• Korean Chemical Engineering Research
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• v.56 no.6
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• pp.878-883
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• 2018

A circulating fluidized bed (CFB) has been used in various chemical industries because of good heat and mass transfer. In addition, the methanol to olefins (MTO) process requiring the CFB reactor has attracted a great deal of interest due to steep increase of oil price. To design a CFB reactor for MTO pilot process, therefore, we has examined the hydrodynamic properties of spherical catalysts with different particle size and developed a correlation equation to predict catalyst holdup in a riser of CFB reactor. The hydrodynamics of micro-spherical catalysts with average particle size of 53, 90 and 140 mm was evaluated in a $0.025m-ID{\times}4m-high$ CFB riser. We also developed a model described by a decay coefficient to predict solid hold-up distribution in the riser. The decay coefficient developed in this study could be expressed as a function of Froude number and dimensionless velocity ratio. This model could predict well the experimental data obtained from this work.

• Applied Chemistry for Engineering
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• v.22 no.6
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• pp.587-593
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• 2011

As a result of increasing environmental concerns related to air quality and maintenance of automobiles, the alkylation of isobutane with olefins has become an even more important process for production of high quality gasoline. However, the widespread use of the alkylation process is limited by the polluting and corrosive liquid acid catalysts (HF and $H_2SO_4$) currently used in industry. For the reason, a large number of solid catalysts, especially zeolites, have been studied as an environmental friendly catalyst in this process. Recently, mesoporous solid acids and ionic liquids have been investigated as a green catalyst. In this review, the research of environmental friendly catalysts for an isobutane alkylation is summarized.

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.185-189
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• 1987

Reactions of $Ir(ClO)_4(CO)(PPh_3)_2$ with dicyano olefins, cis-NCCH = CH$CH_2$$CH_2$CN (cDC1B), trans-NCCH = CH$CH_2$$CH_2$CN (tDC1B), trans-NC$CH_2$CH = CH$CH_2$CN (tDC2B), and NC$CH_2$$CH_2$$CH_2$$CH_2$CN (DCB) produce binuclear dicationic iridium (I) complexes, $[(CO)(PPh_3)_2Ir-NC-A-CN-Ir(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (1a), tDC1B (1b), tDC2B (1c), DCB (1d)). Complexes 1a-1d react with hydrogen to give binuclear dicationic tetrahydrido iridium (Ⅲ ) complexes, $[(CO)(PPh_3)_2(H)_2Ir-NC-A-CN-Ir(H)_2(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (2a), tDC1B (2b), tDC2B (2c), DCB (2d)). Complexes 2a and 2b catalyze the hydrogenation of cDC1B and tDC1B, respectively to give DCB, while the complex 2c is catalytically active for the isomerization of tDC2B to give cDC1B and tDC1B and the hydrogenation of tDC2B to give DCB at $100^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.403-408
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• 2012

In this study, the homogenous Pd nanoparticles (Pd NPs) were first prepared with bayberry tannin (BT) as the stabilizers. Subsequently, the obtained bayberry tannin-stabilized Pd nanoparticles (BT-Pd) were immobilized onto ${\gamma}-Al_2O_3$ to prepare heterogeneous ${\gamma}-Al_2O_3$-BT-Pd catalysts. Fourier Transformation Infrared Spectrum (FTIR) and X-ray Photoelectron Spectroscopy (XPS) analyses confirmed that the Pd NPs were well stabilized by the phenolic hydroxyl groups of BT. Transmission Electron Microscopy (TEM) observation indicated that the diameter of the Pd NPs can be effectively controlled in the range of 4.2-16.0 nm by varying the amount of BT. It is found that the ${\gamma}-Al_2O_3$-BT-Pd catalysts exhibit highly activity for various olefin hydrogenations. For example, the initial TOF (turnover frequency) of the ${\gamma}-Al_2O_3$-BT-Pd in the allyl alcohol hydrogenation is as high as $12804 mol{\cdot}mol^{-1}{\cdot}h^{-1}$. Furthermore, the ${\gamma}-Al_2O_3$-BT-Pd can be reused 5 times without significant loss of activity, exhibiting a superior reusability as compared with conventionally prepared ${\gamma}-Al_2O_3$-Pd catalysts.

• Korean Chemical Engineering Research
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• v.51 no.2
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• pp.181-188
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• 2013

The effect of transition metal ion exchange into UZM-9 zeolite with LTA framework on its deactivation in methanol-to-olefin (MTO) conversion was discussed. The ion exchange of copper, cobalt, nickel, and iron did not induce any notable change in the crystallinity, crystal morphology, and acidity of UZM-9. The small cage entrance of UZM-9 caused the high selectivity to lower olefins in the MTO conversion, while its large cages allowed the rapid further cyclecondensation of active intermediates, polymethylbenzenes including hexamethylbenzene, resulting in a rapid deactivation. The UZM-9 containing copper and cobalt ions showed considerably slow deactivations. The interaction between transition metal ions and polymethylbenzene cation radicals, the active intermediates, generated in the MTO conversion stabilized the radicals and slowed down the deactivation of UZM-9.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.132-136
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• 2002

$Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)\;(OTf=CF_3SO_3^-)$ readily reacts with various amines to afford cationic amine complexes $[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(amine)](OTf)\;(amine=NH_3,\;NHMe_2,\;NHC_4H_8,\;NH_2Ph,\;NH_2(Tol-p))$ in high yields. These complexes have been fully characterized by IR, $^1H-,\;^{19}F{^1H}-,\;and\;^{31}P{^1H}-NMR$ spectroscopy, and elemental analyses. Reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with acrylonitrile quantitatively produced the ${\pi}$-olefinic complex $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)](OTf)$ which is only stable in solution in the presence of acrylonitrile. Attempt at isolating this complex in the pure solid state was failed due to partial decomposition into $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ The equilibrium constants $(K_{eq}=[Pt(PCP)-(NH_2R)^+][CH_2=CHCN]/[Pt(PCP)(CH_2=CHCN)^+][NH_2R]:\;[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(CH_2=CHCN)]^++NH_2R{\rightleftarrows}[Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(NH_2R)]^++CH_2=CHCN=Ph,\;p-tolyl)$ were calculated to be 0.28 (for R = Ph) and 3.1 (R = p-tolyl) at $21^{\circ}C$. The relative stability of the ${\sigma}$-donor amine versus the ${\pi}$-olefinic acrylonitrile complex has been found largely dependent upon the amine-basicity $(pK_b)$, implicating that acrylonitrile practically competes with amine in the platinum coordination sphere. On the contrary to the formation of the acrylonitrile complex, no reaction of $Pt(2,6-(Cy_2PCH_2)_2C_6H_3)(OTf)$ with other olefins such as ethylene, styrene and methyl acrylate was observed.

• 한국연소학회:학술대회논문집
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• 2001.11a
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• pp.169-178
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• 2001

Among the recent research ideas to reduce hydrocarbon emissions emitted from SI engines till light-off of catalyst since cold start are those exploiting non-thermal plasma technique and photo-catalyst that draws recent attention by virtue of its successful application to practical use to clean up the atmosphere using the feature of its relative independence on temperature. Based on the previous research results obtained with model exhaust gases using an experimental emissions reduction system that utilizes the non-thermal plasma and photo-catalyst technique, further investigation was conducted on a production N/A 1.5 liter DOHC engine during cold start to warm-up. For the effects of non-thermal plasma-photocatalyst combined reactor, 10% concentration reduction was achieved with the fuel component paraffins, and the large increase in non-fuel paraffinic components and acetylene concentrations were similar to those of base condition. However the absolute value was locally a bit higher than those of base condition since the products was made from the dissociation and decomposition of highly branched paraffins by plasma-photocatalyst reactor. Olefinic components were highly decomposed by about 75%, due to these excellent decompositions of olefins which have relatively high MIR values, and the SR value was 1.87 that is 30% reduction from that of base condition, then, the photochemical reactivity was lowered.

• Membrane Journal
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• v.27 no.4
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• pp.313-318
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• 2017

For the separation of olefins/paraffins, $Poly(ethylene oxide)(PEO)/AgBF_4/Al(NO_3)_3/Ag_2O$ composite membranes were prepared. When $Ag_2O$ was introduced, the initial selectivity and permeance of composite membranes were observed to be 13.7 and 21.7 GPU, respectively. The increase in performance compared to the initial performance of $PEO/AgBF_4/Al(NO_3)_3$ membrane (selectivity 13 and permeance 7.5 GPU) was thought to be due to the increase of Ag ion activity due to the addition of $Ag_2O$. However, performance degradation over time was observed, which was thought to be due to the polymer matrix PEO. Since the PEO polymer could not stabilize the $Ag_2O$ particles, the $Ag_2O$ particles becmae aggregated together as the solvent evaporates, and $Ag_2O$ acts as a barrier. As a result, the permeance decreases over time.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.744-752
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• 1992

Polymer bonded metalloporphyrins are synthesized by reaction between Fe(III) protoporphyrin or Mn(II) tetrakis(4-N-carboxyphenyl)porphyrin with polystyrene divinylbenzene copolymer. The spectroscopic properties of synthetic polymer bonded metalloporphyrins are investigated by using resonance Raman spectrometer. By synthetic polymer bonded metalloporphyrins as catalyst, which are model of cytochrome P-450 and peroxidases, epoxidation of olefins and oxidation of alkanes are achieved with H2O2 as oxidant. The catalytic efficiencies with polymer bonded metalloporphyrins are improved on that with corresponding nonpolymer bonded metalloporphyrins. Especially those can be reused because of stability against oxidant. Electron donating imidazole derivatives, which are attached in 5th position of central metal of metalloporphyrins, enhance the catalytic efficiencies.

• Journal of the Korean Chemical Society
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• v.22 no.1
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• pp.45-51
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• 1978

The luminescence of N-methyllutidone is studied in ethanol matrix at $77^{\circ}C$K. No fluorescence is observed but a strong phosphorescence with the quantum yield of 0.1 and the lifetime of 0.2 sec is recorded. An unusually high triplet energy of 85.1 kcal/mole is determined for the compound from the O-O band of phosphorescence. The cis ${\leftrightarrow}$ trans photoisomerization of high triplet energy olefins such as 2-hexene and trans-1,4-dichlorobutene-2 is efficiently sensitized by N-methyllutidone substantiating the high triplet energy of the compound. The negative polarization of O-O band reveals the emitting triplet state to be $({\pi},{\pi}^*)^3$ state. Alkaline metal salts such as lithium chloride enhances the phosphorescence intensity through cation-N-methyllutidone coordination widening the gap between $({\pi},{\pi}^*)^3$and $(n,{\pi}^*)^3$ states.