 2유체식 노즐을 통해 분무된 미세 입경의 액적이 액체 질소 표면까지 도달하는 회수률, 분무 노즐의 위치, 운전 조건 및 용기의 설계의 최적화를 수행하였다. 초기 액적속도, 분무노즐의 높이, 흡입구 추가에 따른 액적 유동 및 회수의 특성을 제시하였으며 이를 통한 분사시스템 고도화 가능성을 제시하였다. 구형의 미세 입자가 적층된 제품의 동결건조 공정의 해석은 흡착승화 모델(sorption sublimation model)을 기반으로 다음과 같은 열전달, 물질전달, 상변화 모델을 고려하여 유도되었다. 분무노즐 및 냉동/진공 배기계 시작품을 개발하여, 표면의 고다공도를 갖춘 입경 3~20 m 정도의 시료를 얻을 수 있으며, 동역학적 입경 5 m 충족함을 확인하였다.

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