• Journal of Environmental Science International
• /
• v.30 no.9
• /
• pp.719-726
• /
• 2021

In this study, zeolitic materials were synthesized from Jeju Volcanic Rocks (JVR) using a fusion/hydrothermal method at NaOH/JVR ratios of 0.6 and 1.2. The crystallinities of the zeolitic materials at NaOH/JVR ratios of 0.6 and 1.2 were 25.5% and 59.0%, respectively. It was confirmed through the SEM image that the zeolitic materials covered the zeolite particle with a cube-shaped crystals. The Co ions adsorption by the zeolitic materials were to reach the adsorption equilibrium at 120 min. It could be better simulated in the pseudo-second order adsorption kinetic equation than in the pseudo-first order adsorption kinetic equation. The adsorption capacities (q_m) of Co ions could be to estimate Langmuir isotherm better than Freundlich isotherm. The maximum adsorption capacities (q_m) at NaOH/JVR ratios of 0.6 and 1.2 were 55.3 mg/g and 68.7 mg/g, respectively. It was found that there was a high correlation between the crystallinity of zeolitic materials and the adsorption capacity of Co ions adsorption.

• Bulletin of the Korean Chemical Society
• /
• v.28 no.4
• /
• pp.567-573
• /
• 2007

The crystal structure of ZnI2 molecule synthesized in zeolite A (LTA) has been studied by single-crystal X-ray diffraction techniques. A single crystal of |Zn6|[Si12Al12O48]-LTA, synthesized by the dynamic ion-exchange of |Na12|[Si12Al12O48]-LTA with aqueous 0.05 M Zn(NO3)2 and washed with deionized water, was placed in a stream of flowing 0.05 M KI in CH3OH at 294 K for four days. The resulting crystal structure of the product (|K6Zn3(KI)3(ZnI2)0.5|[Si12Al12O48]-LTA, a = 12.1690(10) A) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm3m. It was refined with all measured reflections to the final error index R1 = 0.078 for 431 reflections which Fo > 4σ (Fo). At four crystallographically distinct positions, 3.5 Zn2+ and nine K+ ions per unit cell are found: three Zn2+ and five K+ ions lie on the 3-fold axes opposite 6-rings in the large cavity, two K+ ions are off the plane of the 8-rings, two K+ ions are recessed deeply off the plane of the 8-rings, and the remaining a half Zn2+ ion lie on the 3-fold axes opposite 6-rings in the sodalite cavity. A half Zn2+ ion and an I- ion per unit cell are found in the sodalite units, indicating the formation of a ZnI2 molecule in 50% of the sodalite cavities. Each ZnI2 (Zn-I = 3.35(5) A) is held in place by the coordination of its one Zn2+ ion to the zeolite framework oxygens and by the coordination of its two I- ions to K+ ions through 6-rings (I-K = 3.33(8) A). Three additional I- ions per unit cell are found opposite a 4-ring in the large cavity and form a K3I2+ and two K2ZnI3+ ionic clusters, respectively.

• Clean Technology
• /
• v.28 no.4
• /
• pp.269-277
• /
• 2022

With the recent development of the biological enzymatic reaction industry, lactic acid (LA) can be mass-produced from biomass sources. In particular, a catalytic process that converts LA into acrylic acid (AA) is receiving much attention because AA is used widely in the petrochemical industry as a monomer for superabsorbent polymers (SAP) and as an adhesive for displays. In the LA conversion process, NaY zeolites have been previously shown to be a high-activity catalyst, which improves AA selectivity and long-term stability. However, NaY zeolites suffer from fast deactivation due to severe coking. Therefore, the aim of this study is to modify the acid-base properties of the NaY zeolite to address this shortcoming. First, base promoters, Ca ions, were introduced to the NaY zeolites to tune their acidity and basicity via ion exchange (IE) and incipient wetness impregnation (IWI). The IWI method showed superior catalyst selectivity and stability compared to the IE method, maintaining a high AA yield of approximately 40% during the 16 h reaction. Based on the NH₃- and CO₂-TPD results, the calcium salts that impregnated into the NaY zeolites were proposed to exit as an oxide form mainly at the exterior surface of NaY and act as additional base sites to promote the dehydration of LA to AA. The NaY zeolites were further treated with KOH before calcium impregnation to reduce the total acidity and improve the dispersion of calcium through the mesopores formed by KOH-induced desilication. However, this KOH treatment did not lead to enhanced AA selectivity. Finally, calcium loading was increased from 1wt% to 5wt% to maximize the amount of base sites. The increased basicity improved the AA selectivity substantially to 65% at 100% conversion while maintaining high activity during a 24 h reaction. Our results suggest that controlling the basicity of the catalyst is key to obtaining high AA selectivity and high catalyst stability.

• Applied Chemistry for Engineering
• /
• v.2 no.2
• /
• pp.97-107
• /
• 1991

Highly-siliceous dealuminated zeolite, silicalite(end member of ZSM-5) was synthesized from a batch composition of 2.55 $Na_2O-5.0$ TPABr-$100SiO_2-2800H_2O $ at $180^{\circ}C$ and at times ranging from one to seven days of reaction time. Autoclaves containing the synthesis mixture were centrifuged within the specially-equipped convection oven to provide an elevated gravitational force field like 30 and 50 G. Tests were also conducted at normal gravity. For synthesis performed under elevated gravities, average and maximum crystal sizes were substantially greater than those synthesized under normal gravity and product yields were also found to be affected by elevated gravity ; that is, product yields were substantially enhanced under elevated gravity from 4 % to 55 % with respect to normal gravity. The average crystal sizes of silicalite synthesized at normal gravity were 50 to $70{\mu}m$ over an entire range of reaction time, one to seven days while the average crystal sizes synthsized under elevated gravities, 30 and 50 G, were 160 to $190{\mu}m$ respectively. For the elevated gravity, in particular, two separate nucleations and growths were observed. For examples, at 50G, large crystals of $200{\mu}m$ were produced through the second growing stage after 5 days of reaction following the rapid first growing stage where fairly large crystals of $135{\mu}m$ were produced only in 2 days of reaction. The maximum crystal sizes obtained through the above two growing stages were 190 and $300{\mu}m$, respectively. A discussion of how elevated gravity affects nucleation, growth, yield and crystal size of silicalite is presented.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.7
• /
• pp.1090-1096
• /
• 2005

$Ag_4Br_4$ nanoclusters have been synthesized in about 75% of the sodalite cavities of fully $K^+$-exchanged zeolite A (LTA). An additional KBr molecule is retained in each large cavity as part of a near square-planar $K_4Br^{3+}$ cation. A single crystal of $Ag_{12}$-A, prepared by the dynamic ion-exchange of $Na_{12}$-A with aqueous 0.05 M $AgNO_3$ and washed with $CH_3OH$, was placed in a stream of flowing 0.05 M KBr in $CH_3OH$ for two days. The crystal structure of the product ($K_9(K_4Br)Si_{12}Al_{12}O_{48}{\cdot}0.75Ag_4Br_4$, a = 12.186(1) $\AA$) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm m. It was refined with all measured reflections to the final error index $R_1$ = 0.080 for the 99 reflections for which $F_o\;{\gt}\;4_{\sigma}\;(F_o)$. The thirteen $K^+$ ions per unit cell are found at three crystallographically distinct positions: eight $K^+$ ions in the large cavity fill the six-ring site, three $K^+$ ions fill the eight-rings, and two $K^+$ ions are opposite four-rings in the large cavity. One bromide ion per unit cell lies opposite a four-ring in the large cavity, held there by two eight-ring and two six-ring $K^+$ ions ($K_4Br^{3+}$). Three $Ag^+$ and three $Br^-$ions per unit cell are found on 3-fold axes in the sodalite unit, indicating the formation of nano-sized $Ag_4Br_4$ clusters (interpenetrating tetrahedra; symmetry $T_d$; diameter ca. 7.9 $\AA$) in 75% of the sodalite units. Each cluster (Ag-Br = 2.93(3) $\AA$) is held in place by the coordination of its four $Ag^+$ ions to the zeolite framework (each $Ag^+$ cation is 2.52(3) $\AA$ from three six-ring oxygens) and by the coordination of its four $Br^-$ ions to $K^+$ ions through six-rings (Br-K = 3.00(4) $\AA$).

• Journal of the Korean Chemical Society
• /
• v.43 no.2
• /
• pp.172-181
• /
• 1999

To develop the manufacturing technique for the powder builder of amorphous solid types, the water glass mixed with caustic soda dispersed into the methanol. Thus soluble sodium silicate was made a form of amorphous solid powder. In order to examine characteristics of water soluble sodium silicate $SiO_2/Na_2O$ mol ratio, we investigated solubility, thermogram, SEM, and BET analysis. pH buffering capacity, calcium-ion binding capacity as temperature change, and surfactant loading capacity were examined for characteristics as laundry detergent builder. $SiO_2/Na_2O$ molar ratio of soluble sodium silicate was 1.0, 2.4, 2.8, and zeolite was used in order to investigate basic characteristics of laundry detergent builder. Silicate used with laundry detergent was good for pH buffering capacity and solubility. But calcium-ion binding capacity and surfactant adsorption ability were lower. $SiO_2/Na_2O$ mol ratio became higher, pH buffering capacity and ion exchange ability were lower and surfactant adsorption ability was a little higher.

• Applied Biological Chemistry
• /
• v.49 no.3
• /
• pp.170-174
• /
• 2006

For the purpose of developing a high quality agricultural microbial inoculant, methods and materials for improving encapsulation were investigated. Preparation of capsule was conducted by improving extrusion system with micro-nozzle and peristaltic pump. The sodium alginate was selected because of its cheapness, stability of cells, and gel formation ability. The yields, physical properties and gel formation abilities of extractable alginate from sea tangle were investigated by hot water extractable and alkali soluble methods. The extraction yields of hot water extractable alginate (HWEA) and alkali soluble alginate (ASA) from sea tangle were 8 and 20%, respectively. The HWEA was almost not viscous even in 1.5% of the sample solution, whereas the ASA was very highly viscous in above 3% sample solution. The gel formation ability of each samples varied from 1.5% to 5% and the ASA showed a good gel formation ability at 3% solution as commercial alginate (CA). The soil microbial inoculant, Bacillus thuringiensis, Bacillus subtilis, Lactobacillus plantarum and Geotrichum candidum encapsulated sodium alginate with starch and zeolite for stabilizer. The survivability of encapsulated soil microbial inoculant using alginate without stabilizer appeared to be 66, 52, 70 and 50%, respectively. Inclusion of starch and zeolite with alginate bead increased viabilities in Bacillus sp. and Geotrichum candidum by 81-83% and 89%, respectively.

• Clean Technology
• /
• v.17 no.4
• /
• pp.389-394
• /
• 2011

A compact adsorption-based process for removal of carbon dioxide and nitrogen from natural gas has been discussed. Among the adsorption-based processes, especially, the pressure swing adsorption (PSA) process has been a suitable unit operation for the purification and separation of gas because of low operation energy and cost. A step cycle is made up of pressurization, feed, equalization, blowdown and rinse. In this work, the PSA process is composed of zeolite 13X and carbon molecular sieve (CMS) for removal of carbon dioxide and nitrogen from mixed gas containing $CH_4/CO_2/N_2$ (75:21:4 vol%). A CMS selectively removes carbon dioxide and a zeolite 13X separates nitrogen from methane. CMS is investigated experimentally due to the high throughput of the faster diffusing component ($CO_2$). The gas composition of top, bottom and feed tank was measured with the gas chromatography (GC) using TCD detector, helium as carrier gas and packed column for analysis of methane, carbon dioxide, and nitrogen.

• Journal of the Korean Institute of Gas
• /
• v.9 no.2 s.27
• /
• pp.50-55
• /
• 2005

The compositional and structural properties of alkali metal ion exchanged Y-zeolites have been investigated by la number of analytical techniques and their catalytic activities were tested for NOx reduction in combination with a non-thermal plasma. The NOx conversion data for LiY, NaY, KY and CsY were measured by chemiluminiscent NOx meter in the temperature range of 100 to $350^{\circ}C$. The initial activities of the catalyst at $150^{\circ}C$ increased in the order LiY < KY < NaY < CsY in alkali series. The activity of CsY and NaY were increased and showed maximum at $200^{\circ}C$ and then decreased in the plasma reactor, as the temperature increased. The activity of KY maintained same by $200^{\circ}C$ and then decreased, whereas the activity of LiY decreased with the increasing temperature. The CsY catalyst, which showed the highest activity in alkali metal series, exhibits a NOx conversion efficiency of $80\%$ between $170{\~}220^{\circ}C$.

• Korean Journal of Mineralogy and Petrology
• /
• v.35 no.2
• /
• pp.141-151
• /
• 2022

The 16 natural zeolites collected from Mongolia (6 types), the United States (1 type), and Korea (9 types) were characterized by XRD, XRF, TGA, DTA, and CEC analysis. All 16 samples are composite minerals. Two or more mineral phases co-exist and consist primarily of minerals such as clinoptilolite, heulandite, mordenite, and chabazite. In certain samples, minerals like illite and quartz were present as impurities. The XRF analysis showed that the 16 natural zeolites contain SiO₂, Al₂O₃, K₂O, CaO, Na₂O, MgO, and Fe₂O₃ oxides. The cation exchange capacity of the U-1 sample was 223.3 meg/100 g, which is higher than the rest of the samples. M-6 sample in Mongolian natural zeolite and K-1 sample in Korean natural zeolite showed the highest cation exchange capacity at 166.6 meg/100 g. As a result of thermal differential and thermos gravimetric analysis, all 16 samples showed excellent thermal stability up to 600℃.