• Korean Chemical Engineering Research
• /
• v.54 no.6
• /
• pp.838-846
• /
• 2016

Most of combustion processess used in industries require recovering or removing flue gas components. Recently a new MBA (moving bed adsorption) process for recovering $CO_2$ using zeolite 13X was developed. In this study, adsorption experiments for carbon dioxide, nitrogen, sulfur dioxide, and water vapor on zeolite 13X were carried out. Adsorption equilibrium and adsorption rate into solid particle were investigated. Langmuir, Toth, and Freundlich isotherm parameters were calculated from the experiment data at various temperatures. Experimental results were consistent with the theoretically predicted values. Also $CO_2$ adsorption amount was measured under the conditions with impurities such as $SO_2$ and $H_2O$. Binary adsorption data were well fitted to the extended Langmuir isotherm using parameters obtained from pure component experiment. However, $H_2O$ impurity less than, roughly, ${\sim}10^{-5}H_2O\;mol/g$ zeolite 13X enhanced slightly $CO_2$ adsorption. Spherical particle diffusion model well described experimentally measured adsorption rate. Diffusion coefficients and activation energies of $CO_2$, $SO_2$, $N_2$, $H_2O$ were obtained. Diffusion coefficients of $CO_2$ and $SO_2$ decreased with small amount of preadsorbed impurity. Parameter values from this study will be helpful to design of real commercial adsorption process.

• Journal of the Korean Chemical Society
• /
• v.39 no.1
• /
• pp.7-13
• /
• 1995

The crystal sructures of $X(Ca_{46}Al_{92}Si_{100}O_{384})$ and $Ca_{32}K_{28}-X(Ca_{32}K_{28}Al_{92}Si_{100}O_{384})$ dehydrated at $360^{\circ}C$ and $2{\times}10^{-6}$ Torr have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ Their structures were refined to the final error indices, R_1=0.096,\;and\;R_2=0.068$ with 166 reflections, and R_1=0.078\;and\;R_2=0.056$ with 130 reflections, respectively, for which I > $3\sigma(I).$ In dehydrated $Ca_{48}-X,\;Ca^{2+}$ ions are located at two different sites opf high occupancies. Sixteen $Ca^{2+}$ ions are located at site I, the centers of the double six rings $(Ca(1)-O(3)=2.51(2)\AA$ and thirty $Ca^{2+}$ ions are located at site II, the six-membered ring faces of sodalite units in the supercage. Latter $Ca^{2+}$ ions are recessed $0.44\AA$ into the supercage from the three O(2) oxygen plane (Ca(2)-O(2)= $2.24(2)\AA$ and $O(2)-Ca(2)-O(2)=119(l)^{\circ}).$ In the structure of $Ca_{32}K_{28}-X$, all $Ca^{2+}$ ions and $K^+$ ions are located at the four different crystallographic sites: 16 $Ca^{2+}$ ions are located in the centers of the double six rings, another sixteen $Ca^{2+}$ ions and sixteen $K^+$ ions are located at the site II in the supercage. These $Ca^{2+}$ ions adn $K^+$ ions are recessed $0.56\AA$ and $1.54\AA$, respectively, into the supercage from their three O(2) oxygen planes $(Ca(2)-O(2)=2.29(2)\AA$, $O(2)-Ca(2)-O(2)=119(1)^{\circ}$, $K(1)-O(2)=2.59(2)\AA$, and $O(2)-K(1)-O(2)=99.2(8)^{\circ}).$ Twelve $K^+$ ions lie at the site III, twofold axis of edge of the four-membered ring ladders inside the supercage $(K(2)-O(4)=3.11(6)\AA$ and $O(1)-K(2)-O(1)=128(2)^{\circ}).$

• Journal of the Korean Chemical Society
• /
• v.21 no.3
• /
• pp.204-209
• /
• 1977

The properties of the natural zeolite produced in Kuryongpo, Kyungsang-Bukdo, were investigated by X-ray diffraction analysis, chemical composition analysis, and nitrogen adsorption experiment. The quality of the acid treated natural zeolite as the catalyst for the disproportionation reaction of toluene was examined experimentally by observing the conversion in a microcatalytic reactor. The quantitative analysis and X-ray diffraction spectrum showed that the zeolite ore of Kuryongpo contained approximately 30 to 40 percent of mordenite structure. The surface area of the zeolite ore was $75m^2$/gm and increased to a maximum value of $320m^2$/gm after treatment with 2 N HCl solution. The catalytic activity for the toluene disproportionation reaction was maximum when the zeolite treated with 2 N HCl solution was used. The selectivity of xylene to benzene decreased with increasing degree of acid treatment.

• Journal of Korean Society of Environmental Engineers
• /
• v.39 no.2
• /
• pp.51-58
• /
• 2017

We investigated the efficiency of natural zeolite with different cation exchange capacity (CEC) as capping material for the remediation of marine sediments contaminated with heavy metals. Three different zeolite with high CEC (HCzeo, 163.74 cmolc/kg), medium CEC (MCzeo, 127.20 cmolc/kg), and low CEC (LCzeo, 70.62 cmolc/kg) were used. The surface area of the zeolite was in decreasing order: HCzeo ($59.43m^2/g$) > MCzeo ($52.10m^2/g$) > LCzeo ($10.12m^2/g$). The results of mineralogical composition obtained from X-ray diffraction (XRD) show that LCzeo was mainly composed of quartz and albite. In the XRD result of MCzeo and HCzeo, the peaks of clinoptilolite, heulandite, and mordenite were also observed along with that of quartz and albite. Sorption equilibrium onto the HCzeo, MCzeo, and LCzeo was reached in 6 h at initial concentration of 10 mg/L and 100 mg/L. Higher adsorption of Cd and Zn onto the zeolite with higher CEC were achieved but adsorption of Cu and Ni were not dependent on the CEC of zeolite. It can be concluded that the zeolite with high cation exchange ability is recommended for the contaminated sediments with Cd and Zn but the inexpensive zeolite with low CEC for Cu and Ni.

• Journal of the Mineralogical Society of Korea
• /
• v.16 no.2
• /
• pp.135-149
• /
• 2003

Domestic zeolite ores are mostly composed of Ca-type clinoptilolite, accompanying a little amounts of mordenite. However, other types of zeolite ores rich in ferrierite, heulandite, or mordenite are less commonly found. Based on the quantitative XRD analysis, zeolite contents are determined to be nearly 50∼90 wt%. Impurities (mostly ＞ 10 wt%) in the zeolite ores chiefly consist of quartz, feldspar, smectite, and opal-CT. The determined CEC values ($CEC_{AA}$ ) of powdery samples (grain size: < 125 $\mu\textrm{m}$) of zeolite ores by the Ammonium Acetate method are mostly higher than 100 meq/100 g. Some zeolites from the Guryongpo area, corresponding to the clinoptilolite ore, are measured to be dominantly high in CEC values ranging 170∼190 meq/100 g. Cation exchange property of the zeolite ores varies greatly depending on the types or zeolite species present in the ores. Despite of the lower grade in zeolite content, the $CEC_{AA}$ of ferrierite ore is comparatively high. Compared to this, the $CEC_{AA }$ of heulandite ore is very low, though the zeolite ore exhibits the highest grade ranging up to about 90 wt%. In addition, the CEC values calculated theoretically from the framework composition of clinoptilolite-heulandite series are not consistent with those determined by the cation exchage experiment. The measured $CEC_{AA}$ of clinoptilolite ores are generally higher than those of heulandite ores. This may be due to the higher Ca abundance in exchangeable cation composition and the presence of probable stacking faults in heulandite. The variation of $CEC_{CEC}$ is roughly proportional, though not strictly compatible, to the zeolite contents in clinoptilolite ores. It seems to be caused by the fact that the $CEC_{AA}$ of clinoptilolite locally varies depending on crystal-chemical diversity, i. e., the variation in framework composition (Si/Al) and exchangeable cation composition (especially, the contents of Ca and K). In addition, the determined CEC values ($CEC_{MB}$ ) of zeolite ores by the Methylene Blue method are much higher than those calculated from smectite contents. It suggests a probable reaction of Methylene Blue ion ($C_{16}$ $H_{18}$ $N_3$S+) with larger-pore zeolites than clinoptlolite-heulandite series, i.e., ferrierite and mordenite as well as with smectite. This can be supported by the fact that the ferrierite ore accompanying little amount of smectite has the highest value in CE $C_{MB}$ .

• Clean Technology
• /
• v.20 no.2
• /
• pp.179-188
• /
• 2014

The effect of desorption pressure on $CO_2/N_2$ breakthrough behaviors for 4 different adsorbents was studied at a fixed bed. Zeolite 3A, 4A, 5A, and 13X pellets were used as adsorbents. Cyclic operations were executed with varying desorption pressure from vacuum (0 bar) to 3 bar while other conditions such as adsorption step pressure (3 bar), temperature (293 K), composition ($CO_2:N_2=10:90$vol%) and flow rate (400 ccm) were fixed at constant values. Each adsorption and desorption step was set as 80 min, which totaled up to 160 min per a cycle. 5 cycles with adsorption and desorption steps were run overall. After the experiment, breakthrough time, saturation time, and adsorption amount were measured and compared in order to find an optimum adsorbent and a proper operating condition for a post combustion $CO_2$ capture process.

• Journal of the Mineralogical Society of Korea
• /
• v.6 no.2
• /
• pp.116-121
• /
• 1993

A single crystla of zeolite $Na_{78}Rb_{28}-X$ (approximate composition) was prepared by exposing $Na_{92}-X$ at $350^{\circ}C$ to 0.1 Torr of rubidium vapor, and its structure was determined by single-crystal x-ray diffraction methods in the cubic space group, Fd3, ${\alpha}=25.045(4){\AA}$. The structure was refined to the final error indices $R_1=0.082$ and $R_2=0.084$ with 353 for which I>$3{\sigma}(I)$. Only about 28 of the 92 $Na^+$ ions per unit cell were reduced and only about 14 of the 28 $Na^0$ atoms produced were retained within the zeolite. A $Na_5{^{4+}}$ cluster is present within each sodalite cavity. It is a centered tetrahedron (like $CH_4$) with bond $length=2.80(2){\AA}$ and angle tetrahedral by symmetry, and shows the full symmetry of its site. $T_d$, at the center of the sodalite cavity. Each of the four terminal atoms of the $Na_5{^{4+}}$ cluster bond to three framework oxygens at $2.36(2){\AA}$. At the centers of some double 6-rings are sodium atoms which bridge linearly between $Na_5{^{4+}}$ clusters to form agglomerations such as short zig-zag chains $Na_5{^{4+}}$ clusters. Delocalized electrons, located primarily on the sodiums at centers of the sodalite and (likely) double-six-ring cavities, contribute to the stability of the clusters.

• Korean Chemical Engineering Research
• /
• v.46 no.4
• /
• pp.783-791
• /
• 2008

The dynamic characteristics of adsorption using an adsorption bed packed with Li-X zeolite (UOP) were studied through the breakthrough experiments of $H_2/CH_4$ (90:10 vol%), $H_2/CO$ (90:10 vol%) and $H_2/CO_2$ (80:20 vol%) mixtures. Effects of feed flow rate (6.24~10.24 LPM) and adsorption pressure (6.1 bar~10.1 bar) in the Li-X zeolite bed with 2.7 cm of inside diameter and 80 cm of bed length were observed. The smaller feed rate or the higher operating pressure, resulted in the longer of the breakthrough time and the breakthrough curve have tailing due to temperature variance in the bed. The adsorption dynamics of the Li-X zeolite bed were predicted by using LDF model with feed flow and pressure dependent diffusivity. The prediction and experimental data were analyzed with a nonisothermal, nonadiabatic model, dual-site langmuir (DSL) isotherm

• Proceedings of the Korean Radioactive Waste Society Conference
• /
• 2003.11a
• /
• pp.207-214
• /
• 2003

Removal efficiency of methyl iodide at high temperature process by TEDA-impregnated activated carbon used for radioiodine retention in nuclear facility was experimentally compared with that of silver ion-exchanged synthetic zeolite(AgX), In temperature ranges of$30^{\circ}C$ to $400^{\circ}C$, adsorption capacity of un-impregnated carbon was sharply decreased, but TEDA-impregnated carbon showed similar values of adsorption capacity of AgX even around $100^{\circ}C$. Especially, loading amount of methyl iodide on TEDA carbon up to$250^{\circ}C$ represented higher values compared to un-impregnated carbon. Breakthrough curves of methyl iodide in fixed bed packed with AgX and TEDA-impregnated carbon at high temperature was compared. Removal mechanism of methyl iodide on AgX was proposed, based on analysis of by-product gas generated from adsorption reaction.

• Korean Chemical Engineering Research
• /
• v.46 no.1
• /
• pp.175-183
• /
• 2008

Adsorption equilibria of the gases $CO_2$, CO, $CH_4$ and $H_2$ and their binary mixtures on Li-X zeolite (UOP) were obtained by static volumetric method in the pressure range of 0 to 20 bar at temperatures of 293.15, 303.15, and 313.15 K. Using the parameter obtained from single-component adsorption isotherm. Multicomponent adsorption equilibra could be predicted and compared with experimental data. Extended Langmuir isotherm, Extended Langmuir-Freundlich isotherm (L-F) and dual-site Langmuir isotherm (DSL) were used to predict the experimental results for binary adsorption equilibria of $H_2/CO_2$, $H_2/CO$, and $H_2/CH_4$ on Li-X Zeolite. Extended Langmuir-Freundlich isotherm predicted equilibria of $CH_4$ and $H_2$ better than any other isotherm. One the other hand DSL isotherm predicted equilibria of $CO_2$ and CO very well.