• Bulletin of the Korean Chemical Society
• /
• v.30 no.8
• /
• pp.1778-1782
• /
• 2009

Mesoporous TS-1 catalysts were prepared via a nanocasting route using two different carbon template sources of CMK-3 and commercial carbon black. Products were characterized by XRD, UV-Vis spectroscopy, SEM, TEM, and $N_2$ adsorption- desorption measurement. The catalytic performances of the samples for allylchloride epoxidation and oxidative desulfurization of the representative refractory sulfur compounds, dibenzothiophene and 4,6-dimethyldibenzothiophene, were compared against those of conventional TS-1. Whilst the allychloride epoxidation activity for the mesoporus TS-1 samples were similar, mesoporous TS-1 exhibited significantly higher catalytic activities than conventional TS-1 in oxidative desulfurization.

• Korean Chemical Engineering Research
• /
• v.46 no.5
• /
• pp.845-851
• /
• 2008

Oxidative desulfurizaton of model sulfur compounds and Industrial diesel fuel(LCO; Light Cycle Oil) over Ti-grafted SBA-15 catalyst was studied in a batch reactor with tert-Butyl Hydroperoxide(TBHP) as oxidant. Effects of Ti loading, TBHP/Sulfur mole ratio, reaction temperature on ODS activity and kinetic parameters were investigated. Ti-grafted SBA-15 catalyst showed higher sulfur removal activity in the oxidative desulfurization reaction of refractory sulfur compounds(DBT and 4, 6-DMDBT) and LCO, suggesting that Ti-grafted SBA-15 catalyst could be a good candidate for ODS catalyst.

• Korean Chemical Engineering Research
• /
• v.57 no.2
• /
• pp.283-288
• /
• 2019

Catalytic removal of sulfur compounds from heavy naphtha (HN) was investigated using a combination of an oxidation process using hydrogen peroxide and an adsorption process using granulated activated carbon (GAC) and white eggshell (WES). This study investigated the impact of changing several operating parameters on the desulfurization efficiency. Specifically, the volume ratio of $H_2O_2$ to HN (0.01~0.05), agitation speed ($U_{speed}$) of the water bath shaker ($100-500{\pm}1rpm$), pH of sulfur solution (1~5), amount of adsorbent (0.1~2.5 g), desulfurization temperature ($25{\sim}85{\pm}1^{\circ}C$) and contact time (10~180 minutes) were examined. The results indicate that the desulfurization efficiency resulting from catalytic and adsorption processes of GAC is better than that of WES for oxidation and removing sulfur compounds from HN due to its high surface area. The desulfurization efficiency depends strongly on all investigated operating parameters. The maximum removal efficiency of GAC and WES achieved by this study was 86 and 65, respectively.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.1
• /
• pp.225-230
• /
• 2013

A new heteropolyanion-based ionic ($[Hmim]_5PMo_{10}V_2O_{40}$) was synthesized by the reaction of molybdovanadophosphoric acid ($H_5PMo_{10}O_{40}$) with N-methylimidazole. [$[Hmim]_5PMo_{10}V_2O_{40}$ showed a high catalytic activity in the oxidative desulfurization of sulfur-containing compounds in 1-methylimidazolium tetrafluoroborate ($[Hmim]BF_4$) ionic liquid using 30% aqueous $H_2O_2$ as the oxidant. The catalytic system was of high activity, simplified workup and flexible recyclability. The catalytic oxidation reactivity of sulfur-containing compounds decreased in the order dibenzothiophene (DBT) > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The influences of various parameters including reaction time (t) and temperature (T), catalyst dosage, and oxidant to sulfur molar ratio n(O)/n(S) on the desulfurization of model oil were investigated in details. 99.1% of DBT conversion in the model oil was achieved at atmospheric pressure under the optimal conditions: n(O)/n(S) = 4:1, $60^{\circ}C$, 100 min and molar ratio of catalyst to sulfur of 0.062. The ionic liquid can be recycled six times without significant decrease in activity.

• Journal of the Korean Applied Science and Technology
• /
• v.30 no.3
• /
• pp.431-443
• /
• 2013

Sulfur content of diesel fuel has been cut down to under 10 ppm ULSD (ultra low sulfur diesel) level by environmental regulation with the aim of reducing exhaust emissions. This review discusses the methods and principles of sulfur reduction in diesel and presents an overview of new approaches for ultra-deep desulfurization. The deep HDS (hydrodesulfurization) problems of diesel streams is exacerbated by the inhibiting effect of co-existing aromatics, nitrogen compounds and $H_2S$. The new approaches to deep desulfurization includes non-HDS type processing schemes such as adsorptive, extractive and oxidative desulfurization.

• Bulletin of the Korean Chemical Society
• /
• v.21 no.8
• /
• pp.828-830
• /
• 2000

• Bulletin of the Korean Chemical Society
• /
• v.34 no.10
• /
• pp.3065-3072
• /
• 2013

Direct synthesis of $H_2O_2$ and in situ oxidative desulfurization of model fuel over Au/Ti-HMS and Au/TS-1 catalysts has been comparatively investigated in water or methanol. Maximum amount (82%) of active $Au^0$ species for $H_2O_2$ synthesis was obtained. Au/Ti-HMS and Au/TS-1 exhibited the contrary performances in $H_2O_2$ synthesis as $CH_3OH/H_2O$ ratio of solvent changed. $H_2O_2$ decomposition and hydrogenation in water was inhibited by the introduction of methanol. Effect of $O_2/H_2$ ratio on $H_2O_2$ concentration, $H_2$ conversion and $H_2O_2$ selectivity revealed a relationship between $H_2O_2$ generation and $H_2$ consumption. The highest dibenzothiophene removal rate (83.2%) was obtained over Au/Ti-HMS in methanol at 1.5 of $O_2/H_2$ ratio and $60^{\circ}C$. But removal of thiophene over Au/TS-1 should be performed in water without heating to obtain a high removal rate (61.3%). Meanwhile, $H_2$ conversion and oxidative desulfurization selectivity of $H_2$ were presented.

• Korean Chemical Engineering Research
• /
• v.55 no.4
• /
• pp.567-573
• /
• 2017

In this work, tungsten oxide ($WO_x$) supported on SBA-15 (mesoporous silica) were prepared and applied for oxidative desulfurization of sulfur compounds in marine diesel containing about 230 ppmw of sulfur concentration. Prepared catalysts were examined by two steps; at first step, oxidation reaction carried out with hydrogen peroxide as oxidant and then the oxidized sulfur compounds were extracted by acetonitrile as solvent. Catalysts were characterized by using X-ray diffraction, X-ray fluorescence, X-ray photoelectron spectroscopy and $N_2$ adsorption-desorption isotherms. Tungsten oxide exists as monoclinic crystal system on SBA-15 and over about 10 wt% of the $WO_x$ loading took the form of multi-layers on SBA-15. The 13 wt% $WO_x$/SBA-15 catalyst exhibite highest activity, achieving about 76.3% sulfur removal in the reaction conditions, such as catalyst amount of 0.1 g, reaction temperature at $90^{\circ}C$, reaction time for 3 h and O/S molar ratio of 10. One time oxidation reaction is enough oxidize the sulfur compounds in marine diesel completely. The repetition experiment of extraction process indicated that sulfur removal could reach 94.4% after 5 times.

• Clean Technology
• /
• v.16 no.1
• /
• pp.12-18
• /
• 2010

The object of the present study is to apply KF/MgO catalysts to remove sulfur dioxide from dibenzothiophene sulfone, a by-product of oxidative desulfurization. Potassium fluoride was deposited via an impregnation method on MgO. The effects KF loading and calcination on the characteristics of the KF/MgO catalysts were investigated through the BET surface area, XRF, XRD, and temperature-programmed desorption of $CO_2$. The catalytic performances of the samples were investigated during the decomposition of dibenzothiophene sulfone to biphenyl and sulfur dioxide gas. KF loaded on MgO prepared by the impregnation method showed high catalytic activities for the decomposition of dibenzothiophene sulfone. The higher activity of KF/MgO just dried at 373 K, avoiding the usual activation at high temperature, than that over the calcined catalyst is ascribed to increase of the amount of basic sites. The high basicity probably may be due to the coordinately unsaturated $F^-$. The simply dried 10 % KF/MgO catalyst, without the usual activation at high temperature, showed the optimal catalytic properties.

• Clean Technology
• /
• v.25 no.1
• /
• pp.91-97
• /
• 2019

Oxidative desulfurization (ODS) has received much attention in recent years because refractory sulfur compounds such as dibenzothiophenes can be oxidized selectively to their corresponding sulfoxides and sulfones, and these products can be removed by extraction and adsorption. In this work, The oxidative desulfurization of marine diesel fuel was performed in a batch reactor with hydrogen peroxide ($H_2O_2$) in the presence of various supported heteropoly acid catalysts. The catalysts were characterized by XRD, XRF, XPS and nitrogen adsorption isotherm techniques. Based on the sulfur removal efficiency of promising silica supported heteropoly acid catalysts, the ranking of catalytic activity was: $30\;H_3PW_{12}/SiO_2$ > $30\;H_3PMo_{12}/SiO_2$ > $30\;H_4SiW_{12}/SiO_2$, which appears to be related with their intrinsic acid strength. The $30\;H_3PW_{12}/SiO_2$ catalyst showed the highest initial sulfur removal efficiency of about 66% under reaction conditions of $30^{\circ}C$, $0.025g\;mL^{-1}$ (cat./oil), 1 h reaction time. However, through the recycle test of the $H_3PW_{12}/SiO_2$ catalyst, significant deactivation was observed, which was attributed to the elution of the active component $H_3PW_{12}$. By introducing cesium cation ($Cs^+$) into the $H_3PW_{12}/SiO_2$ catalyst, the stability of the catalyst was improved with changing the solubility, and the $Cs^+$ ion exchanged catalyst could be recycled for at least five times without severe elution.