• Korean Chemical Engineering Research
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• v.46 no.2
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• pp.291-300
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• 2008

Catalytic cracking of n-octane was carried out over H-ZSM-5 zeolite catalysts after calcination with air and steaming with 100% steam in the temperature range of $550-750^{\circ}C$ for 24 h and compared with the results of thermal cracking. The increase of calcination and steaming temperature resulted in the decrease of surface area, pore volume, and strong acid sites, which was mainly caused by the dealumination of H-ZSM-5 framework. It was found by $^{27}Al$ and $^{29}Si$ MAS NMR that the dealumination was proceeded through the transformation process of tetrahedral framework Al${\rightarrow}$penta-cordinated Al ${\rightarrow}$ octahedral framework Al and the phenomena was much more severe in steaming conditions than that of calcination. In the catalytic cracking of n-octane, as the temperatures of calcination and steaming were increased, the conversion of n-octane, the selectivity of light olefins and ethylene to propylene ratio were decreased due to the dealumination of framework aluminum resulting the loss of acidic strengths. The conversion, selectivity of light olefins and ethylene to propylene ratio reached almost to the level of thermal cracking after steaming at $750^{\circ}C$ for 24 h.

• Clean Technology
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• v.23 no.4
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• pp.429-434
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• 2017

To investigate the effect of magnesium oxide addition, $Cu/ZnO/MgO/Al_2O_3$ (CZMA) catalysts were prepared using co-precipitation method with fixed molar ratio of Cu/Zn/Mg/Al as 45/45/5/5 mol% for low-temperature water gas shift reaction. Synthesized catalysts were characterized by using BET, $N_2O$ chemisorption, XRD, $H_2-TPR$ and $NH_3-TPD$ analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of $200{\sim}320^{\circ}C$. At the same condition, magnesium oxide added catalyst (CZMA 400) showed that the lowest reduction temperature and stable presence of $Cu^+$, that is active species and abundant weak acid site. Also magnesium oxide added catalysts (CZMA) showed higher catalytic activity at temperature range above $240^{\circ}C$ than the catalyst without magnesium oxide (CZA). Consequently, CZMA 400 catalyst is considered to be excellent catalyst showing CO conversion of 77.59% without deactivation for about 75 hours at $240^{\circ}C$, GHSV $28,000h^{-1}$.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.8
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• pp.859-869
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• 2005

The commercial $V_2O_5-WO_3/TiO_2$ catalysts which had been exposed to the off gas from incinerator for a long time were regenerated by physical and chemical treatment. The catalytic properties and NOx conversion reactivity of those catalysts were examined by analysis equipment and NOx conversion experiment. The characterization of the catalysts were performed by XRD(x-ray diffractometer), BET, POROSIMETER, EDX(energy dispersive x-ray spectrometer), ICP(inductively coupled plasma), TGA(thermogravimetric analyzer) and SEM (scanning electron microscopy). NOx conversion experiment were performed with simulated off gas of the incinerator and $NH_3$ was used as a reductant of SCR reaction. Among the regeneration treatment methods which were applied to regenerate the aged catalysts in this study, it showed that the heat treatment method had excellent regeneration effect on the catalytic performance for NOx conversion. The catalytic performance of the regenerated catalysts with heat treatment method were recovered over than 95% of that of fresh catalyst. For the regenerated catalysts with the acid solution(pH 5) and the alkali solution(pH 12), the catalytic performance were recovered over than 90% of that of fresh catalyst. From the characterization results of the regenerated catalysts, the specific surface area was recovered in the range of $85{\sim}95%$ of that of fresh catalyst. S and Ca element, which are well known as the deactivation materials for the SCR catalysts, accumulated on the aged catalyst surface were removed up to maximum 99%. Among the P, Cr, Zn and Pb elements accumulated on the aged catalyst surface, P, Cr and Zn element were removed up to 95%. But the Pb element were removed in the range of $10{\sim}30%$ of that of fresh catalyst.

• Clean Technology
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• v.20 no.4
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• pp.425-432
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• 2014

The effect of two important parameters of a catalytic membrane reactor (CMR), hydrogen selectivity and hydrogen permeance, coupled with an Ar sweep flow and an operating pressure on the performance of a water gas shift reaction in a CMR has been extensively studied using a one-dimensional reactor model and reaction kinetics. As an alternative pre-combustion $CO_2$ capture method, the feasibility of capturing a pressurized and concentrated $CO_2$ in a retentate (a shell side of a CMR) and separating a purified $H_2$ in a permeate (a tube side of a CMR) simultaneously in a CMR was examined and a guideline for a hydrogen permeance, a hydrogen selectivity, an Ar sweep flow rate, and an operating pressure to achieve a simultaneous capture of a concentrate $CO_2$ in a retentate and production of a purified $H_2$ in a permeate is presented. For example, with an operating pressure of 8 atm and Ar sweep gas for rate of $6.7{\times}10^{-4}mols^{-1}$, a concentrated $CO_2$ in a retentate (~90%) and a purified $H_2$ in a permeate (~100%) was simultaneously obtained in a CMR fitted with a membrane with hydrogen permeance of $1{\times}10^{-8}molm^{-2}s^{-1}Pa^{-1}$ and a hydrogen selectivity of 10000.

• Journal of the Korean Chemical Society
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• v.40 no.6
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• pp.445-452
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• 1996

Catalytic hydrogenation of ketones and aldehydes by RuH(NO)$L_3$ ($L_3$: $PPh_3$, PhP($CH_2CH_2PPh_2$)$_2$(etp)) was investigated to examine the reaction mechanism and the competence of hydridonitrosyl complexes as catalysts for organic synthesis. RuH(NO)$L_3$ showed catalytic activity for the hydrogenation and the activities of catalysts were dependent on the steric and electronic factors. The less the steric demands of the substrates become, the more activity the catalysts show. For the electronic effect, the more the partial positive charge on the carbonyl carbon atom in ketones becomes and the more the double bond character of carbonyl group in aldehydes becomes, the more active the catalysts are. These results reflect the difference of reaction mechanisms of two substrates, ketones and aldehydes. Catalytic activities of RuH(NO)(etp) and RuH(NO)($PPh_3$)$_3$ in the presence of extra $PPh_3$ toward hydrogenation showed the existence of a reaction pathway accompanied with the change of the bonding modes of NO ligand. The roles of excess $PPh_3$ change with increase of the mole ratio of $PPh_3$ to catalysts; prevention of ligand dissociation from comlexes → bases → ligands. The activity of RuH(NO)(etp) was lower than that of RuH(NO)($PPh_3$)$_3$ toward the hydrogenation of the same substrates mainly due to the structural difference. These catalysts showed the selectivity toward olefin hydrogenation over carbonyl groups in the competitive reaction.

• Transactions of the Korean hydrogen and new energy society
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• v.26 no.5
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• pp.423-430
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• 2015

$Cu/ZnO/Al_2O_3$ catalysts for water gas shift (WGS) reaction were synthesized by co-precipitation method with the fixed molar ratio of Cu/Zn/Al precursors as 45/45/10. Copper and zinc precursor were added into sodium carbonate solution for precipitation and aged for 24h. During the aging period, aluminum precursor was added into the aging solution with different time gap from the precipitation starting point: 6h, 12h, and 18h. The resulting catalysts were characterized with SEM, XRD, BET surface measurement, $N_2O$ chemisorption, TPR, and $NH_3$-TPD analysis. The catalytic activity tests were carried out at a GHSV of $27,986h^{-1}$ and a temperature range of 200 to $400^{\circ}C$. The catalyst morphology and crystalline structures were not affected by aluminum precursor addition time. The Cu dispersion degree, surface area, and pore diameter depended on the aging time of Cu-Zn precipitate without the presence of $Al_2O_3$ precursor. Also, the interaction between the active substance and $Al_2O_3$ became more stronger as aging duration, with Al precursor presented in the solution, increased. Therefore, it was confirmed that aluminum precursor addition time affected the catalytic characteristics and their catalytic activities.

• Applied Chemistry for Engineering
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• v.22 no.3
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• pp.312-318
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• 2011

We have investigated the kinetics and catalytic activity of $CO_2$-lignite gasification with various metal precursors as catalysts. $K_2CO_3$, $Mn(NO_3)_2$, and $Ce(NO_3)_3$ were used and impregnated on a coal using an evaporator. The gasification experiments were carried out with the low rank coal loaded with 5 wt% catalyst at the temperature range from $700{\sim}900^{\circ}C$ and atmospheric pressure with the $N_2-CO_2$ reactant gas mixture. The catalytic effect on the gasification rate of the low rank coal with $CO_2$ was determined by the thermogravimetric analyzer. It was observed that the low rank coal reached the complete carbon conversion regardless of the kinds of catalysts at $900^{\circ}C$ from the results of TGA. The catalytic activity was ranked as 5 wt% $K_2CO_3$ > 5 wt% $Mn(NO_3)_2$ > 5 wt% $Ce(NO_3)_3$ > Non-catalyst at $900^{\circ}C$. The gasification rate increased with increasing the temperature. The activation energy of the catalytic gasification with 5 wt% $K_2CO_3$ was 119.0 kJ/mol, which was the lowest among all catalysts.

• Journal of the Korean Applied Science and Technology
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• v.21 no.1
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• pp.89-96
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• 2004

The effect of La promoter on the carbon deposition and catalytic activity in the synthesis gas production with supported Ni catalysts was investigated. Active component was Ni and support was $CeO_2$ and the promoter used was La. The reaction was carried out in a fixed bed reactor at 1 atm and $650{\sim}800^{\circ}C$. The catalysts were prepared by two methods, the impregnation method and urea method. The catalysts prepared by the urea method showed 10 times higher surface area than those of prepared by the impregnation method. By the introduction of La promoter in the catalyst system, carbon deposition was remarkably reduced from 16% to 2%. It appears that the promoter facilitates the formation of a stable fluoride-type phase, which reduces the carbon deposition. The best catalytic activity and CO and $H_2$ selectivities were obtained with 2.5wt% $Ni/Ce(La)O_x$ catalyst at $750^{\circ}C$, giving 90% methane conversion, 93 and.80% of CO and $H_2$ selectivities, respectively.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.117-121
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• 2008

Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 5-nitro-8-quinolyl benzoate (5) with alkali metal ethoxides, EtO?M+ (M+ = Li+, Na+ and K+) in anhydrous ethanol (EtOH) at 25.0 0.1 C. The plots of kobsd vs. [EtO?M+] exhibit upward curvatures, while the corresponding plots for the reactions of 5 with EtO?Na+ and EtO?K+ in the presence of complexing agents, 15-crown-5-ether and 18-crown-6-ether are linear with rate retardation. The reactions of 5 with EtO?Na+ and EtO?Li+ result in significant rate enhancements on additions of Na+ClO4, indicating that the M+ ions behave as a catalyst. The dissociated EtO and ion-paired EtOM+ have been proposed to react with 5. The second-order rate constants for the reactions with EtO (kEtO) and EtOM+ (kEtOM+) have been calculated from ion-pairing treatments. The kEtO and kEtOM+ values decrease in the order kEtONa+ > kEtOK+ > kEtOLi+ > kEtO, indicating that ion-paired EtOM+ species are more reactive than the dissociated EtO ion, and Na+ ion exhibits the largest catalytic effect. The M+ ions in this study form stronger complex with the transition state than with the ground state. Coordination of the M+ ions with the O and N atoms in the leaving group of 5 has been suggested to be responsible for the catalytic effect shown by the alkali metal ions in this study.

• Korean Chemical Engineering Research
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• v.48 no.4
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• pp.423-427
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• 2010

Carbon nano sphere(CNS) and nano bowl of carbon(NBC) containing 1.0 wt% copper were prepared by impregnation method and their catalytic activity was compared in the phenol hydroxylation with hydrogen peroxide in the presence of water and acetonitrile as a solvent, respectively. Cu content of catalysts was determined by EDS, and BET, pore volume, pore size and pore size distribution were compared. For both catalysts, phenol conversion, $H_2O_2$ efficiency and yield of catechol and hydroquinone were higher in the presence of water as a solvent than those in the presence of actonitrile. And catalytic activity such as phenol conversion and $H_2O_2$ efficiency of 1.0 Cu/CNS is about two times higher than that of 1.0 Cu/NBC in water solvent.