• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.107.2-107.2
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• 2010

고온건식탈황기술은 고온고압에서 석탄가스에 함유된 황화합물을 제거하는 기술로 석탄가스화에 의해 생성된 고온의 석탄가스의 열손실을 최소화하여 열효율이 높은 기술이다. 본 연구에서는 석탄으로부터 합성원유를 생산하는 0.3 배럴/일 규모 석탄액화(CTL)공정의 연계운전을 통하여 건식탈황공정의 성능을 평가하였다. 0.3 배럴/일 규모 석탄액화공정은 석탄가스화기, 건식탈황공정, 액화공정으로 구성되어 있으며 30 atm의 고압에서 운전된다. 건식탈황공정은 석탄가스화기와 액화공정 사이에 위치하여 석탄가스화로부터 생성된 석탄가스에 함유된 황화합물을 아연계 건식탈황제에 의해 제거한 후 액화반응기로 공급하여 황화합물에 의한 촉매의 피독을 막아주는 역할을 수행한다. 본 연구에서는 기존에 개발된 두 개의 기포유동층 반응기로 구성된 탈황장치를 30 atm에서 운전이 가능하도록 수정/보완하여 실제 운전압력인 30 atm의 고압에서 연속운전을 수행하였다. 실험 결과 탈황효율은 99% 이상이며 탈황반응기 출구 황화합물의 농도는 1 ppmv 이하로 유지하였다.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.871-872
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• 2009

본 연구에서는 석탄가스에 함유된 $H_2O/H_2S$ 농도변화에 따른 세가지 종류의 아연계 탈황제의 반응성능을 회분식 유동층반응기에서 분석하였다. 가스화에서 생성되는 가스의 조성은 모사가스를 이용하여 입구의 $H_2O$와 $H_2S$ 농도를 변화시켜 실험을 수행하였다. $H_2O$의 농도는 5%부터 30%까지 $H_2S$의 농도는 0.5%에서 2%로 변화시켜 탈황성능을 분석하였다. 실험 결과 $H_2O$의 농도가 증가할수록 탈황성능이 감소하였다. 입구의 $H_2S$ 농도가 증가할수록 탈황반응기 후단의 $H_2S$ 농도 역시 증가하였으나, 탈황성능은 최저 99.5%로 건식탈황제를 이용하여 99% 이상의 $H_2S$ 제거 성능을 보이는 것을 확인하였다.

• 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.

• Clean Technology
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• v.12 no.4
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• pp.232-237
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• 2006

The zinc-based desulfurization sorbents for a fluidized-bed system were prepared by a spray drying method and the effects of the pH and viscosity of the slurry on the attrition resistance of the prepared sorbents were investigated in this work. In order to improve the attrition resistance, alumina sol was used for an inorganic binder and pH of the slurry was changed for its better dispersion in slurry. The attrition resistance of the prepared sorbents decreased due to the phase transition of alumina sol to gel as the slurry pH increased to its basicity. The optimum pH condition for the good attrition resistance of the sorbents was about 6.0 in this study. It was confirmed that the attrition property of the sorbents were varied with the viscosity of the slurry. The attrition resistance of the sorbents prepared by the spray drying method increased as their bulk density increased, while it decreased as the surface area and porosity of the sorbents. The optimum viscosity for the high attrition was in the range 400-500 cP.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 1999.05a
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• pp.33-38
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• 1999

CCT(Clean Coal Technology)의 응용분야인 IGCC, PFBC 및 MCFC 등 석탄을 이용한 새로운 발전기술에 활용될 것으로 예견되는 고온건식 탈황기술은 고온(35$0^{\circ}C$~$650^{\circ}C$)과 고압(약 20기압)상태에서 금속 산화물로 된 고체흡수제(고온건식 탈황제)를 이용하여 반응기(유동층, 고속유동층 및 고정층과 이동층 반응기 등)에서 흡수와 재생반응을 통하여 석탄가스중에 있는 H$_2$S 등 황화물을 효율적으로 제거하는 기술이다.(중략)

• Applied Chemistry for Engineering
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• v.10 no.2
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• pp.183-189
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• 1999

Zinc-based sorbents for $H_2S$ removal were prepared. The reactivity of sorbents was investigated by the successive cycles of sulfidation-regeneration at $650^{\circ}C$ in a fixed bed reactor. The desulfurization sorbents were prepared with granulation method to produce a spherical pellet with good attrition resistance. The fresh and reacted sorbents were characterized by X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS) and the characteristics of sorbents on calcination conditons were analysed by Mercury Porosimetery and BET. The reactivity of sorbents decreased as the number of sulfidation-regeneration cycle increased. It is due to the zinc loss and the increase of the diffusion resistance by sintering, cracking and spalling of sorbents at the high temperature.

• 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.

• Korean Chemical Engineering Research
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• v.47 no.6
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• pp.710-714
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• 2009

In this study, we analyzed the desulfurization performance of Zn-based dry sorbents according to the reducing power, water vapor content and $H_2S$ inlet concentration of coal gas in a batch-type fluidized-bed reactor. We used three different coal gas composition with different reducing power such as KRW air-blown coal gas, Shell oxygenblown coal gas and IAE coal gas. The experiments were performed by changing the inlet concentration of water vapor and $H_2S$ in a coal gas. Water vapor content was varied from 5% to 30% and $H_2S$ inlet concentration from 0.5% to 2.0%. As both the water vapor content and $H_2S$ inlet concentration increased, desulfurization performance of Zn-based sorbents decreased regardless of the reducing power of the coal gas. The minimum desuflurization performance was, however, above 99.5% for all experimental conditions, which implied that Zn-based dry sorbents could be used to remove $H_2S$ up to 99%.

• Journal of Energy Engineering
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• v.11 no.3
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• pp.247-253
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• 2002

Natural manganese ore was selected as main active component for a non-zinc desulfurization sorbent used in the gas clean-up process of the integrated gasification combined cycle (IGCC) because of excellent H$_2$S removal efficiency and economical aspect . In this study, the regeneration characteristics of sorbent after desulfurization reaction were determined in a thermobalance reactor and a fixed bed reactor in the temperature range of 350~55$0^{\circ}C$. The mixed gases of oxygen and nitrogen are used as the regeneration reaction gases for manganese sorbent. According to Mn-S-O phase diagram, the manganese sorbent has a low regeneration efficiency in medium temperature due to formation of MnSO$_4$ and the regeneration temperature must be over 85$0^{\circ}C$. To improve that problem, ammonia and steam was added in regeneration mixed gases. Effect of new regeneration method was determined by XRD and difference of desulfurization through multicycle tests.