• Journal of the Mineralogical Society of Korea
• /
• v.4 no.1
• /
• pp.22-31
• /
• 1991

Three crystal structures of dehydrated $Ag^+$-and $Ca^{2+}$- exchanged zeolite $A(Ag_4Ca_4-A,\;Ag_^Ca_3-A,\;and\;Ag_8Ca_2-A)$ treated at 250${\circ}C$ with 0.1 Torr of Rb vapor have been determined by single-crystal x-ray diffraction techniques in the cubic space group Pm3m at 21(1)${\circ}C$ (a=12,271(1)${\AA}$, 12.255(1)${\AA}$, and 12.339(1)${\AA}$, respectively). Their structures were refined to the final error indices. R(weighted) of 0.072 with 130 reflections, 0.050 with 110 reflections, and 0.083 with 86 reflections, respectively, for which $I>3{\rho}(I)$. In each structure, Rb species are found at three different crystallographic sites:3$Rb^+$+ions per unit cell are located at 8-ring centers, ca. 5.6 to 6.4 $Rb^+$ ions are found opposite 6-rings on threefold axes in the large cavity, and ca. 2.5 to 3.0 $Rb^+$ ions are found on threefold axes in the sodalite unit. Also, Ag species are found at two different crystallographic stites: ca. 0.7 to 2.1 $Ag^+$ lie opposite 4-rings and ca. 2.2 to 4.8 Ag atoms are located near the center of the large cavity. In these structures, the numbers of Ag atoms per unit cell are 2.2, 2.4, and 4.8, respectively, and these may form hexasilver clusters at the centers of the large cavities. The $Rb^+$ ions, by blocking 8-rings, may have prevented silver from migrating out of the structure. Each hexasilver cluster is stabilized by coordination to up to 13 $Rb^+$ions. An excess absorption of about 0.8 Rb atom per unit cell indicates that the presence of a triangular symmetric $(Rb_3)2^{+}$ cation in sodalite cavity. At least one large-cavity six-ring $Rb^+$ ion must necessarily approach this cluster and may be viewed as a member of it to give $(Rb)_4^{3+}$, $(Rb)_5^{4+}$ or $(Rb)_6^{5+}$.

• Journal of Life Science
• /
• v.17 no.12
• /
• pp.1701-1708
• /
• 2007

Seed pelleting is generally conducted in order to save the labor for sowing and thinning by enabling the precision mechanical planting. In the present study, the influence of physical and chemical properties of pelleting solid materials was investigated on carrot seed germination. Among the pelleting solid materials evaluated, dialite, kaolin, and talc showed low bulk density and high porosity. Bentonite and dialite carried high water holding capacities of 184% and 173%, respectively, while calcium carbonate, calcium oxide, and fly ash showed relatively low water holding capacity. The pH of kaolin (6.8) and dialite (7.4) were close to neutral, while limestone (12.8), calcium oxide (13.0), and bentonite (10.0) were highly basic. High electro-conductivity was shown in limestone and calcium oxide. EDS analysis revealed that the main elemental compositions of talc were Si (71.0%) and Mg (29.0%), and those of calcium carbonate were Ca (66.6%), Si (22.9%), and Mg (10.5%). High granulation capacity was observed from talc and the mixture of talc and calcium carbonate. Seeds pelleted with bentonite showed the highest hardness. The dissolving type of the pellet layer after imbibition was split type in talc, limestone, zeolite, and fly ash, melt type in calcium carbonate and calcium oxide, and swell type in bentonite and vermiculite. The shortest dissolving time of pellet layer was observed from calcium carbonate and kaolin. The germination speed $(T_{50})$ was delayed as the size of pelleted seeds increased. The optimum size of pelleting was 19 ratio in carrot.

• Applied Chemistry for Engineering
• /
• v.4 no.2
• /
• pp.365-372
• /
• 1993

$CO_2$ methanation was performed over Ni supported on cation-exchanged Y zeolites under atmospheric pressure at $250{\sim}550^{\circ}C$ and $H_2/CO_2$ mole ratio of 4. Adsorption strength between carbon dioxide and nickel was found to be Influenced by the cation exchanged in the zeolite. TPD(Temperature-programmed desorption) results show that the adsorption strength decreases in the order of Ni/NaY>Ni/MaY>Ni/HY. TPSR(Temperature-programmed surface reaction) results indicate that enhanced methanation activity is obtained when the adsorption strength between carbon dioxide and nickel is stroing. As the reduction temperature increases, the methantion activity of the catalyst increase. From this result the larger size nickel particle seems advantageous for $CO_2$ methanation reaction. The maximum activity is obtained when nickel loading is 3.3wt%. Carbon monoxide is produced as a by-product throughout the reaction temperature range, and as the contact time increases, the selectivity to methane increases and the selectivity to carbon monoxide decreases steadily. Thus methane seems to be produced from $CO_2$ via CO as an intermediate species. In the temperature range of $410{\sim}450^{\circ}C$, the methane production rate is found to be dependent on the orders of 3.3~-0.5 and 1.4~3.6 with respect to $CO_2$ and $H_2$ partial pressures, respectively. This clearly shows that $CO_2$ and $H_2$ are competing for adsorption sites and as the reaction temperature increases, it becomes increasingly difficult for $H_2$ to be adsorbed on the catalyst surface.

• Korean Chemical Engineering Research
• /
• v.47 no.4
• /
• pp.424-429
• /
• 2009

The effects of $Na_2O$, $SiO_2$ and $H_2O$ contents of the synthetic mixtures prepared from water glass on the crystallinity and crystallite size of sodalite were studied. The composition of the synthetic mixtures described by $x\;Na_2O{\cdot}y\;SiO_2{\cdot}Al_2O_3{\cdot}z\;H_2O$ was varied within x=2.5~7.5, y=1.4~3.0, z=140~400. The hydrothermal reaction was carried out at $140^{\circ}C$ for 2 days. High content of $Na_2O$ resulted in the high crystallinity and small crystallite of sodalite. The $SiO_2/Al_2O_3$ molar ratios of around 2 were suitable for the synthesis of sodalite, and produced zeolite species were varied by the $H_2O$ content. Sodalite was mainly obtained with a high crystallinity from the synthetic mixtures with $SiO_2/Al_2O_3$ molar ratio of around 2 and high content of $Na_2O$. The high content of sodium ions caused a decrease in the particle sizes because of their role of structure directing agent.

• Journal of the Korean Chemical Society
• /
• v.43 no.4
• /
• pp.384-385
• /
• 1999

Two anhydrous crystal structures of fully dehydrated, $Ca^{2+}$- and $Tl^+$-exchanged zeolite X, TEX>$Ca_{18}Tl_{56}Si_{100}Al_{92}O_{384}($Ca_{18}Tl_{56}$-X;\alpha=24.883(4)\AA)$ and TEX>$Ca_{32}Tl_{28}Si_{100}Al_{92}O_{384}($Ca_{32}Tl_{28}$-X;\alpha=24.973(4)\AA)$ per unit cell, have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ $Ca_{18}Tl_{56}-X$ was prepared by ion exchange in a flowing stream of 0.045 M aqueous $Ca(NO_3)_2$ and 0.005 M $TlNO_3$. $Ca_{32}Tl_{28}-X$ was prepared similarly using a mixed solution of 0.0495 M $Ca(NO_3)_2$ and 0.0005M $TlNO_3$. Each crystal was then dehydrated at 360 $^{\circ}C$ and $2{\times}10^{-6}$ Torr for 2 days. Their structures were refined to the final error indices, $R_1=0.039\;and\;R_2=0.036$ with 382 reflections for $Ca_{18}Tl_{56}-X$ , and $R_1=0.046\;and\;R_2=0.045$ with 472 reflections for $Ca_{32}Tl_{28}$-X for which $/>3\sigma(I).$ In the structures of dehydrated $Ca_{18}Tl_{56^-}X\;and\;Ca_{32}Tl_{28}$-X, $Ca^{2+}\;and\;Tl^+$ ions are located at six crystallographic sites. Sixteen $Ca^{2+}$ ions fill the octahedral sites I at the centers of double six rings ($Ca_{18}Tl_{56}$-X:Ca-O=2.42(1) and O-Ca-O=93.06(4)$^{\circ}$; $Ca_{32}Tl_{28}$-X Ca-O=2.40(1) $\AA$ and O-Ca-O=93.08(3)$^{\circ}$). In the structure of $Ca_{18}Tl_{56}$-X, another two $Ca^{2+}$ ions occupy site II (Ca-O=2.35(2) $\AA$ and O-Ca-O=111.69(2)$^{\circ}$) and twenty six $Tl^+$ ions occupy site II opposite single six-rings in the supercage; each is 1.493 $\AA$ from the plane of three oxygens $(Tl-O=2.70(8)\AA$ and O-Tl-O=92.33(4)$^{\circ}$). About four $Tl^+$ ions are found at site II',1.695 $\AA$ into sodalite cavity from their three oxygen plane (Tl-O=2.81 (1) and O-Tl-O=87.48(3)). The remaining twenty six $Tl^+$ ions are distributed over site III'(Tl-O=2.82 (1) $\AA$ and Tl-O=2.88(3)$^{\circ}$). In the structure of $Ca_{32}Tl_{28}$-X, sixteen $Ca^{2+}$ ions and fifteen $Tl^+$ ions occupy site III' (Ca-O=2.26(1) $\AA$ and O-Ca-O=119.14(4)$^{\circ}$; Tl-O=2.70(1) $\AA$ and O-Tl-O=92.38$^{\circ}$) and one $Tl^+$ ion occupies site II'. The remaining twelve $Tl^+$ ions are distributed over site III'. It appears that $Ca^{2+}$ ions prefer sites I and II in that order and $Tl^+$ ions occupy the remaining sites.

• Applied Chemistry for Engineering
• /
• v.8 no.3
• /
• pp.543-549
• /
• 1997

The direct reaction of carbon dioxide($CO_2$) with butane($C_4H_{10}$) to obtain synthesis gas and hydrocarbon compounds have been studied on nickel loaded catalysts. In the reaction of $CO_2$ with $C_4H_{10}$, Ni loaded catalysts showed similar activity with Pt catalyst and Coke deposition on the catalyst was severe by dehydrogenation of butane. The main products were carbon monoxide and hydrogen, when alumina and Y type zeolite were used as a support. Instead, a great deal of aromatic hydrocarbons were obtained on the Ni loaded ZSM-5 catalyst. The conversion of $CO_2$ increased with the increasing molar ratio of $CO_2$/$C_4H_{10}$ on Ni/ZSM-5, Ni/NaY and Ni/alumina catalyst, but the conversion decreased again from the ratio of 2. The value of $CO_2$ conversion was the highest at the 5wt% of Ni loading on ZSM-5 catalyst. A part of cokes deposited on the catalysts diminished when only $CO_2$ gas or water steam flowed into the reactor. The coke deposited on the catalysts was very reactive and it may be an important intermediate for the carbon dioxide reforming reaction.

• Korean Chemical Engineering Research
• /
• v.43 no.6
• /
• pp.675-682
• /
• 2005

Al containing mesoporous molecular sieve (Al-MMS) was synthesized by hydrolysis of $H_2SiF_6$ and $Al(NO_3)_3{\cdot}9H_2O$. The material obtained was characterized by XRD, $N_2$-physisorption. The specific surface area was $981m^2/g$, and the average pore size was uniformity $39{\AA}$. It was confirmed that the acidity of Al-MMS was milder than that of zeolite Y based on the results of $NH_3$-TPD. Active materials, Pt and Pd, were loaded on Al-MMS in order to examine the feasibility of using Al-MMS as a catalyst support in the hydrogenation of aromatic compounds included in the residue oil of a naphtha cracker. The hydrogenation activity of PtPd/Al-MMS has been studied by following the kinetics of the hydrogenation of naphthalene, and by comparing the kinetic parameters obtained with Pt and Pd catalysts supported on the other mesoporous material support and commercial conventional support materials. PtPd/Al-MMS catalyst shows the highest activity of hydrogenation and sulfur resistance. The high activity of PtPd/Al-MMS was confirmed again in the hydrogenation of PGO (pyrolized gas oil), which is residue oil obtained from a naphtha cracker. Therefore, PtPd/Al-MMS can be applied to the hydrogenation of aromatic compounds included in the residue oil of a commercial naphtha cracker commericially.

• Applied Chemistry for Engineering
• /
• v.17 no.3
• /
• pp.235-242
• /
• 2006

Liquid phase alkylation of biphenyl (BP) was studied over large pore zeolites. Selective formation of the least bulky products, 4,4'-diisopropylbiphenyl (4,4'-DIPB) occurred only in the isopropylation of BP over some large pore molecular sieves. H-mordenites (MOR) gave the highest selectivity among them. The dealumination of MOR enhanced catalytic activity and the selectivity of 4,4'-DIPB because of the decrease of coke-deposition. Non-selective catalysis occurs on external acid sites over MOR with the low $SiO_2/Al_2O_3$ ratio because severe coke-deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with reaction temperature. Selective formation of 4,4'-DIPB was observed at moderate temperatures such as $250^{\circ}C$, whereas the decrease of the selectivity of 4,4'-DIPB occurred at higher temperatures as $300^{\circ}C$. However, 4,4'-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores even at high temperatures. These decreases of the selectivity of 4,4'-DIPB are due to the isomerization of 4,4'-DIPB on the external acid sites. Some 12-membered molecular sieves, such as SSZ-24, MAPO-5 (M:Mg, Zn, Si), SSZ-31, and ZSM-12, which have straight channels, gave 4,4'-DIPB with moderate to high selectivity; however; SSZ-55, SSZ-42, and MAPO-36 (M: Mg, Zn) gave lower selectivity because of cages in 12-membered one dimensional channels. Three dimensional H-Y and Beta zeolites also yield 4,4'-DIPB in low yield because of their wide circumstances for the isopropylation of BP. The increasing the size of alkylating agent enhanced the shape-selective alkylaiton even for the zeolites, such as UTD-1. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) over MOR was non-selective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivity of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4'-DEBP was less selective. The least bulky 4-EBP and 4,4'-DEBP have the highest reactivity among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of MOR pores are too loose for shape selective formation of the least bulky isomers, 4-EBP and 4,4'-DEBP in the ethylation of BP, and that MOR pores have enough space for the further ethylation of 4,4'-DEBP.

• The Korean Journal of Pesticide Science
• /
• v.2 no.3
• /
• pp.36-44
• /
• 1998

To develope cost-effective new granular formulation of mixture with 7.0% chlomethoxyfen and 3.5% butachlor, this study was conducted by investigation of floatability, dispersibility or collapsability and released concentration of active ingredients in water and bio-efficacies of the granules formulated by different formulation methods compared to commercial pellet-extruded granules. They were formulated by coating on or impregnation into extruded pellets, sands and zeolites with two active ingredients, binders, friction reducer, dispersing agents and bentonite. Pellet-coated method showed similar floatability, collapsability and bio-efficacy to the commercial pellet-extruded one or better than that but unstable patterns of released concentration of chlomethoxyfen because of easy isolation of coated technical particles from the surface of granules. Sand-coated methods showed similar physical properties, released pattern of two active ingredients, and bio-efficacy to the commercial one. Liquid binders and/or dispersing agents are more important than powdered ones to control released concentration of active ingredients from the granule mixtures, to improve the floatability and dispersibility, and to show good bio-efficacy. Sand-coated one might be a suitable method if types and amount of liquid binders and dispersing agents are selected.

• Korean Chemical Engineering Research
• /
• v.49 no.5
• /
• pp.657-663
• /
• 2011

Structure directing agent(SDA) containing piperidine moiety such as piperidine(PI), 2-methylpiperidine (MPI), 2,6-dimethylpiperidine(DMPI) and 2,2,6,6,-tetramethylpiperidine(TMPI), respectively has been utilized to synthesize aluminophosphate zeolite using hydrothermal method. The gel composition was $1.0Al_2O_3:1.0P_2O_5:0.76SDA:45H_2O$ and the hydrothermal heating was performed in an oven at 443 K and for 7 days at static mode. The obtained zeolitic material contained a lamellar structure when PI was used as the SDA. With a progressive increase of the SDA size, various structures of aluminophosphate including AlPO-5 of AFI structure were obtained. The aluminophosphate of SAS structure was formed when the largest TMPI was utilized as the SDA, which was confirmed by the Rietveld refinement. The result of $^{27}Al$ and $^{31}P$ MAS NMR of the sample suggested that Al and P were incorporated into the framework of the aluminophosphate.