• Transactions of the Korean hydrogen and new energy society
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• v.25 no.5
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• pp.482-490
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• 2014

Gaseous sulfur compound such as $H_2S$ or COS in coal- or biomass-derived hot syngas can be purified by solid sorbents at high temperatures. In this study, we investigated the physical properties and reactivity of solid regenerable desulfurization sorbents with 37.2, 41.9, and 46.5wt% ZnO to look into the ZnO content effect. The sorbents were produced by spray-drying method to apply to a fluidized-bed process. Sulfidation and regeneration reaction were carried out using a thermogravimetric analyzer. Sorbent prepared with 46.5wt% ZnO had physical properties suitable for a fluidized-bed process applications such as spherical shape, sufficient mechanical strength and density, high porosity and surface area. It showed high sulfur sorption capacity of 10.4wt% (ZnO utilization of 57%) at reaction temperatures of 500 and $650^{\circ}C$ for sulfidation and regeneration, respectively. However, the sulfur sorption capacity and ZnO utilization were significantly reduced and dimple shape appeared when the ZnO content decreased to 37.2 and 41.9wt%. Sulfur sorption capacity and regenerability were improved as reaction temperature increased within the experimental temperatures used in this work. The reaction temperature zones of $1500{\sim}550^{\circ}C$ and $650{\sim}700^{\circ}C$ are recommended for sulfidation and regeneration, respectively, to lead best reaction performances of the ZnO-based spray-dried sorbents developed in this work.

• Journal of Energy Engineering
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• v.12 no.4
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• pp.302-308
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• 2003

The peformence tests of zinc-based desulfurization sorbents using the yellow earth as support for the hot gas clean up were carried out. The zinc-based sorbent with 25 wt％ yellow earth was prepared, and their properties such as the reaction rate, the sulfur capacity and the attrition resistance, were investigated. The reactivity tests for hot gas desulfurization was performed at middle temperatures (sulfidation/regeneration：480$^{\circ}C$/580$^{\circ}C$). During multi-cyclic desulfurization, the deactivation of zinc-based sorbent was decreased by the addition of yellow earth, and their efficiency was enhanced. The ZnO/yellow earth sorbent had high reactivity, good regenerability, long-term durability (about 19 gS/100 g sorbent for 10-cycles) and high attrition resistance (AI=19.1％). It was concluded that the peroperties of zinc-based sorbent were improved by metal oxides (Fe$_2$O$_3$, Na$_2$O, MnO$_2$, etc) in the yellow earth. From these results, it was confirmed that the desulfurization properties of zinc-based sorbents at middle temperatures could be improved by the yellow earth using as support.

• Journal of Energy Engineering
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• v.7 no.1
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• pp.24-34
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• 1998

In this research, effects of the types and amounts of binders and additives on desulfurization and regeneration reactivities of zinc titanate were investigated. Bentonite and kaolinite were used as binders and Mo-based, Ni-based, and Cu-based compounds were used as additives. A thermogravimetric analyzer (TGA) was utilized to investigate reactivities of desulfurization and regeneration for each sorbent. Two-cycle reactions of desulfurization-regeneration were performed in the TGA reactor. Results of XRD analysis showed that all sorbents had the crystalline phases of $Zn_2TiO_2$ and $Zn_2Ti_3O_8$ irrespective of the type and amount of binder and additive. Kaolinite-bound sorbents gave higher surface areas than bentonite-bound ones and the surface areas and pore volumes of sorbents increased with amount of binder increased. It was found that the most suitable temperatures for desulfurization and regeneration were 680$^{\circ}$C and 730$^{\circ}$C, respectively, and the sorbent prepared by the addition of 3 mol% CuO showed the best performance in terms of desulfurization and regeneration. Nio-added sorbents had good regenerability whereas $MoO_3-based$ sorbents showed poor performance. In cycle experiments in a fixed bed reactor 3 mol% CuO-added sorbents showed high reactivity.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2000.11a
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• pp.73-77
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• 2000

A great deal of research has been carried out in the last twenty some years to develop high temperature desulfurization. For example, the efficiency of advanced power generation processes based on the integrated gasification combined cycle (IGCC) can be increased significantly with high temperature desulfurization. Much of the recent high temperature desulfurization research has concentrated on zinc-based sorbents such as zinc ferrite(ZnFe$_2$O$_4$) and zinc titanate(ZnO.xTiO$_2$) due to its thermodynamic advantage in capturing H$_2$S molecules.(omitted)

• Korean Chemical Engineering Research
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• v.50 no.3
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• pp.492-498
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• 2012

In this study, hydrodynamics such as solid circulation rate and voidage in the desulfurizer and the reaction characteristics of Zn-based solid sorbents were investigated using lab-scale high pressure and high temperature desulfurization process. The continuous HGD (Hot Gas Desulfurization) process consist of a fast fluidized bed type desulfurizer (6.2 m tall pipe of 0.015 m i.d), a bubbling fluidized bed type regenerator (1.6 m tall bed of 0.053 m i.d), a loop-seal and the pressure control valves. The solid circulation rate was measured by varying the slide-gate opening positions, the gas velocities and temperatures of the desulfurizer and the voidage in the desulfurizer was derived by the same way. At the same gas velocities and the same opening positions of the slide gate, the solid circulation rate, which was similar at the temperature of $300^{\circ}C$ and $550^{\circ}C$, was low at those temperatures compared with a room temperature. The voidage in the desulfurizer showed a fast fluidized bed type when the opening positions of the slide gate were 10~20% while that showed a turbulent fluidized bed type when those of slide gate were 30~40%. The reaction characteristics of Zn-based solid sorbent were investigated by different desulfurization temperatures at 20 atm in the continuous operation. The $H_2S$ removal efficiency tended to decrease below the desulfurization temperature of $450^{\circ}C$. Thus, the 10 hour continuous operation has been performed at the desulfurization temperature of $500^{\circ}C$ in order to maintain the high $H_2S$ removal efficiency. During 10 hour continuous operation, the $H_2S$ removal efficiency was above 99.99% because the $H_2S$ concentration after desulfurization was not detected at the inlet $H_2S$ concentration of 5,000 ppmv condition using UV analyzers (Radas2) and the detector tube (GASTEC) which lower detection limit is 1 ppmv.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2008.04a
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• pp.127-130
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• 2008

• Resources Recycling
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• v.25 no.5
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• pp.14-27
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• 2016

Theoretical reviews of integrated gasification combined cycle one of the clean coal technologies and trends in the study and technology development for high temperature desulfurization sorbents were investigated. Reactivity, durability and abrasion resistance is an important key for development of high temperature desulfurization sorbents, the kind of things include calcium, zinc, manganese, iron and copper-based sorbents. Current status of high temperature desulfurization sorbents, manufacturing techniques of zinc-based sorbent in advanced countries has commercialized. In case of Korea, various research studies are underway to commercialize the Zn and non Zn-based high temperature desulfurization sorbents to cheaper and superior capability using various supports.