• Clean Technology
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• v.30 no.2
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• pp.145-156
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• 2024

Carbon has a large specific area and excellent chemical stability, so research on its use as a catalyst support is actively conducted. When using carbon as a support, the pretreatment process is essential. Through pretreatment of carbon, the growth of metal nanoparticles can be controlled and the bonding strength between the support and metal particles can be improved. In this study, carbon was pretreated for surface modification and 5 wt% Pd/C catalysts were synthesized using it as a support. Catalytic activity was evaluated through phenol hydrogenation. To compare with nitric acid, which is commonly used in carbon pretreatment, carbon pretreatment was performed using organic acid. Pd/C treated with gluconic acid showed the highest activity, with 94.93% phenol conversion and 92.76% cyclohexanone selectivity. Therefore, it is expected that pretreatment of the carbon support using organic acid will not only overcome the disadvantages of inorganic acid treatment but also improve catalyst performance.

• Korean Chemical Engineering Research
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• v.53 no.3
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• pp.391-396
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• 2015

To investigate the effect of the catalyst synthesis method on the oxidative dehydrogenation (ODH) of nbutenes, $BiFe_{0.65}MoP_{0.1}$ oxide catalysts were prepared with various synthesis methods such as co-precipitation, citric acid method, hydrothermal method, and surfactant templated method. The catalysts were characterized by X-ray Diffraction (XRD), $N_2$ sorption, and $NH_3/1$-butene-temperature programmed desorption ($NH_3/1$-butene-TPD) to correlate with catalytic activity in ODH reaction. Among the catalysts studied here, $BiFe_{0.65}MoP_{0.1}$ oxide catalyst prepared with co-precipitation method marked the highest activity showing 1-butene conversion, 79.5%, butadiene selectivity, 85.1% and yield, 67.7% after reaction for 14 h. From the result of $NH_3$-TPD, the catalytic activity is closely related to the acidity of the $BiFe_{0.65}MoP_{0.1}$-x oxide catalyst and acidity of the $BiFe_{0.65}MoP_{0.1}$ oxde catalyst prepared with co-precipitation method was higher than that of other catalysts. In addition, combined with the 1-butene TPD, the higher catalytic activity is closely related to the amount of weakly adsorbed intermediate (< $200^{\circ}C$) and the desorbing temperature of strongly adsorbed intermediates (> $200^{\circ}C$).

• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.34-40
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• 2014

Mesoporous SAPO-34 catalyst was successfully synthesized by the hydrothermal method using carbon nanotube (CNT) as a secondary template. The effects of CNT contents (0.5, 1.5, 2.5, and 4.5 mol%) on catalytic performances were investigated. The synthesized catalysts were characterized with XRD, SEM, nitrogen physisorption isotherm and $NH_3$-TPD. Among the synthesized catalysts, SAPO-34 catalyst prepared by the addition of 1.5 mol% CNT (1.5C-SAPO-34) observed not only the largest amounts of mesopore volume but also acid sites. However, the mesopore volume was relatively decreased by further increasing of CNT contents due to the formation of small crystalline. The catalytic lifetime and the selectivity of light olefins ($C_2{\sim}C_4$) were examined for the dimethyl ether to olefins reaction. As a result, the 1.5C-SAPO-34 catalyst showed an improvement of ca. 36% in a catalytic lifetime and a better selectivity to light olefins as compared with the general SAPO-34 catalyst.

• Korean Chemical Engineering Research
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• v.50 no.4
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• pp.723-728
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• 2012

The production of biodiesel by transesterification of soybean oil was performed on $MoO_3$, $SnO_2$ and $CeO_2$ mixed oxides. The catalysts were characterized using XRD and $NH_3$-TPD. $MoO_3$ showed the highest activity among the three metal oxides. When 7 wt% of catalysts was introduced into the reactants, the highest activity was obtained and the water added to reactant decreased the catalytic activity. $MoO_3$ and $SnO_2$ mixed with 50:50 showed the highest activity and $CeO_2$ added with 20% on the $MoO_3-SnO_2$ mixed oxide also showed the highest activity. The catalytic activity showed to have a good relationship with the amount of acid site of catalysts. When the waste soybean oil was used as a reactant, the conversion was decreased about 30%.

• Applied Chemistry for Engineering
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• v.32 no.1
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• pp.20-27
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• 2021

Effects of the etching treatment of SAPO-34 catalyst were investigated to improve the catalytic lifetime in DTO reaction. The aqueous NH3 solution was a more appropriate treatment agent which could control the degree of etching progress, compared to that of using a strong acid (HCl) or alkali (NaOH) solution. Therefore, the effect on characteristics and lifetime of SAPO-34 catalyst was observed using the treatment concentration and time of aqueous NH3 solution as variables. As the treatment concentration or time of aqueous NH3 solution increased, the growth of erosion was proceeded from the center of SAPO-34 crystal plane, and the acid site concentration and strength gradually decreased. Meanwhile, it was found that external surface area and mesopore volume of SAPO-34 catalyst increased at appropriate treatment conditions. When the treatment concentration and time were 0.05 M and 3 h, respectively, the lifetime of the treated SAPO-34 catalyst was the longest, and was significantly enhanced by ca. 36% (based on DME conversion of > 90%) compared to that of using the untreated catalyst. The model for the etching progress of SAPO-34 catalyst in a mild treatment process using aqueous NH3 solution was also proposed.

• Applied Chemistry for Engineering
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• v.29 no.2
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• pp.185-190
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• 2018

The dimer of bicyclo [2.2.1] hepta-2,5-diene (norbornadiene) can be used as a high-energy-density fuel. The purpose of this study is to investigate the effect of Co loading on the acid properties of HY zeolite catalyst and the catalytic activity in norbornadiene dimerization. When the cobalt was loaded on the HY zeolite catalyst, the amount of acid sites did not change, but the acid strength weakened. This can be attributed to the decrease in $Br{\ddot{o}}nsted$ acid site and the increase in Lewis acid site. The norbornadiene conversion and yield of norbornadiene dimer over the Co/HY catalyst showed higher than those over the HY zeolite catalyst. The higher activity of the Co/HY catalyst can be ascribed to the higher amount of Lewis acid sites over the Co/HY catalyst. Density and calorific values of the norbornadiene dimer prepared by using the Co/HY catalyst agreed well with the known values in the literature. It was confirmed that the norbornadiene dimer prepared in this study can be used as a high-energy-density fuel.

• Applied Chemistry for Engineering
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• v.5 no.2
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• pp.327-336
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• 1994

The synergistic effects in mechanical mixture catalysts of Mo-V-O and metal oxide were investigated for the selective oxidation of acrolein. The metal oxides used are $SnO_2$, ${\alpha}-Sb_2O_4$, $WO_3$, ${\alpha}-Al_2O_3$, CuO, $MnO_2$, $Cu_2O$, MgO, CoO, and ZnO. Mechanical mixtures of Mo-V-O plus $SnO_2$ or ${\alpha}-Sb_2O_4$ had resulted in higher conversion of acrolein and higher yield of acrylic acid than Mo-V-O. The origin of the synergy is attributed to the cooperation of Mo-V-O and $SnO_2$ or ${\alpha}-Sb_2O_4$, in which $SnO_2$ or ${\alpha}-Sb_2O_4$ forms dissociated oxygens at their oxygen vacancies and transports them to Mo-V-O. $Cu_2O$, MgO, CuO, and $MnO_2$, increased conversion of acrolein but decreased yield of acrylic acid. CoO and ZnO inhibited the catalytic performance of Mo-V-O. The different role of these metal oxides is explained in terms of their oxidation-reduction properties.

• Applied Chemistry for Engineering
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• v.5 no.5
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• pp.819-824
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• 1994

A membrane-like $H_3PMo_{12}O_{40}$-polysulfone film was prepared by blending $H_3PMo_{12}O_{40}$ with polysulfone using dimethylformamide as a common solvent. SEM and EDX analysis showed that $H_3PMo_{12}O_{40}$ was uniformly and finely distributed in the film catalyst. The ESCA measurement also revealed that the oxidation state of Mo was not changed. The $H_3PMo_{12}O_{40}$-polysulfone catalyst showed lower activity for acid-catalyzed reaction and higher activity for oxidation reaction than $H_3PMo_{12}O_{40}$ in ethanol conversion reaction. The oxidation activity of the film catalyst was about 10 times higher than $H_3PMo_{12}O_{40}$. The decrease of acidic activity was due to DMF strongly adsorbed in acid sites of $H_3PMo_{12}O_{40}$, whereas the increase of oxidation activity was mainly due to uniform distribution of $H_3PMo_{12}O_{40}$. Adsorption results showed that the surface character of $H_3PMo_{12}O_{40}$ was drastically increased, while the bulk property of that was almost same after blending. It is suggested that the control of surface/bulk property as well as acid/redox property of heteropoly acid would be possible by blending it with a polymer.

• 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.8 no.5
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• pp.749-755
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• 1997

Molybdenum phosphate(P/Mo = 0.6) has been synthesized with ammonium molybdate and phosphoric acid under aqueous solution. The kinetics of the ammoxidation of methylpyrazine over molybdenum phosphate catalyst was investigated with the variation of reaction temperature and partial pressure of methylpyrazine, oxygen and ammonia, respectively at atmospheric pressure. The catalytic activity was constant for 300hrs operation under our experimental conditions. Under the steady-state condition, the rate equation of methylpyrazine was shown as $-r=kP_{MP}P_{NH3}{^0}P_{O2}{^{\gamma}}({\gamma}=2.2;1.3{\leq}P_{O2}(kPa){\leq}4)$. The apparent activation energy was 29.6kcal/mol below 623K. The main product obtained in the ammoxidation of methylpyrazine is cyanopyrazine whose selectively was kept always over 90% regardless of conversion.