• Clean Technology
• /
• v.20 no.1
• /
• pp.88-94
• /
• 2014

During the past decades much attention has been paid to the desulfurization of diesel oil which is important as a source for the fuel cells to prevent the sulfur poisoning of both diesel steam reforming catalyst and electrode of fuel cell. Although alternative desulfurization techniques have been investigated, desulfurization for ultra-low sulfur diesel (ULSD) is still challenged. Therefore, this research focuses on the desulfurization of commercial ULSD for the application to molten carbonate fuel cell (MCFC). Herein, the performances of several kinds of commercial adsorbents based on activated carbons, zeolites, and metal oxides for desulfurization of ULSD were screened. The results showed that metal oxides based materials can feasibly reduce sulfur concentration in ULSD to a level of 0.1 ppmw while activated carbons and zeolites did not reach this level at current conditions.

• 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.

• 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.

• Korean Chemical Engineering Research
• /
• v.55 no.6
• /
• pp.874-880
• /
• 2017

In this study, we performed numerical simulation of the adsorptive desulfurization reactor for a 100 kW fuel cell. Using experimental results and the adsorption kinetics theory, the adsorption rate of sulfur in diesel was estimated and verified by numerical analysis. By analyzing the performance of desulfurization according to reactor size, the optimal reactor size was determined. By maximizing processed diesel amount, optimal diesel flow rate was determined. Regeneration process was also confirmed for the obtained optimal reactor size. The present work will be utilized to design a diesel desulfurization reactor for a fuel cell used in a ship by further process modeling and economic analysis.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.10
• /
• pp.3213-3217
• /
• 2012

Reactive adsorption desulfurization (RADS) experiments were conducted over a series of commercial metal oxide supports ($Al_2O_{3-}$, $SiO_{2-}$, $TiO_{2-}$ and $ZrO_{2-}$) supported Ni/ZnO adsorbents. The adsorbents were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), and Fourier transform infrared spectroscopy (FTIR) in order to find out the influence of specific types of surface chemistry and structural characteristics on the sulfur adsorptive capacity. The desulfurization performance of all the studied adsorbents decreased in the following order: Ni/ZnO-$TiO_2$ > Ni/ZnO-$ZrO_2$ > Ni/ZnO-$SiO_2$ > Ni/ZnO-$Al_2O_3$. Ni/ZnO-$TiO_2$ shows the best performance and the three hour sulfur capacity can achieve 12.34 mg S/g adsorbent with a WHSV of $4h^{-1}$. Various characterization techniques suggest that weak interaction between active component and support component, high dispersion of NiO and ZnO, high reducibility and large total Lewis acidity of the adsorbents are important factors in achieving better RADS performance.

• Korean Chemical Engineering Research
• /
• v.43 no.5
• /
• pp.588-594
• /
• 2005

We have investigated Y zeolite and activated carbon for an adsorptive desulfurization of diesel. In batch experiments, cation ($Cu^{2+}$, $Ni^{2+}$) exchanged Y zeolites showed high equilibrium adsorption capacity for sulfur compounds in model diesel, which contained BT, DBT and 4,6-DMDBT of each 50 ppmw in n-octane. But the cation exchanged Y zeolites lost its capacity in commercial diesel (186 ppmw). On the other hand, activated carbon showed reasonable adsorption capacity for sulfur compounds in both model and commercial diesel. The adsorption capacity of sulfur on Ni-Y zeolite was decreased with the increase of benzene concentration in model diesel but the sorption capacity on activated carbon was insensitive to aromatic concentration. In breakthrough test, activated carbon of 1 g could treat 15 ml of commercial diesel with 186 ppmw sulfur. Toluene showed good solvent for regenerating activated carbon among several solvents.

• Korean Chemical Engineering Research
• /
• v.48 no.4
• /
• pp.534-539
• /
• 2010

The adsorptive removal of organic sulfur compounds including tert-butylmercaptane(TBM), tetrahydrothiophene(THT) and dimethylsulfide(DMS) in methane was investigated over NaY and copper-exchanged NaY(CuNaY) zeolites at 303 K and atmospheric pressure. In the ternary adsorption system, the preferential adsorption of THT over other sulfur compounds on NaY and the concurrent adsorption of all sulfur compounds on CuNaY were achieved, which could be explained by the breakthrough curve, the temperature-programmed desorption, and the apparent activation energy for desorption. The sulfur uptake capacity of CuNaY(2.90~3.20 mmol/g) was much higher than that of NaY(0.70~0.90 mmol/g). A comparative study indicated that the $Cu^{1+}$ sites and acidity of CuNaY were probably responsible for the strong interaction with sulfur atom and high sulfur uptake abilities.

• Clean Technology
• /
• v.15 no.1
• /
• pp.60-66
• /
• 2009

Adsorptive removal of tetrahydrothiophene (THT) and tert-butylmercaptan (TBM) that were widely used sulfur odorants in pipeline natural gas was studied using various ion-exchanged NaY zeolites at ambient temperature and atmospheric pressure. In order to improve the adsorption ability, ion exchange was performed on NaY zeolites with alkali metal cations of $Li^+,\;Na^+,\;K^+$ and transition metal cations of $Cu^{2+},\;Ni^{2+},\;Co^{2+},\;Ag^+$. Among the adsorbents tested, Cu-NaY and Ag-NaY showed good adsorption capacities for THT and TBM. These good behaviors of removal of sulfur compound for Cu-NaY and Ag-NaY zeolites probably was influenced by their acidity. The adsorption capacity for THT and TBM on the best adsorbent Cu-NaY-0.5, which was ion exchanged with 0.5 M copper nitrate solution, was 1.85 and 0.78 mmol-S/g at breakthrough, respectively. It was the best sulfur capacity so far in removing organic sulfur compounds from fuel gas by adsorption on zeolites. While the desorption activation energy of TBM on the Cu-NaY-0.5 was higher than NaY zeolite, the difference of THT desorption activation energy between two zeolites was comparatively small.

• Clean Technology
• /
• v.13 no.1 s.36
• /
• pp.64-71
• /
• 2007

The selection of a suitable adsorbent for removing organic sulfur compounds tetrahydrothiophene (THT) and t-butylmercaptan (TBM) from natural gas has been carried out. The saturation adsorption capacity for the sulfur compounds were determined by pulse adsorption method for a group of nanoporous materials, including Na-Y, Na-ZSM-5, Na,K-ET(A)S-10, Na-Mordenite, Na,K-Clinoptitolite, Ti/MCM-41, Ti/SBA-15 and amorphous titanosilicates. Among the materials tested, Na-Y and Na,K-ET(A)S-10 zeolites showed high adsorptive capacities for THT and TBM. The saturation capacity for THT on Na,K-ETS-10 was comparable with that on Na-Y zeolite, which is well known as an effective adsorbent. The capacity and adsorptivity for THT and TBM on Na,K-ETAS-10 were improved by an increase in crystallinity of Na,K-ETAS-10. An investigation of the competitive adsorption between THT and TBM from the breakthrough test using a simulated natural gas indicates that Na,K-ETS-10 selectively adsorbs THT. The breakthrough capacity for THT on Na,K-ETS-10 was 1.19 mmol/g. The results show that the high adsorption performance of Na.K-ETS-10 and Na,K-ETAS-10 is due to the highly exchanged cations in the zeolitic structure which exhibit the strong electrostatic interactions with organic sulfur compounds and their wide pore nature.