• Korean Chemical Engineering Research
• /
• v.51 no.4
• /
• pp.418-425
• /
• 2013

The catalytic conversion of ethanol to aromatic compounds ETA was studied over ZSM-5 heterogeneous catalysts. The effect of reaction temperature, weight hourly space velocity (WHSV), and addition of water and methanol, which are the potential impurities of bio-ethanol, on the catalytic performance was investigated in a fixed bed reactor. Commercial ZSM-5 catalysts having different Si/$Al_2$ ratios of 23 to 280 and modified ZSM-5 catalysts by addition of metal (Zn, La, Cu, and Ga) were used for the activity and stability tests in ETA reaction. The catalysts were characterized with ammonia temperature programmed desorption ($NH_3$-TPD) and nitrogen adsorption-desorption techniques. The results of catalytic performance revealed that the optimal Si/$Al_2$ ratio of ZSM-5 is about 50~80 and the selectivity to aromatic compounds decreases in the order of Zn/La > Zn > La > Cu > Ga for the modified ZSM-5 catalysts. Among these catalysts from the ETA reaction, Zn-La/ZSM-5 showed the best catalytic performance for the ETA reaction. The selectivity to aromatic compounds was 72% initially and 56% after 30 h over the catalysts at reaction temperature of $437^{\circ}C$ and WHSV of $0.8h^{-1}$.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.02a
• /
• pp.319-319
• /
• 2011

Hydrolysis of sodium borohydride provides a safe and clean approach to hydrogen generation. Having the proper catalytic support for controlling this reaction is therefore a valuable technology. Here we demonstrate the capability of hydroxyapatite as a novel catalytic support material for hydrogen generation. Aside from being inexpensive and durable, we reveal that Ru ion exchange on the HAP surface provides a highly active support for sodium borohydride hydrolysis, exemplifying a high total turnover number of nearly 24,000 mol $H_2$/ mol Ru. Moreover, we observe that the RuHAP support exhibits a high catalytic lifetime of approximately one month upon repeated exposure to $NaBH_4$ solutions. In addition to examining surface area effects, we also identified the role of complex surface morphology in enhancing hydrolysis by the catalytic transition metal covered surface. Particularly, we found that a polycrystalline RuHAP catalytic support exhibits shorter induction times for the initial bubble formation as well as increased hydrogen generation rates as compared to a single crystal supports. The independent factor of a complex surface morphology is believed to provide enhanced sites for gas release during the initial stages of the reaction. By demonstrating the ability to shorten induction time and enhance catalytic activity through changes in surface morphology and Ru content, we find it feasible to further explore this catalyst support in the construction of a practical hydrogen generator.

• Clean Technology
• /
• v.21 no.2
• /
• pp.130-139
• /
• 2015

The NO oxidation process has been applied to improve a removal efficiency of NO included in exhaust gas. In this study, to produce a dry oxidant for the NO oxidation process, the catalytic H₂O₂ decomposition method was proposed. A variety of the heterogeneous solid-acidic Mn-based catalysts were prepared for the catalytic H₂O₂ decomposition and the effect of their physico-chemical properties on the catalytic H₂O₂ decomposition were investigated. The results of this study showed that the acidic sites of the Mn-based catalysts has an influence on the catalytic H₂O₂ decomposition. The Mn-based catalyst having the abundant acidic sites within the wide temperature range in NH₃-TPD shows the best performance for the catalytic H₂O₂ decomposition. Therefore, the NO oxidation efficiency, using the dry oxidant produced by the H₂O₂ decomposition over the Mn-based catalyst having the abundant acidic properties under the wide temperature range, was higher than the others. As a remarkable result, the best performances in the catalytic H₂O₂ decomposition and NO oxidation was shown when the Mn-based Fe₂O₃ support catalyst containing K component was used for the catalytic H₂O₂ decomposition.

• Journal of Environmental Science International
• /
• v.17 no.2
• /
• pp.211-224
• /
• 2008

Characteristics of the esterification reaction between free fatty acid in rice bran oil and methanol was investigated in the presence of catalysts, such as PTS(p-toluene sulfonic acid), Amberlyst 15 dry and SCX(silica gel based strong cation exchange resin). While reaction temperature was kept constant at $65^{\circ}C$, initial feed content of free fatty acid was varied from 100% to 1% by addition of pure free fatty acid which was previously made from rice bran oil. Also, the effect of mole ratio of methanol to fatty acid on the final conversion was examined. When esterification of pure free fatty acid was catalyzed by several acids, final conversions were increased in order of Amberlyst 15 dry, SCX and PTS. Using PTS catalyst, initially the reaction proceeded in homogeneous 2nd oder reaction mechanism. However, phase of reaction mixture changed from homogeneous to heterogeneous along the reaction time and then reaction rate was retarded by mass transfer resistance of methanol. Final conversion of free fatty acid in reaction mixture was depended on initial feed content of free fatty acid, and had maximum value at 30% of initial feed free fatty acid content for all kinds of catalysts used. And the final conversion was increased with mole ratio of methanol by the improvement of reaction rate. When initial feed free fatty acid content below 10% and the reaction was catalyzed by PTS, concentration of free fatty acid in reaction mixture was increased in the middle of reaction time by hydrolysis of triglyceride in reaction mixture. Also, if silica gel was added into the reaction mixture which had initial feed free fatty acid content below 50%, final conversion was increased by the adsorption of moisture produced. The SCX catalyst made the esterification reaction of free fatty acid to progress like in case of PTS catalyst. However, when initial feed free fatty acid content below 10%, concentration of free fatty acid in. reaction mixture was decreased monotonically and not increased in the middle of reaction time on the contrary to the case of PTS. Thus, SCX catalyst accomplished more high value of final conversion than PTS catalyst for the initial feed fatty acid content range from 50% to 5% In case of initial feed free fatty acid content of 1% and mole ratio of methanol was 2, concentration of free fatty acid in reaction mixture increased over the initial feed free fatty acid content for all kind of catalysts used. Although SCX catalyst was added into reaction mixture which had 1% of initial feed fatty acid content, final conversion was hardly raised by mole ratio of methanol.

• Clean Technology
• /
• v.14 no.2
• /
• pp.71-86
• /
• 2008

In this review we discussed the effective ways to catalytically derive value-added chemicals from propane which has been utilized only as an energy source so far. Among various propane-derived products, the most valuable chemicals such as propylene and acrylonitrile were mainly focused herein. Propylene could be manufactured through oxidative dehydrogenation of propane using $O_2,\;CO_2$, etc. as an oxidant for the purpose of overcoming thermodynamic limitations of propane dehydrogenation. On the other hand, propane ammoxidation would be an alternative to propylene ammoxidation for producing acrylonitrile since propane is much cheaper than propylene as a starting material. Although effective $MoVTeNbO_x$ catalysts have been developed fur propane ammoxidation in recent years, more detailed studies should be thoroughly performed. In carrying out both oxidative dehydrogenation and ammoxidation of propane fur a long period, the most critical issue is definitely considered to find out the most active and selective catalysts, which makes it possible to commercialize both reactions into economically viable processes.

• Carbon letters
• /
• v.6 no.1
• /
• pp.31-40
• /
• 2005

The carbon nanofibers (CNFs) were synthesized through the catalytic decomposition of hydrocarbons in a quartz tube reactor. The CNFs prepared from $C_3H_8$ at $550^{\circ}C$ was selected as the purification sample due to the higher content of impurity than that prepared from other conditions. In this study, we carried out the purification of CNFs by oxidation in air or carbon dioxide after acid treatment, and investigated the influence of purification parameters such as kind of acid, concentration, oxidation time, and oxidation temperature on the structure of CNFs. The metal catalysts could be easily eliminated from the prepared CNFs by liquid phase purification with various acids and it was verified by ICP analysis, in which, for example, Ni content decreased from 2.51% to 0.18% with 8% nitric acid. However, the particulate carbon and heterogeneous fibers were not removed from the prepared CNFs by thermal oxidation in air and carbon dioxide. This result can be explained by that the direction of graphene sheet in CNFs is vertical to the fiber axis and the CNFs are oxidized at about the similar rate with the impurity carbon.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.10
• /
• pp.2835-2840
• /
• 2010

A series of $MoO_3/CeO_2-ZrO_2$ catalysts with different Mo content (8 - 20 wt %) were prepared by simple co-precipitation followed by impregnation method and were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), energy dispersive spectroscopic (EDS) techniques. The prepared materials were tested for catalytic activity by the synthesis of benzimidazole derivatives using condensation of aromatic aldehydes and o-phenylenediamine by conventional and microwave method. Obtained results reveal that the catalytic activity increases with increase in Mo wt % loading. The best catalytic activity was obtained with 20 wt % $MoO_3/CeO_2-ZrO_2$. The particle size or crystallite size was estimated using Debye-Scherrer equation. After completion of reaction, the catalyst can be recovered efficiently and reused with consistent activity.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.2
• /
• pp.355-362
• /
• 2009

The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, hydroxyl functionalized oxovanadium(IV) Schiff-base; N,N'-bis(4-hydroxysalicylidene)-ethylene-1, 2-diamineoxovanadium(IV), [VO($(OH)_2$-salen)]; has been covalently anchored on modified MWNTs. The new modified MWNTs ([VO($(OH)_2$-salen)]-MWNTs]) have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), UV-Vis, Diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The analytical data indicated a composition corresponding to the mononuclear complex of tetradentate Schiff-base ligand. The characterization of the data showed the absence of extraneous complex, retention of MWNTs and covalently anchored on modified MWNTs. Liquid-phase oxidation of cyclohexane with $H_2O_2$ to a mixture of cyclohexanone, cyclohexanol and cyclohexane-1,2-diol in $CH_3$CN have been reported using oxovanadium(IV) Schiff-base complex covalently anchored on modified MWNTs as catalysts. This catalyst is more selective toward cyclohexanol formation.

• Proceedings of the KSME Conference
• /
• 2008.11b
• /
• pp.1996-2000
• /
• 2008

In autothermal reforming reaction, oxygen to carbon ratio (OCR) and steam to carbon ratio (SCR) are significant factors, which control temperature and carbon deposition into the reactor. The OCR is more sensitive than the SCR to affect the temperature distribution and reforming efficiency. In conventional operation, hydrocarbon fuel, steam, and oxygen was homogeneously mixed and injected into the reactor in order to get hydrogen-rich gas. The temperature was abruptly raised due to fast oxidation reaction in the former part of the reactor. Deactivation of packed catalysts can be accelerated there. In the present study, therefore, the effect of the oxygen distribution is introduced and investigated to suppress the carbon deposition and to maintain the reactor in the mild operating temperature (e.g., $700{\sim}800^{\circ}C$). In order to investigate the effect numerically, the following models are adopted; heterogeneous reaction model and two-medium model for heat balance.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2010.02a
• /
• pp.35-35
• /
• 2010

Understanding the mechanistic details of heterogeneous catalytic reactions will provide a way to tune the selectivity between various competing reaction channels. In this regard, catalytic decomposition of alcohols over the rutile $TiO_2$(110) surface as a model oxide catalyst has been studied to understand the reaction mechanism employing the temperature-programmed desorption (TPD) technique. The $TiO_2$(110) model catalyst is found to be active toward alcohol dehydration. We find that the active sites are bridge-bonded oxygen vacancies where RO-H heterolytically dissociates and binds to the vacancy to produce alkoxy (RO-) and hydroxyl (HO-). Two protons adsorbed onto the bridge-bonded oxygen atoms (-OH) readily react with each other to form a water molecule at ~500 K and desorb from the surface. The alkoxy (RO-) undergoes decomposition at higher temperatures into the corresponding alkene. Here, the overall desorption kinetics is limited by a first-order decomposition of intermediate alkoxy (RO-) species bound to the vacancy. We show that detailed analysis on the yield and the desorption temperatures as a function of the alkyl substituents provides valuable insights into the reaction mechanism. After the catalytic role of the oxygen vacancies has been established, we employed x-ray photoelectron spectroscopy to further study the surface electronic structure related to the catalytically active defective sites. The defect-related state in valence band has been related to the chemically reduced $Ti^{3+}$ defects near the surface region and are found to be closely related to the catalytic activity of the $TiO_2$(110) surface.