The physicochemical similarities of hydrogen isotopes have made their separation a challenging task. Conventional methods such as cryogenic distillation, Girdler sulfide process, chromatography, and thermal cycling absorption have low separation factors and are energy-intensive. To overcome these limitations, research has focused on kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS) effects for selective separation of hydrogen isotopes. Porous materials such as metal-organic frameworks (MOF), covalent organic frameworks (COF), zeolites, carbon, and organic cages have been studied for hydrogen separation. This study have the literature review for previous research on D2/H2 adsorption and analyzes the D2/H2 adsorption behaviors of hydrogen isotopes for various zeolite using BET at 77 K. The study predicts the D2/H2 adsorption selectivity based on the results obtained with BET. These hydrogen isotope adsorption fundamentals provide a foundation for future processes for tritium separation.

Molten salt consisting primarily of eutectic LiCl-KCl is currently being used in electrorefiners in the Fuel Conditioning Facility at Idaho National Laboratory. Options are currently being evaluated for storing this salt outside of the argon atmosphere hot cell. The hygroscopic nature of eutectic LiCl-KCl makes is susceptible to deliquescence in air followed by extreme corrosion of metallic cannisters. In this study, the effect of occluding the salt into a zeolite on water sorption/desorption was tested. Two zeolites were investigated: Na-Y and zeolite 4A. Na-Y was ineffective at occluding a high percentage of the salt at either 10 or 20wt% loading. Zeolite-4A was effective at occluding the salt with high efficiency at both loading levels. Weight gain in salt occluded zeolite-4A (SOZ) from water sorption at 20% relative humidity and 40℃ was 17wt% for 10% SOZ and 10wt% for 20% SOZ. In both cases, neither deliquescence nor corrosion occurred over a period of 31 days. After hydration, most of the water could be driven off by heating the hydrated salt occluded zeolite to 530℃. However, some HCl forms during dehydration due to salt hydrolysis. Over a wide range of temperatures (320–700℃) and ramp rates (5, 10, and 20℃ min−1), HCl formation was no more than 0.6% of the Cl− in the original salt.

[Ga]-MFI and H-ZSM-5 catalysts were synthesized under atmospheric pressure and used in the propylene aromatization. The effect of temperature on the product distribution was also investigated. The catalytic activities of the prepared catalysts were compared with the commercialized H-ZSM-5 which was converted from NH4-ZSM-5. In the propylene aromatization, product distribution does not depend on the ratio of Si/Ga2 with [Ga]-MFI catalyst, but depend on the ratio of Si/Al2 with H-ZSM-5 catalyst [Ga]-MFI catalyst shows better dehydrogenation and alkylation activities than H-ZSM-5 catalyst The addition of Ga to H-ZSM-5 catalyst increases the conversion of propylene, selectivity to aromatics, and alkylation. In the propylene aromatization, the selectivity to aromatics slightly increased with increasing temperature with [Ga]-MFI catalyst, while slightly decreased with increasing temperature with H-ZSM-5 catalyst

The alkylation benzene with 1-dodecene of Mordenite, Zeolite β and Zeolite Y was studied in the stirring batch reactor. The kinds of zeolites were found to have influenced the reaction conversion and distribution of phenyldodecane isomer in the product. Compared to the alkylation conducted over Zeolite Y and Zeolite β, the alkylation over Mordenite exhibited higher distribution of 2-phenyldodecane and the alkylation conducted over Zeolite Y and Mordenite, the alkylation over Zeolite β exhibited higher distribution of heavy alkylate which formed through oligomerization reaction readily deactivated the Lewis acid sites. A special feature of the effect of the benzene to 1-dodecene ratio the reaction conversion and selectivity of phenyldodecane isomer was found. At alkylation of benzene with 1-dodecene over Zeolite β, when the catalyst content in the system was high, the reaction will reach the optimal conversion at the higher B/D. When the benzene to 1-dodecene ratio was high, the selectivity of phenyldodecane isomer is high. It was also found that at the similar reaction conversion there was the same product distribution regardless of D/C ratio.

The adsorption characteristics of four pesticides (phosphamidon, fenitrothion, triadimefon, and diniconazole) on natural clinoptilolite (CLIN) and three synthetic zeolites were investigated. The synthetic zeolites included faujasite (FAUF) synthesized from coal fly ash; the mixture of FAU and Na-P1 (FAU + Na-P1)SF synthesized using Jeju scoria and coal fly ash at the ratio of 1.5 by weight; and waste fluid catalytic cracking catalyst (FCCW). The distribution coefficient, KD and the Freundlich constant, KF decreased in the following sequence: FCCW > FAUF > (FAU + Na-P1)SF > CLIN among the zeolites and diniconazole>fenitrothion> triadimefon> phosphamidon among the pesticides. The pesticide adsorptivity increased with increasing temperature for FAUF, (FAU+Na-P1)SF and FCCW, however, it decreased for CLIN, regardless of the type of pesticide. The adsorptivity of pesticides was independent of pH for phosphamidon, fenitrothion and triadimefon, whereas it decreased with increasing pH for diniconazole, regardless of zeolite type.

몽골(6종), 미국(1종), 한국(9종)지역에서 채취한 총 16종의 천연 제올라이트를 X-선 회절 분석, X-선 형광 분석, 열 시차, 열 중량 분석 및 양이온 교환능 분석을 통해 특성분석을 수행하였다. 16종의 시료 모두 두 종류 이상의 광물상이 공존하는 혼합광 형태이며, 주로 클라이놉틸로라이트, 휼란다이트, 모데나이트 및 차 바자이트와 같은 광물의 조합으로 이루어져 있으며, 일부 시료에서는 운모 점토광물인 일라이트와 석영과 같은 광물이 불순물로 함유되어 있었다. X-선 형광 분석 결과 16종의 천연 제올라이트는 SiO2, Al2O3, K2O, CaO, Na2O, MgO 및 Fe2O3 산화물이 함유되어 있었다. 미국 천연 제올라이트인 U-1 시료가 223.3 meq/100 g으로 양이온 교환능이 가장 높게 나타났으며 몽골 천연 제올라이트에서는 M-6 시료가, 한국 천연 제올라이트에서는 K-1 시료가 각각 166.6 meq/100 g으로 가장 높게 나타났다. 열시차 및 열중량 분석 결과 16종의 시료 모두 600℃까지 열적으로 안정성이 우수한 것을 확인 하였다.

Industrial gas drying, dilute gas mixtures purification, air fractionation, hydrogen production from steam reformers and petroleum refinery off-gases, etc are conducted by using adsorptive separation technology. The pressure swing adsorption (PSA) has certain advantages over the other methods, such as absorption and membrane, that are a low energy requirement and cost-effectiveness. A key component of PSA systems is adsorbents that should be highly selective to a gas being separated from its mixture streams and have isotherms suitable for the operation principle. The six standard types of isotherms have been examined in this review, and among them the best behavior in the adsorption of CO2 as a function of pressure was proposed in aspects of maximizing a working capacity upon excursion between adsorption and desorption cycles. Zeolites and molecular sieves are historically typical adsorbents for such PSA applications in gas and related industries, and their physicochemical features, e.g., framework, channel structure, pore size, Si-to-Al ratio (SAR), and specific surface area, are strongly associated with the extent of CO2 adsorption at given conditions and those points have been extensively described with literature data. A great body of data of CO2 adsorption on the nanoporous zeolitic materials have been collected according to pressure ranges adsorbed, and these isotherms have been discussed to get an insight into a better CO2 adsorbent for PSA processes.

The purpose of this work is to study the desorption characteristics of water vapor on zeolites saturated with water vapor. Three kinds of zeolite; zeolite 3A, zeolite 4A, and zeolite 5A were used as adsorbent. The desorption experiments with several different temperatures in the range of 90∼150℃ and several different flow rates in the ranges of 0∼0.4 L/min on zeolite bed were carried out. The desorption ability of water vapor was most effective on zeolite 5A among the compared zeolites. The higher the desorption temperature of water vapor was, the faster the desorption velocity was. The desorption ability of water vapor with an air supply was higher than that without an air supply. The most appropriate air flow rate was considered as 0.1 L/min.

The adsorption performance of lead ion was studied using five zeolites (Na-P1, sodalite (SOD), analcime (ANA), nepheline hydrate (JBW), cancrinite (CAN)) synthesized from Jeju scoria. The adsorption performances of lead ion decreased in the order of Na-P1 > SOD > ANA > JBW > CAN. These results showed that the synthetic zeolite with a higher cationic exchange capacity showed a higher adsorption performance. The uptake of lead ion by synthetic zeolites were described by Freundlich model better than Langmuir model. The adsorption kinetics of lead ion by synthetic zeolites fitted the pseudo 2nd order kinetics better than pseudo 1st order kinetics. The effective diffusion coefficients of lead ion by synthetic zeolites were ten times higher than the zeolite A synthesized from coal fly ash.

제주도 응회구 및 응회환과 지하 서귀포층 화산쇄설암에서 화산유리 변질산물로서 불석광물들이 생성되었다. X선회절분석과 전자현미화학분석으로 확인된 주요 불석광물은 필립사이트와 아날심이다. 아날심과 필립사이트의 Si/(Si+Al) 원자비는 모물질인 현무암 유리와 유사하다. 아날심의 화학조성은 매우 단순하지만, 필립사이트는 구조 내 공극 양이온들의 비율이 매우 다양하다. 아날심이 산출되는 당산봉 및 용머리 응회암에서는 Na, 그리고 시추코아에서는 K와 Ca가 필립사이트의 주요 공극양이온이었다. 변질조직의 주사전자현미경 관찰에 의하면 필립사이트가 먼저 침전되고, 후기에 아날심이 충전하였다. 제주도의 여러 응회환/구 중에서도 층서적으로 가장 오래된 당산봉과 용머리 응회암에서 지표수와의 오랜 반응으로 불석광물들이 다량 생성되었고 비교적 연대가 젊은 다른 응회환/구에는 볼석이 거의 생성되지 않았다.

Two different kinds of cases, with and without addition of noncrystalline silica to the Hadong kaolin were studied to obtain useful information on the synthesis of zeolite. The research was carried out to investigate the formation area and the crystalized degree of zeolite according to a synthetic time, the water content of raw material mixture, KOH concentration, and stirring intensity. In the case of without addition of noncrystalline silica to the Hadong kaolin and the low concentration range of KOH, the structure of the kaolin was not changed. However, when the mole ratio of K2O/SiO2 in natural kaolin was increased, Linde-L zeolite and unknown structure of kaolins, U-1 and U-2 were produced. While in the high concentration range of KOH, the unknown structure of kaolins, U-6 and U-2, were produced and the production rate of U-6 was increased with the increased of K2O/SiO2 mole ratio. In the case of with addition of noncrystalline silica to the Hadong kaolin and treatment with KOH hydrothermal processing, ZSM-5, ZSM-35, and Linde-L zeolites and the mixture of unknown structure of zeolites, U-1, U-2, U-3, and U-4, were obtained. Both cases demonstrated that the synthesis of zeolite from the Hadong kaolin was highly influenced by KOH concentration of raw material mixture.

Various kinds of zeolites, such as analcime (ANA), cancrinite (CAN), Na-P1 and sodalite octahydrate (SOD) could be synthesized from Hwangto by hydrothermal reaction in a high-pressure vessel. The adsorption characteristics of Cu(II) and Cd(II) by Hwangto and its synthetic zeolites were investigated using the chemical and electrochemical surface parameters of these adsorbents. The heavy metal adsorptivity among the adsorbents decreased in the following sequences: Na-P1>SOD>ANA>CAN>Hwangto. This sequence was the same with the values of surface site density (Ns) of these adsorbents and was correlated inversely with the values of pHpzc (pH of the point of zero charge) and the values of Ka2(int) (intrinsic surface deprotonation constant) of the adsorbents for synthetic zeolites, i.e., the adsorbents with higher values of Ns and with lower values of pHpzc and Ka2(int) for synthetic zeolites showed higher heavy metal adsorptivity. With increasing pH, the heavy metal adsorptivity increased greatly between pHpzc and pH 6 or 7 because of the steep increase of negatively charged sites for synthetic zeolites, but for Hwangto, it increased broadly because of slow increase of negatively charged sites based on its lower surface sites.

Adsorption characteristics of triadimefon and diniconazole(pesticide) by natural zeolite(CLIN) and several synthetic zeolites were investigated. The synthetic zeolites used in this study were as follows: Faujasite synthesized from coal fly ash(FAUF); Zeolite synthesized from the mixture of FAU and Na-Pl synthesized from the ratio of Cheju scoria 6 to coal fly ash 4 by weight((FAU + Na-Pl)SF); Waste fluid catalytic cracking catalyst(FCCw). The distribution coefficient, KD and Freundlich constant, KF decreased in the following sequence : FCCW>FAUF>(FAU+Na-Pl)SF > CLIN among the zeolites. The distribution coefficient and the adsorption capacity of (FAU + Na-Pl)SF for pesticides were 4.4 and 2.6 times higher for triamefon, and 2.0 and 2.4 times higher for diniconazole than those of CLIN, respectively.

Siliceous mudstones are embedded on a large scale in the Tertiary formations of Pohang area. Some useful zeolites such as NsP, (Na, TMA)P, analcime and hydroxysodalite were synthesized from the siliceous mudstones by treating with the variety of solution, i.e ., NaOH, NaOH+NaCl, NaOH, NaOH+NaAlO2and NaOH+TMAOH at the low-temperature hydrothermal system ranging 60~120℃. Major precursor of zeolites is found as opal-CT in the zeolite-forming reaction. Smectite, which is included in considerable amounts in the mudstone, appears to play a major role of Al-source in the zeolite synthesis. In comparison, chalcedonic quartz and mica are rather insoluble in alkaline solution, and thus, these are observed as major impurities in the reaction products. An addition of NaAlO2to NaOH solution is effective for eliminating these impurities in the reaction procedure, through these are partly dissolved when elevating the reaction temperature, concentration, and time. Phase change from NaP to hydroxysodalite takes place at the NaOH concentrations of 3.0~4.0 M, and the reaction is not sensitive to the temperature shift. NaP is more stable at lower NaOH concentration and higher activity of Na+ whereas analcime is sensitive to the temperature change and stable at higher than 100℃ and 2.0~4.0 M in NaOH concentration. For the pure NaP synthesis without any other products, the treatment of mudstones with 1:1 solution of NaOH and NaAlO 2 turns out to be quite effective. NaP was successfully synthesized together with analcime at 100℃ as well as lower concentrations of NaOH+NaCl solution. In addition, the organic type, (Na, TMA)P was formed together with smectite in the 1:1 solution of NaOH and TMAOH.

The three domestic natural zeolites(Yong dong-ri (Y), Daesin-ri (D), Seogdong-ri (S)) harvested in Kyeongju-shi and Pohang-shi, Kyungsangbug-Do, were pretreated with each of the NaOH, Ca(OH)2, and NaOH following HCl solutions, and the removal performances of divalent heavy metals(Cu, Mn, Pb, and Sr) for natural and pretreated zeolites were investigated and compared in the single and mixed solutions. The natural zeolite-heavy metal system attained the final equilibrium plateau within 20 min, irrespective of initial heavy metal concentration. The heavy metal uptakes increased with increasing initial heavy metal concentration and pH. The heavy metal uptakes for natural zeolites decreased in the following sequences : D>Y>S among the natural zeolites; Pb>Cu>Sr>Mn among the heavy metals. The pretreated zeolites showed higher heavy metal removal performances than natural zeolites and decreased in the order of NaOH, NaOH following HCl, Ca(OH)2 treatment among the pretreatment methods. The heavy metal ion exchange capacity by natural and pretreated zeolites was described either by Freundlich equation or Langmuir equation, but it followed the former better than the latter. The heavy metal uptakes for natural zeolites decreased in the mixed solution, in comparing with those in the single solution and especially, the manganese uptake decreased greatly in the mixed solution. The pretreated zeolites showed the improved removal performances of heavy metals in the mixed solution than in the single solution and the heavy metal uptakes by those in the mixed solution showed the same trends in the single solution among the chemical treatment methods and heavy metals.

경북 구룡포에 소재한 구룡광산에서 산출하는 불석(클리놉틸로라이트와 모데나이트의 집합체)에 대한 Pb2+, Cd2+, Zn2+, Co2+, Fe2+ 및 NH4+ 등 양이온의 치환성질을 알아보기 위하여 베치실험을 실시하였다. 60∼80 메쉬 및 230 메쉬의 시료를 사용하여 각각 50ppm의 농도를 가진 용액과 반응시켰다. 반응후의 용액은 AA 및 전극 (NH4+)으로 분석하여 치환양을 측정하였다. 본 연구결과 Pb2+와 NH4+가 다른 이온들보다 훨씬 높은 선택성을 보여 주었다. 불석에 대한 이온들의 선택성은 NH4+, Pb2+》Zn2+, Cu2-, Co2->Cd2-, Fe2+와 같다. 실험결과 불석시료가 용액으로부터 흡착한 양이 시료로부터 용액으로 추출된 양보다 훨씬 높게 나타나고 있는 바 이는 이온치환보다는 불석의 시브(sieve) 효과에 의한 이온흡착현상이 우세하게 일어났다는 것을 지시해준다. 본 실험은 이 불석이 중금속과 암모니아와 같은 오염물을 제거하는데 사용될 수 있음을 보여준다.

The three natural zeolites collected in Yungil-gun, Kyungsangbuk-do, Korea, were analyzed by means of chemical wet methods and X-ray diffraction. The results indicated that the primary species of those zeolites were clinoptilolite mixed with heulandite, feldspar, montmorillonite, and quartz. These zeolites were chemically treated with NaOH, Ca(OH)_2, and HCl solution and their differences were also studied with X-ray diffraction method. The capabilities of removing Cs^+ and Sr^2+ ions with chemically untreated zeolites, chemically treated zeolites, and also with synthetic zeolites were compared. The effect of other cations in removing Sr^2+ ions was also studied. The experimental results showed that Cs+ and Sr^2+ ions could be removed up to 98% and 95% respectively out of 5 ppm with chemically untrearted natural zeolites. The treatment of 0.02N-Ca(OH)_2 and that of 2N-NaOH were most effective in removing Cs^+ and Sr^2+ ions, respectively. It was found that the mountaintop of Sangjung 1-dong natural zeolite treated with 2N-NaOH was most efficient in removing Sr^2+ ions mixed with other cations, compared with any other chemically treated and untreated natural zeolites in this work.

클라이놉타일로라이트와 모데나이트는 호소환경에서 퇴적된 제3기 장기충군에 속하는 눌대리조면암질 응회암과 구룡포데사이트질 응회암의 주요구성 광물이다. 이들 광물의 생성과정을 알아보기 위하여 서로 다른 응회암질 퇴적암에서 불석광물들의 속성정출순서와 이들의 화학적 동향에 대한 연구가 수행되었다. 현미경적 조직관찰과 화학조성으로부터 밝혀진 생성순서, 즉 Ca-스멕타이트 →(Ca, K)-클라이놉타일로라이트 →(K, Na)-모데나이트는 공극유체의 알칼리이온의 활동도와 Si/Al활동도 비가 속성변질작용과 함께 체계적으로 변화했다는 것을 지시해준다. 불석광물형성의 화학적 진행 추이는 눌대리조면암질 응회암에서는 Ca와 Mg의 감소, Na의 증가 및 K의 증가-감소방향으로 진행되었다. 유리질 물질로부터 스멕타이트를 거쳐 알칼리 불석으로 이어지는 생성순서는 분해용융과 그 직후의 정출작용의 결과이다. 각 불석광물의 화학조성상의 불균질성은 이와 같은 광물생성과정에 기인한다.

화산 유리질 암석인 진주암을 대상으로 60-150˚C의 온도 범위에서 다양한 농도의 알칼리 용액으로 수열 처리하므로서, 유리질 성분의 변질 양상 및 제올라이트의 합성 과정을 폐쇄계의 조건에서 연구하였다. 진주암을 속성 기원 제올라이트의 생성 환경에 해당되는 80˚C 및 pH=8-12의 조건에서 100일간 처리하여도, 양간의 단순 용해 양상이 인지될 뿐 제올라이트는 합성되지 않았다. 여기서 처리 용액의 pH가 증가함에 따라, Si과 Al의 농도는 점진적으로 증가되지만 Si/Al의 농도비는 감소하는 경향을 나타내었다. 진주암을 0.1M 이상의 NaOH 용액으로 수열 처리하여 Na-P, 아날심, 체바자이트, Na-X와 같은 제올라이트를 합성하였다. 대개 100˚C를 경계로 60-100˚C의 온도 범위에서 Na-P, 그리고 100-150˚C에서 아날심이 주로 합성되었다. Na-P의 합성 과정에서 시료에 대한 용액의 혼합 조성비가 낮은 경우(〈10ml/g)에 체바자이트, 그리고 처리 용액의 NaOH 농도가 높을 경우 (〉3M)에 Na-X가 Na-P에 수반되어 생성되는 양상을 볼 수 있다. 제올라이트 합성 과정에 있어서 진주암질 유리의 알칼리 용액에 의한 변질은 화산 유리의 속성 변질에 의한 천연 제올라이트 생성 과정과 같은 용해·변질 반응(incongruent dissolution)의 형식으로 진행되는 것으로 해석된다. 그러나 반응 속도론적인 측면에서 보면, 이 실험으로부터 도출된 제올라이트의 합성 조건들은 화산 유리의 속성 변질에 의한 천연 제올라이트 생성 조건의 해석에 직접 적용될 수 없을 것으로 생각된다.