• Clean Technology
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• v.28 no.4
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• pp.269-277
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• 2022

With the recent development of the biological enzymatic reaction industry, lactic acid (LA) can be mass-produced from biomass sources. In particular, a catalytic process that converts LA into acrylic acid (AA) is receiving much attention because AA is used widely in the petrochemical industry as a monomer for superabsorbent polymers (SAP) and as an adhesive for displays. In the LA conversion process, NaY zeolites have been previously shown to be a high-activity catalyst, which improves AA selectivity and long-term stability. However, NaY zeolites suffer from fast deactivation due to severe coking. Therefore, the aim of this study is to modify the acid-base properties of the NaY zeolite to address this shortcoming. First, base promoters, Ca ions, were introduced to the NaY zeolites to tune their acidity and basicity via ion exchange (IE) and incipient wetness impregnation (IWI). The IWI method showed superior catalyst selectivity and stability compared to the IE method, maintaining a high AA yield of approximately 40% during the 16 h reaction. Based on the NH₃- and CO₂-TPD results, the calcium salts that impregnated into the NaY zeolites were proposed to exit as an oxide form mainly at the exterior surface of NaY and act as additional base sites to promote the dehydration of LA to AA. The NaY zeolites were further treated with KOH before calcium impregnation to reduce the total acidity and improve the dispersion of calcium through the mesopores formed by KOH-induced desilication. However, this KOH treatment did not lead to enhanced AA selectivity. Finally, calcium loading was increased from 1wt% to 5wt% to maximize the amount of base sites. The increased basicity improved the AA selectivity substantially to 65% at 100% conversion while maintaining high activity during a 24 h reaction. Our results suggest that controlling the basicity of the catalyst is key to obtaining high AA selectivity and high catalyst stability.

• Applied Chemistry for Engineering
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• v.26 no.2
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• pp.217-223
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• 2015

Effects of the post-acid treatment of SAPO-34 sample by hydrochloric acid were investigated to enhance the catalytic performance in DTO reaction. Uniformly sized SAPO-34 samples with cubic-like morphology were prepared by hydrothermal method using TEAOH and DEA as the structure directing agents. It was modified in terms of the HCl concentration and treating time. As a result, the total surface area and micropore volume for the well modified samples increased and the total acid site was somewhat decreased along with the erosion of the external surface. Especially, the catalytic lifetime and light olefins selectivity for acid treated SAPO-0.2 M (3 h) samples were considerably enhanced compared with those of untreated SAPO-34 samples. It indicates that the deactivation by coke formation proceeds mainly at the pore entrance on the external surface. Therefore, the acid treatment was confirmed to be a simple method which can significantly improve the catalytic performance by modifying the external surface of SAPO-34 catalyst.

• Journal of Korean Society of Environmental Engineers
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• v.35 no.5
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• pp.356-362
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• 2013

An attempt has been made to optimize elongated rotating arc plasma $NH_3$ scrubber. Among diverse semiconductor processes, diffusion and implantation process inevitably produce $NH_3$ as byproduct and efficient dry process for the decomposition of $NH_3$ is required. Plasma process does not produce NOx that is commonly produced in combustion process and there is no problem of deactivation, usually experienced in catalyst process. However, plasma process uses electrical energy and needs to be optimized to achieve feasibility of application. In this work, mode control of rotating arc is presented as tentative solution for the possible optimization of the process. Based on existing rotating arc, scale-up and following mode mapping was tried. Proposed reactor design was evaluated in the $NH_3$ decomposition process and revealed that optimization scheme is at hand. In the experiment of full scale scrubber including heat exchanger, the process gave more stable and efficient process of $NH_3$ decomposition.

• Applied Chemistry for Engineering
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• v.7 no.4
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• pp.645-652
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• 1996

Selective catalytic oxidation of $H_2S$ to elemental sulfur using $TiO_2/SiO_2$ catalysts was investigated in this study. The reaction test with pure $TiS_2$ and $Ti(SO_4)_2$ and cyclic temperature operation revealed that $TiO_2$ had a good resistance to sulfation and sulfidation, which are known as the main cause of catalytic deactivation in sulfur recovery process. With the increase of $TiO_2$ loading amount in $TiO_2/SiO_2$ catalysts, the conversion of $H_2S$ increased and the selectivity of elemental sulfur was very slightly decreased. As the ratio of $O_2/H_2S$ increased, the selectivity to elemental sulfur was drastically decreased. In the presence of 10 vol.% water vapor to a stoichiometric mixture of $H_2S$ and $O_2$($H_2S$= 5 vol.% O=2.5 vol.% ), both activity and selectivity of 10 wt.% $TiO_2/SiO_2$ catalyst are decreased, but it still showed more than 80% of sulfur yield.

• Journal of the Korean Chemical Society
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• v.20 no.6
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• pp.469-478
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• 1976

Clinoptilolite zeolite samples were treated with hydrochloric acid, sulfuric acid and phosphoric acid of different strength and the adsorption characteristics and crystal structures of the original and acid-treated clinoptilolites were studied. By treating with hydrochloric acid, the adsorbed amount increased to 5-fold for nitrogen, to 3-fold for benzene, but for methanol no significant change was observed. As acid strength increased further, there were declines both in adsorption capacity and crystallinity. The results showed that the increase of adsorbed amount was caused by the rearrangement of the pore entrance and cation exchange. A method for determination of clinoptilolite content in natural mineral based on benzene adsorption on acid-treated sample is proposed. By this method, the original sample used in this study was found to contain approximately 40% of clinoptilolite. Using pulse technique in micro-catalytic reactor system, the catalytic activities of hydrochloric acid-treated clinoptilolites in cumene cracking and toluene disproportionation reactions were measured. For cumene cracking reaction, the maximum conversion was observed for the 0.5 N hydrochloric acid-treated sample. It is instructive to note that the maximum benzene adsorption was also observed for the sample treated with 0.5 N HCl. This suggest that the conversion rate was determined mainly by the rate of transport of reactants and the products through the pore structure. In the toluene disproportionation reaction, the same trend was observed. But the rate of deactivation was high for samples with strong acid sites. Since catalyst having higher activity was deactivated more easily, the conversion maximum was shifted to the sample treated with higher concentration of acid, -1N. The catalytic activity of $Ca^{2+} and La^{3+} ion exchanged samples for the toluene disproportion was much lower than that of acid-treated samples. Introduction of Ca^{2+} and La^{3+}$ into the pore structure apparently decreases the effective pore diameter of acid-treated clinoptilolite thus limiting the diffusion of reactants and products.

• Applied Chemistry for Engineering
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• v.32 no.6
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• pp.613-620
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• 2021

A flow channel shape of PEMFC has an influence on the internal flow uniformity. If the reactant distribution in a flow path is not uniform during operation, both catalyst deactivation and mechanical damage of membrane could occur resulting in decreasing the membrane electrode assembly (MEA) durability. Numerous studies concerning flow design have been conducted to make smooth supply and uniform distribution of reactants in fuel cells. The baffle of flow path could improve fuel cell performance through the forced convection effect. A sub-channel, as an additional air flow path, could increase the reactant concentration and reduce the mass transfer loss via a smooth water discharge. In this study, computational fluid dynamics (CFD) was used to analyze the effect of blocks and sub-channels on the current density and oxygen concentration of the fuel cell. As a result, the limit current density and oxygen concentration at a rear block increased when using blocks and sub-channels in a flow channel. In particular, the current density increased significantly when the sub-channel was placed between two blocks. Also, the sub-channel position was optimized by analyzing the oxygen concentration, and the oxygen concentration was recovered at a rear block in the fuel cell.

• Korean Chemical Engineering Research
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• v.60 no.4
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• pp.620-629
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• 2022

By varying various experimental conditions such as heating rate, molar hourly space velocity (MHSV), and nitridation reaction temperature, vanadium oxynitride was prepared through temperature programmed reduction/nitridation reaction (TPRN) of vanadium pentoxide and ammonia, and characterization were performed. In order to investigate the physico-chemical properties of the prepared catalyst, N₂ adsorption-desorption analysis, X-ray diffraction analysis (XRD), hydrogen temperature programmed reduction (H₂-TPR), temperature programmed oxidation (TPO), ammonia temperature programmed desorption (NH₃-TPD), transmission electron microscopy (TEM) was performed. Transformation of V₂O₅ with 5 m² g^-1 low specific surface area by reduction at 340 ℃ to V₂O₃ showed a high specific surface area value of 115 m² g^-1 by micropore formation. As the nitridation temperature increased beyond that, the specific surface area continued to decrease due to sintering. The nitridation reaction variable that had the greatest influence on the specific surface area was the reaction temperature, and the x + y value of VN_xO_y of a single phase approached from 1.5 to 1.0 as the nitridation reaction temperature increased. At a high reaction temperature of 680 ℃, the cubic lattice constant a was VN. close to the value. At 680 ℃, the highest nitridation temperature among the experimental conditions, the ammonia conversion rate was 93%, and no deactivation was observed.

• Clean Technology
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• v.21 no.1
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• pp.68-75
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• 2015

In this study, we investigated the structure and properties of a highly heat conductive metal-ceramic core-shell CoAl₂O₄@Al micro-composite for heterogeneous catalysts support. The CoAl₂O₄@Al was prepared by hydrothermal surface oxidation of Al metal powder, which resulted in the structure with a high heat conductive Al metal core encapsulated by a high surface area CoAl₂O₄ shell. For comparison, CoAl₂O₄ was also prepared by co-precipitation method and also utilized for a catalyst support. Rh catalysts supported on CoAl₂O₄@Al and CoAl₂O₄ were prepared by incipient wetness impregnation and characterized by N₂ adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), CO chemisorption, and temperature-programmed reduction (TPR). The properties of catalysts were investigated for glycerol steam reforming reaction for hydrogen production at 550 ℃. Rh/CoAl₂O₄@Al exhibited about 2.8 times higher glycerol conversion turnover frequency (TOF) than Rh/CoAl₂O₄ due to facilitated heat transport through the core-shell structure. The CoAl₂O₄@Al and CoAl₂O₄ also showed some catalytic activities due to a partial reduction of Co on the support, and a higher catalytic activity was also found on the CoAl₂O₄@Al core-shell than CoAl₂O₄. These catalysts, however, displayed deactivation on the reaction stream due to carbon deposition on the catalysts surface.

• Applied Chemistry for Engineering
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• v.5 no.5
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• pp.808-818
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• 1994

Effects of ceria additive on the activity and thermal aging behavior of supported Ru catalysts were investigated using Ru/${\gamma}$-$Al_2O_3$and Ru/$CeO_2$-${\gamma}$-$Al_2O_3$. The catalysts were characterized by $^{129}Xe$-NMR and $H_2$ chemisorption. The cataltic activity for conversion of CO, HC and $NO_x$ was measured using simulated automobile engine exhausts under lean, rich and stoichiometric conditions. For both fresh and aged catalysts, Ru/$CeO_2$-${\gamma}$-$Al_2O_3$ was more active than Ru/${\gamma}$-$Al_2O_3$ for all three pollutants. Results of $^{129}Xe$-NMR and $H_2$ chemisorption indicated that sintering of Ru particles occurred to the same extent for both catalysts during the thermal aging process. After thermal aging at 673K, however, the catalytic activity of the aged Ru/$CeO_2$-${\gamma}$-$Al_2O_3$ was substantially higher than that of the fresh one, while the activity of Ru/${\gamma}$-$Al_2O_3$ decreased after the thermal aging. This finding may suggest new active sites were created during the thermal aging, probably in the vicinity of the interface between Ru and Ce. For more quantitative investigation of the effect of a cation such as Ce on the thermal aging of Ru metal particles, Ru catalysts supported on cation-exchanged Y-zeolites were used as the model catalysts. The results indicated that when Ba, Ca, La, Y or Ce was used for the cation exchange, the exchanged cation did not affect the thermal aging behavior of Ru in Y-zeolite, as evidenced by $^{129}Xe$-NMR and EXAFS.