• Clean Technology
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• v.22 no.2
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• pp.82-88
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• 2016

The loss of activity by coke is an important cause of catalyst deactivation during industrial operation. In this study, hydrogen ratio of reaction condition, which has influenced on coke formation over Pt-Sn catalyst, and regeneration of catalysts activity by coke burning, Pt sintering of coke burning as coke contents, effects of coke formation and deactivation with different Sn contents were confirmed. Pt-Sn-K catalyst supported on θ-alumina and γ-alumina was prepared progressively. Activity of regenerated catalyst for propane dehydrogenation was compared with fresh catalyst by coke burning, after propane dehydrogenation was carried out with different hydrogen ratio at 620 ℃ on fresh catalyst. Regenerated catalyst’s physical characterization such as BET, coke analysis and XRD was investigated. Through catalytic activity test and characterization, Sn contents of catalyst and hydrogen ratio in feed stream could affect coke formation on catalyst surface. Excessive coke makes loss of activity and Pt sintering during air regeneration process.

• Clean Technology
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• v.19 no.3
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• pp.327-332
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• 2013

Space- and time-resolved in-situ optical and fluorescence microspectroscopy techniques have been applied to investigate the coke formation during aromatization of C5 paraffin and olefin over H-ZSM-5 crystal. In-situ UV/vis absorption measurement offers space- and time-resolved information for the coke formation. Different coking trends have been observed with respect to the location of a crystal as well as the reactant types. From in-situ confocal fluorescence microspectroscopy study, it is revealed that the concentration of certain species photo-excited at 488 nm becomes high at the central region, whereas the compounds emitting fluorescence by 561 nm laser move towards the boundary region of the crystal. The different fluorescence patterns obtained varying excitation lasers suggest the existence of distinct fluorescence emitting species having different degree of coke growth.

• Korean Chemical Engineering Research
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• v.56 no.2
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• pp.176-185
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• 2018

As global warming accelerates, greenhouse gas reduction becomes more important. Carbon dioxide dry reforming is a promising green-house gas reduction technology that can obtain CO and $H_2$ which are high value-added materials by utilizing $CO_2$ and $CH_4$ which are greenhouse gases. However, there is a significant coking problem during operation of the dry reforming reactor. Because the carbon dioxide dry reforming is a strong endothermic reaction, the temperature of the reactor drops near the reactor inlet and causes coke formation. To solve this problem, it is important to ensure that the reaction takes place in a temperature range where coke production is minimized. In this study, we proposed a design method that can maintain reaction temperature in the region where the coke is rarely generated by using the new catalyst configuration method. The design method also optimizes the reactor by solving the optimization problem which minimizes the reactor length for a given reaction conversion by using the fuel flow rate, catalyst density, and output temperature by section as optimization variables.

• Korean Chemical Engineering Research
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• v.57 no.2
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• pp.244-252
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• 2019

This study investigated the effect of addition of aromatics such as Toluene/LCO/resin on the coke depression and asphaltene conversion. The experiment was carried out with vacuum residue as a feedstock with Molybdenum dispersed catalysts under the slurry-phase hydrocracking condition (Temp. of $425^{\circ}C$, $H_2$ pressure of 80 bar at $80^{\circ}C$, reaction time of 4 hr, Mo-concentration of 500 ppm). As results, the coke reduction was shown to be similar irrespective of types of aromatics, while asphaltene was more converted to gas and maltene when LCO and resin with higher dipole moment were added. The addition of aromatics with change of reaction time showed no difference in terms of depression of coke formation. But the addition of LCO rather increased the coke yield after 2 hr. And it was found that asphaltene in liquid phase had the higher aromaticity index so that asphaltene is difficult to disperse in oil phase.

• Applied Chemistry for Engineering
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• v.8 no.4
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• pp.685-693
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• 1997

We have studied the reforming of carbon dioxide with methane over various supported nickel catalysts. The nickel supported on natural zeolite showed the highest activity and the nickel on acidic support showed higher activity and slow deactivation compared to nickel on basic support. The activity of nickel on natural zeolite increased with increasing loading ratio and showed almost constant activity above 10wt.% loading of nickel. The conversion and yield of products were affected by the mole ratio of reactants and the highest yields of CO and $H_2$ were obtained at $CH_4/CO_2=1$. The deactivation of catalyst was caused by deposition of coke which was formed by the decomposition of methane. The shape of coke was shown to be whisker tripe carbon, and it brought out the slow deactivation of catalyst.

• Applied Chemistry for Engineering
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• v.8 no.3
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• pp.543-549
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• 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
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• v.46 no.4
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• pp.813-818
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• 2008

Various additives were added in small amounts on Ni/YSZ anode of SOFC (solid oxide fuel cell) in order to improve reactivity and to inhibit deactivation due to coke deposition during methane reforming using a low mole ratio steam ($H_2O/CH_4=1.5$) at $800^{\circ}C$. Ni/YSZ catalysts added with various perovskites did not show any improvement but exhibited a gradual decrease in the methane conversion. K-doped Ni/YSZ showed a steady increase and maintenance of the conversion up to 42 hours, after which there was an abrupt deactivation of catalyst owing to potassium loss by volatilization. Addition of 5% of $K_2Ti_2O_5$ on Ni/YSZ showed a stable maintenance of the conversion without K loss, and was able to prevent coke formation during a long time operation. Deactivation of catalyst during the reaction was mainly caused by the accumulation of graphidic carbon on the catalyst surface.

• Korean Chemical Engineering Research
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• v.57 no.4
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• pp.575-583
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• 2019

The results of the catalytic reaction by pulsed injection of reactants are useful for studying the initial reaction characteristics in the case of many coke invloved reactions. The dehydrogenation characteristics of alumina supported platinum tin catalysts were investigated by pulsed injection of propane. The yield of propylene was maximized when the reduction time of propane injection catalyst was $550^{\circ}C$. Raman analysis showed that the amount of coke was very small when PtSn (4.5) catalyst was used and the short contact time was simulated by propane pulse injection. n order to differentiate the degree of dispersion of platinum, PtSn (4.5) catalyst was sintered at $900^{\circ}C$ with hydrogen, and then the temperature of air - redispersion was varied and propane pulse was injected. As a result, conversione and yield were the highest when air-redispersion temperature is $600^{\circ}C$. The lower the air-redispersion temperature, the higher the selectivity. As the tin content in the platinum catalyst increased, the propane conversion was lowered, but the selectivity to propylene increased and the yield increased. From this, it can be seen that the tin-added platinum catalyst is less active than the platinum catalyst from the beginning of the reaction, which is less affected by coke. The dehydrogenation reaction by the propane pulse injection shows a higher conversion rate than the result of continuous injection due to the formation of COx, and the amount of coke is very small. Decrease in selectivity due to the formation of COx can be reduced by increasing the reduction temperature and time.

• Korean Chemical Engineering Research
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• v.57 no.5
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• pp.611-619
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• 2019

This study was carried out to investigate fuel decomposition characteristics and coke formation according to types of endothermic fuels and methods of catalyst molding. Methylcyclohexane (MCH), n-dodecane, and exo-tetrahydrodipentadiene (exo-THDCP) were used as the endothermic fuels. As a catalyst, USY720 supported with platinum was used. It was manufactured by only using pressure to disk-type, or pelletized with a binder and a silica solution. The characteristics of the catalysts according to the molding method were analyzed by X-ray diffraction analysis, scanning electron microscopy, nitrogen adsorption-desorption isotherm, and ammonia temperature programmed desorption analysis. The reaction was carried out under conditions of high temperature and high pressure ($500^{\circ}C$, 50 bar) in which the fuel could exist in a supercritical state. The product was analyzed by gas chromatograph/mass spectrometer and the coke produced by the catalyst was analyzed by thermogravimetric analyzer. After the reaction, the composition of the products varied greatly depending on the structure of the fuel. In addition, the crystallinity and surface properties of the catalysts were not changed by the method of catalyst molding, but the changes of the acid sites and the pore characteristics were observed, which resulted in changes in the amount and composition of products and coke.

• 한국연소학회:학술대회논문집
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• 2006.10a
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• pp.36-41
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• 2006

A simplified model of plastic layer and internal gas pressure In a coke oven is presented. We calculate internal gas pressure using presented model. And results are compared with calculated results using experimental data. Results show the difference of internal gas pressure by coal composition. The model is used to show that the permeability at the resolidification end of the plastic layer is a key determinant of the magnitude of the internal gas pressure.