• Korean Chemical Engineering Research
• /
• v.45 no.2
• /
• pp.160-165
• /
• 2007

The synthesis and the characterization of Low Silica X (LSX) zeolite for nitrogen adsorption have been studied. The performance of LSX zeolite for nitrogen adsorption was compared to that of the commercial zeolite. The $Na_2O/(Na_2O+K_2O)$ ratio in the gel and the crystallization time were fixed as the synthetic factor. The LSX zeolite was formed at the $Na_2O/(Na_2O+K_2O)$ ratio of 0.75. The formation of LSX zeolite was confirmed by XRD and SEM. The Si/Al ratio was investigated by using XRF and FT-IR. The synthesized LSX zeolite showed a lower Si/Al ratio than the NaY and NaX zeolites although they have a same faujasite structure. The Si/Al ratio of the LSX zeolite converged close to 1. 1A (Li, Na, K) and 2A (Mg, Ca, Ba) group elements were ion-exchanged to the LSX zeolite. As the charge density of cation rises, the amount of nitrogen adsorbed increased. $Li^+$ ion-exchanged LSX zeolite showed the highest nitrogen adsorption weight. When the Li/Al ratio was over 0.65, nitrogen adsorption increased remarkably. $Li^+$ ions located on the supercage (site III, III') in the LSX zeolite played a role as nitrogen adsorption sites. When the $Ca^{2+}$ ions were added to the LiLSX zeolite by ion-exchange method, the performance for nitrogen adsorption increased more. The performance for the nitrogen adsorption was the highest at the Ca/Al ratio of 0.26. Nitrogen adsorption capacity of LiCaLSX (Ca/Al=0.26) zeolite was superior to the commercial NaX zeolite.

• Korean Journal of Mineralogy and Petrology
• /
• v.33 no.3
• /
• pp.251-258
• /
• 2020

Single crystal of fully dehydrated and partially Ca²⁺-exchanged zeolites A (|Ca₄Na₄|[Si₁₂Al₁₂O₄₈]-LTA) was brought into contact with Se in fine pyrex capillary at 523 K for 5 days. Crystal structure of Se-sorbed |Ca₄Na₄|[Si₁₂Al₁₂O₄₈]-LTA has been determined by single-crystal X-ray diffraction techniques at 294 K in the cubic space group $Pm{\bar{3}}m$ (a = 12.2787(13) Å). The crystal structure of yellow |Ca₄Na₄Se₄|[Si₁₂Al₁₂O₄₈]-LTA has been refined to the final error indices of R₁/wR₂ = 0.0960/0.3483 with 327 reflections for which F_o > 4s(F_o). In this structure, 4 Na⁺ and 4 Ca²⁺ ions fill every 6-ring site: These ions are all found at three crystallographic positions, on 3-fold axes equipoints of opposite 6-rings. Selenium atoms are found at three crystallographically distinct positions: 2 Se atoms per unit cell at Se(1) are located opposite 6-rings in the sodalite cavity (Se(1)-Na(1) = 2.53(5) Å) and 1 at Se(2) opposite 4-rings (Se(2)-O(1) = 2.76(10) Å) and 1 at Se(3) opposite 6-rings in the large cavity (Se(3)-Na(1) = 2.48(5) Å). Two molecular of Se₂ (Se(1)-Se(1) = 2.37(7) or 2.90(8) Å and Se(2)-Se(3) = 2.91(5) ) Å) are found in all sodalite cavity and large cavity. Other clusters such as Se₄ and Se₈ could be existed in large cavity. The inter-selenium distances turned out to be longer that of gases Se₂ molecule.

• Journal of the Korean Applied Science and Technology
• /
• v.34 no.1
• /
• pp.1-11
• /
• 2017

Bio-oil has attracted considerable interest as one of the promising renewable energy resources because it can be used as a feedstock in conventional petroleum refineries for the production of high value chemicals or next-generation hydrocarbon fuels. Zeolites have been shown to effectively promote cracking reactions during pyrolysis resulting in highly deoxygenated and hydrocarbon-rich compounds and stable pyrolysis oil products. In this study, catalytic pyrolysis was applied to upgrade bio-oil from yellow poplar and then fuel characteristics of upgraded bio-oil was investigated. Yellow Poplar(500 g) which ground 0.3~1.4 mm was processed into bio-oil by catalytic pyrolysis for 1.64 seconds at $465^{\circ}C$ with Control, Blaccoal, Whitecoal, ZeoliteY and ZSM-5. Under the catalyst conditions, bio-oil productions decreased from 54.0%(Control) to 51.4 ~ 53.5%, except 56.2%(Blackcoal). HHV(High heating value) of upgraded bio-oil was more lower than crude bio-oil while the water content increased from 37.4% to 37.4 ~ 45.2%. But the other properties were improved significantly. Under the upgrading conditions, ash and TAN(Total Acid Number) is decrease and particularly important as transportation fuel, the viscosity of bio-oil decreased from 6,933 cP(Control) to 2,578 ~ 4,627 cP. In addition, ZeoliteY was most effective on producing aromatic hydrocarbons and decreasing of from the catalytic pyrolysis.

• Applied Chemistry for Engineering
• /
• v.5 no.5
• /
• pp.808-818
• /
• 1994

Effects of ceria additive on the activity and thermal aging behavior of supported Ru catalysts were investigated using Ru/${\gamma}$-$Al_2O_3$and Ru/$CeO_2$-${\gamma}$-$Al_2O_3$. The catalysts were characterized by $^{129}Xe$-NMR and $H_2$ chemisorption. The cataltic activity for conversion of CO, HC and $NO_x$ was measured using simulated automobile engine exhausts under lean, rich and stoichiometric conditions. For both fresh and aged catalysts, Ru/$CeO_2$-${\gamma}$-$Al_2O_3$ was more active than Ru/${\gamma}$-$Al_2O_3$ for all three pollutants. Results of $^{129}Xe$-NMR and $H_2$ chemisorption indicated that sintering of Ru particles occurred to the same extent for both catalysts during the thermal aging process. After thermal aging at 673K, however, the catalytic activity of the aged Ru/$CeO_2$-${\gamma}$-$Al_2O_3$ was substantially higher than that of the fresh one, while the activity of Ru/${\gamma}$-$Al_2O_3$ decreased after the thermal aging. This finding may suggest new active sites were created during the thermal aging, probably in the vicinity of the interface between Ru and Ce. For more quantitative investigation of the effect of a cation such as Ce on the thermal aging of Ru metal particles, Ru catalysts supported on cation-exchanged Y-zeolites were used as the model catalysts. The results indicated that when Ba, Ca, La, Y or Ce was used for the cation exchange, the exchanged cation did not affect the thermal aging behavior of Ru in Y-zeolite, as evidenced by $^{129}Xe$-NMR and EXAFS.

• Journal of Korean Society of Environmental Engineers
• /
• v.30 no.6
• /
• pp.659-665
• /
• 2008

This study is about zeolite synthesis from the sewage sludge incinerator fly ash of "S" sewage treatment center located in Seoul. For this purpose, the properties of raw fly ash as starting material, the hydrothermal conditions for zeolite synthesis and the environmental applicabilities of synthesized zeolites were examined. Fly ash from sewage sludge incinerator has large quantities of SiO$_2$ and Al$_2$O$_3$ and their contents are 42.8 wt.% and 21.2 wt.% respectively. So fly ash is considered to be possible starting material for zeolite synthesis. The results from leaching test of fly ash showed that the concentration of hazardous metals were very low as compared with the Korea leaching standard of the Waste Management Law. But the concentration from total recoverable test of fly ash were higher than the fertilizer standard of Fertilizer Management Law. Major zeolite products synthesized by hydrothermal reaction are analcime in teflon vessel and zeolite P1 in borosilicate flask. Optimum conditions for the synthesis of analcime were 1 N of NaOH concentration, 16 hour of reaction time and 135$^{\circ}C$ of reaction temperature. For the zeolite P1 formation, the proper conditions were demonstrated to be 5 N of NaOH concentration, 16 hour reaction time and 130$^{\circ}C$ of reaction temperature in this study. Hazardous metal contents in the analcime product are similar with those in raw fly ash. In case of the zeolite P1, the contents are reduced to nearly a half. Raw fly ash and the analcime product showed NH$_4{^+}$ ion exchange capacity of 0$\sim$1.0 mg of NH$_4{^+}$g$^{-1}$ and 3.0$\sim$7.4 mg of NH$_4{^+}$g$^{-1}$, respectively. However, the zeolite P1 product reached exchange capacity to 14.6$\sim$17.8 mg of NH$_4{^+}$g$^{-1}$. This values are in the range of those of natural clinoptilolite and phillipsite. From this point of view, zeolite synthesis from sewage treatment sludge incinerator fly ash is a good alternative for solid waste recycling.

• Journal of the Mineralogical Society of Korea
• /
• v.21 no.1
• /
• pp.37-44
• /
• 2008

This study was performed to synthesize Na-A type zeolite with melting slag from the Mapo incineration site and recycle the zeolite as an environmental remediation agent. The melting slag used had a favorable composition containing 26.6% $SiO_2$, 10.9% $Al_2O_3$ and 2.7% $Na_2O$ for zeolite synthesis although there were high contents of iron oxides, including 19.6% $Fe_2O_3$ and 18.9% FeO, which had been used as a flux for the melting. It was confirmed that the Na-A type zeolite could be successfully synthesized at $80^{\circ}C$ and $SiO_2/Al_2O_3\;=\;0.80{\sim}1.96$. The cation exchange capacities (CEC) of the zeolites was determined to be about 220 cmol/kg leveled off at the synthetic time more than 10hrs. The adsorption capacities of zeolite to heavy metals (Cd, Cu, Mn and Pb) were high except for As arid Cr. It was also confirmed through the Eh and pH analysis that As and Cr existed in the forms of $HAsO_4^{2-}$ and $CrO_4^{2-}$. The low absorption rates of zeolite for As and Cr are attributed to the fact that the pore size ($4\;{\AA}$) of Na-A type is smaller than those of $HAsO_4^{2-}$ and $CrO_4^{2-}$ ions ($4\;{\AA}$ ionic radii and $8\;{\AA}$ diameter).

• Journal of the Mineralogical Society of Korea
• /
• v.30 no.2
• /
• pp.45-57
• /
• 2017

Two single crystals of fully dehydrated $Cd^{2+}$-exchanged zeolites Y were prepared by the exchange of ${\mid}Na_{75}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$ ($Na_{75}-Y$, Si/Al = 1.56) with aqueous $0.05M\;Cd(NO_3)_2$ (pH = 3.65) at 294 K, followed by vacuum dehydration at 723 K (crystal 1) and a second crystal, similarly prepared, was exposed to zeolitically dried benzene for 72 hours at 294 K and evacuated (crystal 2). Their structures were determined crystallographically using synchrotron X-rays and were refined to the final error indices using $F_o$>$4{\sigma}(F_o)$ of $R_1/wR_2=0.040/0.121$ and 0.052/0.168, respectively. In crystal $1({\mid}Cd_{36}H_3{\mid}[Si_{117}Al_{75}O_{384}]-FAU)$, $Cd^{2+}$ ions primarily occupy sites I and II, with additional $Cd^{2+}$ ions at sites I', II', and a second site II. In crystal $2({\mid}Cd_{35}(C_6H_6)_{24}H_5{\mid}[Si_{117}Al_{75}O_{384}]-FAU)$, $Cd^{2+}$ ions occupy five crystallographic sites. The 24 benzene molecules are found at two distinct positions within the supercages. The 17 benzene molecules are found on the 3-fold axes in the supercages where each interacts facially with one of site IIa $Cd^{2+}$ ions. The remaining 7 benzene molecules lie on the planes of the 12-rings where each is stabilized by multiple weak electrostatic and van der Waals interactions with framework oxygens.

• Economic and Environmental Geology
• /
• v.18 no.4
• /
• pp.399-410
• /
• 1985

Bentonites from the Janggi Group of the Lower Miocene age from the Geumgwangdong area, Korea, have been studied for mineralogical and genetic characterization. The Janggi Group is subdivided, in ascending order, into the Janggi Conglomerate, the Nuldaeri Tuff, the Geumgwangdong Shale, the Lower Coal-bearing Formation, the Basaltic Tuff, and the Upper Coalbearing Formation. Bentonites occur as thin or thick beds in all sedimentary units of the Janggi Group, except for the Janggi Conglomerate. Significant bentonite deposits are found in the Nuldaeri Tuff, the Lower Coal-bearing Formation and the Basaltic Tuff. Bentonites consist mainly of smectite (mainly montmorillonite), with minor quartz, cristobalite, opal-CT and feldspar. Occasionally, kaolinite, clinoptilolite or gypsum is associated with bentonites. Bentonites were studied by the methods of petrographic microscopy, X-ray diffraction, thermal analysis (DT A and TG), infrared absorption spectroscopic analysis, SEM, intercalation reaction, and chemical analysis. Smectites commonly occur as irregular boxwork-like masses with characteristic curled thin edges, but occasionally as smoothly curved to nearly flat thin flakes. Most of smectites have layer charge of 0.25-0.42, indicating typical montmorillonite. Crystal-chemical relations suggest that Fe is the dominant substituent for Al in the octahedral layer and there are generally no significant substituents for Si in the tetrahedral layer. Ca is the dominant interlayer cation in montmorillonite. Therefore, montmorillonite from the study area is dioctahedral Ca-montmorillonite. Occurrence and fabrics of bentonites suggest that smectites as well as cristobalite, opal-CT and zeolites have been formed diagenetically from tuffaceous materials. The precursor of smectites is trachytic or basaltic tuff. Smectites derived from the former contain relatively more $Al_2O$ a and less $Fe_2O_3$ than those from the latter.

• Journal of the Mineralogical Society of Korea
• /
• v.31 no.4
• /
• pp.235-248
• /
• 2018

The present work was performed in order to study the effect of competing cation of $Ca^{2+}$ ion on ion exchange of $Cs^+$ on zeolite Y (Si/Al = 1.56). Three single-crystals of fully dehydrated and partially $Cs^+$-exchanged zeolites Y (Si/Al = 1.56) were prepared by the flow method using mixed ion-exchange solutions. The $CsNO_3:Ca(NO_3)_2$ molar ratios of the ion exchange solution were 1 : 1 (crystal 1), 1 : 100 (crystal 2), and 1 : 250 (crystal 3) with a total concentration of 0.05 M. The single-crystals were then vacuum dehydrated at 723 K and $1{\times}10^{-4}Pa$ for 2 days. The structures of the crystals were determined by single-crystal synchrotron X-ray diffraction technique in the cubic space group $Fd{\bar{3}}m$, at 100(1) K. The unit-cell formulas of crystals 1, 2, and 3 were ${\mid}Cs_{21}Ca_{27}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, ${\mid}Cs_2Ca_{36.5}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, and ${\mid}Cs_1Ca_{37}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, respectively. In all three crystals, the $Ca^{2+}$ ions preferred to occupy site I in the D6Rs, with the remainder occupying sites I', II', and II. On the other hand, the significant differences in the fractional distribution of $Cs^+$ ions are observed depending on the intial $Cs^+$ concentrations in given ion exchange solution. In Crystal 1, $Cs^+$ ion are located at sites II', II, III, and III', and in crystal 2, at sites II, IIIa, and IIIb. In crystal 3, $Cs^+$ ions are only located at sites IIIa and IIIb. The degree of $Cs^+$ ion exchange decreased sharply from 28.0 to 2.7 to 1.3 % as the initial $Ca^{2+}$ concentration increases and the $Cs^+$ content decreases.

• KSCE Journal of Civil and Environmental Engineering Research
• /
• v.29 no.3B
• /
• pp.303-310
• /
• 2009

Natural zeolite is widely used as sorbents and bio-media materials because it is cheap as well as it has efficient porous structures and large cation exchange. In this study, the effect of metal cations $(Na^+,\;Ca^{2+},\;Mg^{2+},\;Al^{3+})$ adsorbed to natural zeolite on the microorganism attachment was investigated. Metal-modified zeolites (MMZ) were prepared with 0.01 M, 0.02 M and 0.1 M NaCl, $CaCl_2$, $MgCl_2$ and $AlCl_3$ solutions respectively, which concentrations were equivalent to 10%, 20% and 100% of cation exchange capacity (CEC) of natural zeolite. Pseudomonas putida was used as microorganism which was cultivated in Beef Extract Medium at $26^{\circ}C$. The microorganism attachment to MMZ was increased more than natural zeolite. The amount of bacterial adhesion to MMZ and natural zeolite were $Mg^{2+}>natural>Na^+>Al^{3+}>Ca^{2+}$ under 10% of CEC, $Mg^{2+}>Ca^{2+}>Al^{3+}>natural>Na^+$ under 20% of CEC and $Ca^{2+}>Mg^{2+}>natural>Al^{3+}>Na^+$ under 100% of CEC. Especially, Mg-modified zeolite (Mg-MZ) showed the highest amount of bacterial adhesion, which increased the microorganism attachment 60% higher than natural zeolite under 10% of CEC. However, the amount of bacterial adhesion was decreased as the concentration of metal cations modified to zeolite were increased, showing that the increased amounts were 60% under 10% of CEC, 50% under 20% of CEC and 10% under 100% of CEC in Mg-MZ. Additionally, the effect of $Mg^{2+}$ in solution on the bacterial adhesion was investigated in order to compare it with the effect of $Mg^{2+}$ adsorbed to zeolite. The maximum quantity of bacterial adhesion to Mg-MZ was not different from the amount of microorganism attachment to the natural zeolite when $Mg^{2+}$ solution was added.