In this study, the adsorption/desorption performance of toluene was evaluated using zeolite adsorbent to replace activated carbon with one-off and ignition characteristics. For the proper operation of the VOCs adsorption/desorption and condensate recovery steps, the operating range by various adsorption/desorption temperatures was selected. The adsorbent is a bead-type zeolite, which was put into an adsorption tower of 10 LPM scale. As a result, it was demonstrated that 0.079 mg/g was adsorbed at a low temperature (20°C) during adsorption. In the case of desorption, it was found that VOCs adsorbed on the adsorbent were completely recovered after the desorption operation at 220°C for about 160 minutes. However, in the heating rate step for desorption, it was not possible to maintain an appropriate heating rate by filling the tower with zeolite. This was complemented by applying a copper plate with high thermal conductivity, and it was shown that the time was shortened by about 10 minutes or more. When VOCs are emitted at high concentrations during the desorption process, they can be reused as energy resources through low-temperature maintenance, and a condensation method was attempted. The efficiency of condensing chiller (cooler) with temperature control and liquid nitrogen condensing was compared. It was found that the chiller condensing efficiency increased as the temperature decreased. In the case of liquid nitrogen condensation, the liquid nitrogen temperature was maintained at -196°C, showing a stable efficiency of 90%.

To develop flexible adsorbents for compact volatile organic compound (VOC) air purifiers, flexible as-spun zeolite fibers are prepared by an electrospinning method, and then zeolite particles are exposed as active sites for VOC (toluene) adsorption on the surface of the fibers by a thermal surface partial etching process. The breakthrough curves for the adsorption and temperature programmed desorption (TPD) curves of toluene over the flexible zeolite fibers is investigated as a function of the thermal etching temperature by gas chromatography (GC), and the adsorption/desorption characteristics improves with an increase in the thermal surface etching temperature. The effect of acidity on the flexible zeolite fibers for the removal of toluene is investigated as a function of the SiO2/Al2O3 ratios of zeolites. The acidity of the flexible zeolite fibers with different SiO2/Al2O3 ratios is measured by ammonia-temperature-programmed desorption (NH3-TPD), and the adsorption/desorption characteristics are investigated by GC. The results of the toluene adsorption/desorption experiments confirm that a higher SiO2/ Al2O3 ratio of the flexible zeolite fibers creates a better toluene adsorption/desorption performance.

본 연구에서는 Na형 Faujasite 제올라이트 분리막의 프로필렌/프로페인 분리 거동을 예측하기 위하여 제올라이트 13X 입자의 프로필렌 및 프로페인 단일기체에 대한 중량식흡착 거동을 관찰하고자 하였다. 제올라이트 13X 입자의 프로필렌 및 프로페인에 대한 중량식흡착 거동은 자성부유평형저울(MSB)을 이용하여 323, 343, 363 K의 온도와 0.02-1 bar의 압력 범위에서 0.1 bar씩 증가시키면서 측정되었다. 그 결과, 온도가 증가할수록 프로필렌 및 프로페인의 흡착량은 감소하였으며, 프로필렌/프로페인의 흡착 선택도는 증가하였다. 또한 흡착 온도가 증가함에 따라 프로필렌과 프로페인의 확산계수는 증가하여 아레니우스 식을 따랐고, 프로필렌/프로페인 확산 선택도는 323 K에서 0.9753으로 최대값을 가졌다. 흡착 특성을 통해 분리막의 투과선택도를 계산하였고, Na형 Faujasite 제올라이트 분리막의 단일 기체 투과 특성과 비교하였다. 그 결과 계산된 투과선택도와 측정된 투과선택도가 모두 323 K에서 최대값을 갖는 것을 확인하였다. 따라서 본 연구에서는 중량식 흡착법으로 예측된 분리막의 프로필렌/프로페인 분리거동 예측이 합리적이며 또한 표면확산에 기반한 프로필렌/프로페인 분리용 제올라이트 분리막의 분리성능예측에 적용될 수 있음을 알 수 있었다.

Adsorption technology can effectively handle the volatile organic compounds (VOCs) from waste gas. However the adsorption of VOCs at elevated temperature (>30oC) and high humidity conditions results in competitive adsorption between VOCs and the moisture. Furthermore, physical adsorption at an elevated temperature is the cause of degradation in the regeneration process performance. In this study, toluene as waste organic solvent in air at elevated temperature and high humidity was used to measure performance. The effects of the SiO2/Al2O3 ratio of zeolites, the adsorbent material coated on adsorption regenerative rotors, on the adsorption performance of toluene with respect to temperature (30~50oC) and relative humidity (50~90%RH) have been investigated. The adsorption of toluene decreased as relative humidity and adsorption temperature rose. The result shows that Htype ZSM5 (SiO2/Al2O3=100) zeolite exhibited the highest adsorption capacity for toluene at elevated temperature and humidity conditions. The physical and chemical adsorption of toluene on acid sites of zeolite were confirmed by this study.

본 연구는 AgX (Ag-함침 X zeolite)에 의해 고방사성해수폐액 (HSW)의 발생초기에 함유되어 있는 고방사성 요오드(131I)의 흡착, 제거를 목표로 수행하였다. AgX에 의한 I의 흡착 (AgX-I 흡착)은 AgX 내 Ag-함침농도가 증가할수록 증가하며, 함침농 도 30wt% 정도가 적당하였다. AgX (Ag-함침 약 30~35wt%)로부터 Ag의 침출농도는 해수폐액에 함유되어 있는 chloride 이 온에 의한 AgCl 침전 등으로 증류수보다 덜 침출 (<1 mg/L) 되었다. AgX-I 흡착은 초기 I 농도 0.01~10 mg/L의 경우 m/V (흡착제량/용액부피의 비)=2.5 g/L에서 99% 이상 흡착제거 되어 I의 효율적 제거가 가능함을 알 수 있다. AgX-I 흡착제거 는 해수폐액 보다는 증류수에서 수행하는 것이 효과적이고, 온도의 영향은 미미한 것 같으며, 흡착평형등온선은 Languir 보 다는 Freundlich 등온선으로 표현하는 것이 양호하였다. 한편 AgX-I 흡착속도는 유사 2차 속도식을 만족하고 있으며, 속도 상수 (k2)는 Ci 증가에 따라 감소하고 있지만, m/V 비 및 온도 증가에 따라서는 증가하고 있다. 이때 흡착 활성화에너지는 약 6.3 kJ/mol 로 AgX-I 흡착은 약한 결합형태의 물리적흡착이 지배적일 것으로 보인다. 그리고 열역학적 매개변수를 평가 (음수 값의 Gibbs 자유에너지 및 양수 값의 엔탈피)에 의해 AgX-I 흡착이 자발반응(정반응)의 흡열반응이며, 고온에서 반응 이 양호함을 나타내었다.

본 연구는 고방사성해수폐액 (HSW)으로부터 Barium (Ba)이 함침된 4A 제올라이트 (BaA)에 의한 고방사성핵종 중에 하나인 Sr의 흡착 제거를 수행하였다. BaA에 의한 Sr의 흡착 (BaA-Sr)은 Ba의 함침농도 20.2wt% 이상에서 Ba의 함침농도가 증가 할수록 감소하며 Ba 함침농도는 20.2wt% 정도가 적당하였다. 그리고 BaA-Sr 흡착은 BaA 내 4A에 의한 Sr 흡착 (4A-Sr)에 BaSO4 침전에 따른 Sr 공침이 첨가되어, Sr의 농도가 0.2 mg/L 이하 (HSW 내 실제 Sr 농도 수준)에서 BaA는 m/V (흡착제 량/용액 부피)=5 g/L, 4A는 m/V >20 g/L에서 99% 이상의 Sr 제거가 가능하였다. 이는 흡착제 단위 g 당 Sr의 처리용량 및 2 차 고체폐기물 (폐흡착제 등) 발생량 저감화 차원에서 BaA-Sr 흡착이 4A-Sr 흡착보다 우수함을 나타낸다. 또한 BaA-Sr 흡 착이 증류수보다 해수폐액에서 Sr의 제거능이 우수하여 HSW로부터 직접 Sr을 제거하는 데 효과적일 것으로 보인다. 반면 에 BaA에 의한 Cs의 흡착 (BaA-Cs)은 주로 BaA 내 4A에 의해서 이루어지고 있어 함침 Ba의 영향은 거의 없는 것 같다. 한 편 BaA-Sr 흡착속도는 유사 2차 속도식으로 표현할 수 있으며, Sr의 초기농도 및 V/m 비 증가에 따라서 속도상수 (k2)는 감 소하지만 평형흡착량 (qe)은 증가하고 있다. 그러나 용액의 온도증가에 따라서는 반대로 k2는 증가하지만 qe는 감소하고 있 다. BaA-Sr 흡착 활성화에너지는 약 38 kJ/mol 로 강력한 결합 형태를 이룬 화학흡착은 아니더라도 물리적 흡착보다 화학적 흡착이 지배적일 것으로 보인다.

In this study, CO₂ adsorbent was produced for minimizing energy loss due to ventilation within the building. For improved selectivity about low concentration of CO₂ in multiple-use facilities, the ball type adsorbent was modified from a commercial zeolite, alumina, alkali metals and activated carbon with mixing LiOH, binder, and H₂O. We measured specific surface area, pore characteristic, and crystal structure of the modified adsorbent. Effects of alkalization on the absorptive properties of the adsorbents were investigated. Continuous column tests (2,000 ppm) and batch chamber tests (4m3, 5,000ppm) showed that the modified adsorbent indicated about the selectivity of CO₂ more than 9.7% (0.613 mmol/g) compared with ordinary adsorbents and CO₂ removal efficiency of 88.8% within l hour, respectively. It was estimated that the modified adsorbent was applicable to indoor environments.

The conversion of coal fly ash into zeolites contributes to the mitigation of environmental problems and turns this by-product into useful material. In this work, zeolitic sorbents for CO₂ adsorption were prepared by waste fly ash from Boryeong coal power plants through the alkali fusion method including hydrothermal treatment at various ratios of NaOH/FA and NaAlO₂/FA. In addition, in order to improve the adsorption capacity for CO₂ molecules a few metal cations were impregnated into the synthesized zeolitic sorbents through the ion exchange. The fusion step could decompose the fly ash to very small amorphous particulate zeolite forms. The fly ash was converted into Na-P1 type with 0.5 NaOH/FA and Na-A type from the ratio of 0.53, NaAlO₂/FA. Although the crystallinity of Na-A increased with increasing temperature, Na-A was transformed into sodalite at 140℃. Thus, the optimum reaction temperature was determined to be 100℃. Alkali metal and alkaline earth metal cations were impregnated into the synthesized zeolite Na-P1 and Na-A through ion exchanged method. The completed zeolitic sorbents were applied to adsorption the CO₂. As a result of the examination, Ca²⁺ was found to be the best for CO₂ adsorption owing to its electrostatic interactions and acid-base surface properties.

The structure of nitrogen adsorption complex of fully dehydrated Cd2+ ion exchanged zeolite-X, |Cd46(N)18|[Si100Al92O384], was determined in the cubic space group Fd3 at 21(1) ℃ [a = 24.863(4) ] by single crystal X-ray diffraction analysis. The crystal was prepared by ion exchange in a flowing steam of 0.05 M aqueous solution Cd(NO3)2 : Cd(O2CCH3)2 = 1:1 for five days, followed by dehydration at 500℃ and 2×10-6 Tor. for two days, and exposured to 100 Tor. zeolitically dry nitrogen gas at 21(1) ℃. The structure was determined in atmosphere, and was refined within F0 〉 4Σ(F0) using reflection for which the final error can appear in indices R1 = 0.097 and wR2 = 0.150. In this structure, Cd2+ ions occupied four crystallographic sites. Nine Cd2+ ions filled the octahedral site I at the centers of hexagonal prisms (Cd-O = 2.452(16) a). Eight Cd2+ ions filled site I' (Cd-O = 2.324(19) a). The remaining 29 Cd2+ ions are found at two nonequivalent sites II (in the supercages) with occupancy of 11 and 18 ions. Each of these Cd2+ ions coordinated to three framework oxygens, either at 2.159(15) or 2.147(14) a, respectively. Eighteen nitrogen molecules were adsorbed per unit cell and three per supercage.

Zeolite에 의(依)한 의 흡착반응(吸着反應)에 영향(影響)을 미치는 열처리(熱處理)에 의(依)해 조사(調査)하고 배양실험(培養實驗)을 통하여 Zeolite에 흡착(吸着)된 의 소실량(消失量)을 조사(調査)하였다. Zeolite의 주구성점토광물(主構成粘土鑛物) Clinoptiolite와 mordenite였다. Zeolite에 의(依)한 의 흡착반응(吸着反應)은 4시간(時間) 진탕으로 흡착평형(吸着平衡)에 도달(到達)하였다. 열처리온도(熱處理溫度)가 높을수록 치환성(置換性) 의 합량(合量)은 증가(增加)하였으나 의 흡착량(吸着量)은 감소(減少)하였다. 유안(硫安)을 처리(處理)한 토양(土壤)을 담수상태(湛水狀態)에서 배양(培養)한 결과(結果) 시간(時間)이 경과(經過)할수록 토양중(土壤中) 잔류량(殘留量)이 감소(減少)한 반면(盤面) Zeolite에 흡착(吸着)된 는 동일기간(同一期間) 내(內)에 소실(消失)되지 않았다. 그러므로 Zeolite에 흡착(吸着)된 은 여러 가지 작용(作用)에 의(依)한 소실(消失)에 대(對)해 저항성(抵抗性)이 크다고 할 수 있다.

국내 포항 소재 R사의 구룡포산 천연 제올라이트의 물리·화학적 특성을 규명하기 위해 X-선 회절 분석, X-선 형광 분석, 열 시차·열 중량 분석, 양이온 교환능 분석 및 세슘(Cs), 스트론튬(Sr) 흡착 실험을 수행하였다. X- 선 회절 분석 결과 모데나이트, 휼란다이트, 클라이놉티로라이트 및 일라이트와 같은 광물이 함유되어 있으며, X- 선 형광 분석 결과 SiO2, Al2O3, CaO, K2O, MgO, Fe2O3 및 Na2O 원소가 함유되어 있었다. 양이온 교환능은 148.6 meq/100 g이었으며 열시차 및 열중량 분석 결과 600℃까지 열적으로 안정성이 우수한 것을 확인하였다. 시 간에 따른 흡착 평형 실험 결과 세슘(Cs)의 경우 30분이내 스트론튬(Sr)의 경우 8시간이내에 평형에 도달하였으며 세슘(Cs) 및 스트론튬(Sr)의 흡착률은 각각 80% 및 18%를 보이고 있었다. 단일 성분 등온 흡착 실험 결과 Langmuir model에 부합하였으며 세슘(Cs) 최대 흡착량은 131.5 mg/g으로 높게 나타났으며 반면 스트론튬(Sr) 최 대 흡착량은 29.5 mg/g로 낮은 흡착량을 나타내었다. 본 연구에 사용된 천연 제올라이트의 경우 클라이놉티로라 이트, 휼란다이트 및 모데나이트와 같은 8-ring을 포함하는 광물의 함량이 높아 세슘(Cs)에 대한 높은 선택성을 보 여주고 있다.

The characteristics of heavy metal ion (Ni2+, Zn2+, and Cr3+) adsorption by zeolite synthesized from Jeju scoria using the fusion and hydrothermal method, were studied. The synthetic zeolite was identified as a Na-A zeolite by X-ray diffraction analysis and scanning electron microscopy images. The equilibrium of heavy metal ion adsorption by synthetic zeolite was reached within 60 min for Ni2+ and Zn2+, and 90 min for Cr3+. The uptake of heavy metal ions increased with increasing pH in the range of pH 3-6 and the uptake decreased in the order of Cr3+ > Zn2+ > Ni2+. For initial heavy metal concentrations of 20-250 mg/L at nonadjusted pH, the adsoption of heavy metal ions was well described by the pseudo second-order kinetic model and was well fitted by the Langmuir isotherm model. The maximum uptake of heavy metal ions obtained from the Langmuir model, decreased in the order of Zn2+ > Ni2+ > Cr3+, differing from the effect of pH on the uptake, which was mainly based on the different pH of the solutions.

A zeolitic material (Z-Y2) was synthesized from Coal Fly Ash (CFA) using a fusion/hydrothermal method under low-alkali condition (NaOH/CFA = 0.6). The adsorption performance of the prepared zeolite was evaluated by monitoring its removal efficiencies for Sr and Cs ions, which are well-known as significant radionuclides in liquid radioactive waste. The XRD (X-ray diffraction) patterns of the synthesized Z-Y2 indicated that a Na-A type zeolite was formed from raw coal fly ash. The SEM (scanning electron microscope) images also showed that a cubic crystal structure of size 1~3㎼ was formed on its surface. In the adsorption kinetic analysis, the adsorption of Sr and Cs ions on Z-Y2 fitted the pseudo-second-order kinetic model well, instead of the pseudo-first-order kinetic model. The second-order kinetic rate constant (k2) was determined to be 0.0614 g/mmol·min for Sr and 1.8172 g/mmol·min for Cs. The adsorption equilibria of Sr and Cs ions on Z-Y2 were fitted successfully by Langmuir model. The maximum adsorption capacity (qm) of Sr and Cs was calculated as 1.6846 mmol/g and 1.2055 mmol/g, respectively. The maximum desorption capacity (qdm) of the Na ions estimated via the Langmuir desorption model was 2.4196 mmol/g for Sr and 2.1870 mmol/g for Cs. The molar ratio of the desorption/adsorption capacity (qdm/qm) was determined to be 1.44 for Na/Sr and 1.81 for Na/Cs, indicating that the amounts of desorbed Na ions and adsorbed Sr and Cs ions did not yield an equimolar ratio when using Z-Y2.

The adsorption characteristics of Cu ions were studied using the zeolite Na-A synthesized from Jeju volcanic rocks. The effects of various operating parameters such as initial concentration of Cu ions, contact time, solution pH, and solution temperature were investigated in batch experiments. The adsorption of Cu ions by Na-A zeolite was fitted well by pseudo-second-order kinetics and the Langmuir isotherm model. The maximum adsorption capacity determined using the Langmuir isotherm model was 152.95 mg/g. In addition, the adsorption of Cu ions by zeolite Na-A was primarily controlled by particle diffusion model in comparison with the film diffusion model. As the temperature increased from 303 K to 323 K, ΔG˚ decreased from -2.22 kJ/mol to –3.41 kJ/mol, indicating that the adsorption of Cu ions by Na-A zeolite is spontaneous process.

In this study, zeolite (Z-C2) was synthesized using a fusion/hydrothermal method on coal fly ash (FA) discharged from a thermal power plant in the Ulsan area and then analyzed via scanning electron microscopy (SEM) and X-ray diffraction (XRD). The Z-C2 was characterized in terms of mineralogical composition and morphological analysis. The XRD results showed that its peaks had the characteristics of Na-A zeolite in the range of 2θ of 7.18~34.18. The SEM images confirmed that the Na-A zeolite crystals had a chamfered-edge crystal structure almost identical to that of the commercial zeolite. The adsorption kinetics of Cu, Co, Mn and Zn ions by Z-C2 were described better by the pseudo-second-order kinetic model more than by the pseudo-first-order kinetic model. The Langmuir model fitted the adsorption isotherm data better than the Freundlich model did. The maximum adsorption capacities of Cu, Co, Mn and Zn ions obtained from the Langmuir model were in the following order : Cu (94.7 mg/g) > Co (77.7 mg/g) > Mn (57.6 mg/g) > Zn (51.1 mg/g). These adsorption capacities are regarded as excellent compared to those of commercial zeolite.

In order to investigate the adsorption characteristics for Sr ion using the Na-X zeolite synthesized from coal fly ash, batch tests and response surface analyses were carried out. The adsorption kinetic data for Sr ions, using Na-X zeolite, fitted well with the pseudo-second-order model. The uptake of Sr ions followed the Langmuir isotherm model, with a maximum adsorption capacity of 196.46 mg/g. Thermodynamic studies were conducted at different reaction temperatures, with the results indicating that Sr ion adsorption by Na-X zeolite was an endothermic (ΔHo>0) and spontaneous (ΔGo<0) process. Using the response surface methodology of the Box-Behnken method, initial Sr ion concentration (X1), initial temperature (X2), and initial pH (X3) were selected as the independent variables, while the adsorption of Sr ions by Na-X zeolite was selected as the dependent variable. The experimental data fitted well with a second-order polynomial equation by multiple regression analysis. The value of the determination coefficient (R2=0.9937) and the adjusted determination coefficient (adjusted R2=0.9823) was close to 1, indicating high significance of the model. Statistical results showed the order of Sr removal based on experimental factors to be initial pH > initial concentration > temperature.

국내 경상북도 포항 지역에서 채취한 6종의 천연 제올라이트를 X-선 회절, X-선 형광분석, 열 시차 분석, 열중량 분석 및 양이온교환능 분석을 통해 특성분석을 수행하였다. 이들 제올라이트의 주 성분은 구룡포A (Ku-A), 구룡포B (Ku-B), 구룡포C (Ku-C), 동해A (Dh-A), 동해B (Dh-B), 동해C (Dh-C) 모두 모데나이트, 알바이트 및 석영이 함유되어 있었다. 6종의 제올라이트는 Si, Al, Na, K, Mg, Ca, Fe을 함유하고 있었으며 구룡포C (Ku-C) 제올라이트의 양이온 교환능이 다른 지역의 제올라 이트 보다 높게 나타났다. 6종의 천연 제올라이트를 이용하여 Pb2+, Cd2+ 및 Cu2+ 등의 중금속 이온을 제거하는데 소요되는 반응 시간의 효과를 비교하였다. 6종의 천연 제올라이트 모두 Pb2+, Cd2+ 및 Cu2+ 제거율이 매우 낮게 나타났다. 이는 6종의 천연 제올라이트에 함유된 제올라이트의 함량이 매우 낮기 때문으로 판단된다. 본 연구 결과는 제올라이트 광석의 중금속 흡착능력은 제올라이트의 함량, 즉 광석의 품위에 크게 의존되는 경향을 보여주고 있다.

The adsorption characteristics of Sr and Cs ions were investigated by using PS-zeolite beads prepared by immobilizing zeolite with polysulfone (PS). The adsorption kinetics of Sr and Cs ions by PS-zeolite beads was described well by the pseudo-second-order model. The maximum adsorption capacities of Sr and Cs ions calculated from Langmuir isotherm model were 65.0 mg/g and 76.4 mg/g, respectively. In the binary system of Sr ion and Cs ion, the adsorption capacities of each ion decreased with increasing mole ratio of mixed counterpart ion, and Cs ion showed the higher hinderance than Sr ion. We found that thermodynamic properties of Sr and Cs ions on absorption reaction were spontaneous and endothermic at 293 to 323 K.