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순산소연소 조건에서 Drop tube furnace를 이용한 운전변수에 따른 석회석의 탈황특성 연구
최욱 ( Wook Choi ),조항대 ( Hang Dae Jo ),최원길 ( Won Kil Choi ),박영성 ( Yeong Sung Park ),길상인 ( Sang In Keel ),이형근 ( Hyung Keun Lee ) 한국화학공학회 2011 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.49 No.6
순산소연소는 높은 연소 효율과 적은 배가스량, 낮은 질소산화물 농도를 장점으로 하고 있으며 연소온도 조절을 위한 배가스 재순환에 의해 배출되는 연소가스중의 CO2 농도를 95%까지 농축이 가능하므로 석탄 연소설비에 대한 유망한 CCS 기술로 부각되고 있다. 본 연구는 순산소연소 조건에서 배가스의 재순환을 통한 CO2 농도 증가에 기인하는 직접 황화반응이 탈황효율에 미치는 영향을 평가하고 반응온도, CO2 농도, SO2 농도상승이 SO2 제거효율에 미치는 영향과 배가스 중 수분 등이 SO2 제거효율에 미치는 영향을 실험적으로 고찰하였다. 반응온도 1,200 ℃까지 온도 상승에 따라 SO2의 제거효율은 증가하였고 Ca/S비, CO2 농도와 수분이 증가할수록 SO2 제거효율이 증가하였다. 이러한 운전변수는 영향인자 평가를 통하여 Ca/S 비>체류시간>O2농도>반응온도>SO2농도>CO2농도>수분농도의 순으로 탈황반응에 영향을 미치는 것으로 나타났다. 또한 운전변수별 실험결과를 이용하여 로내 건식탈황에 있어서 각 운전변수별 성능 영향인자를 평가할 수 있는 반경험적 모델식을 도출하였다. Oxy-fuel combustion with many advantages such as high combustion efficiency, low flue gas flow rate and low NOx emission has emerged as a promising CCS technology for coal combustion facilities. In this study, the effects of the direct sulfation reaction on SO2 removal efficiency were evaluated in a drop tube furnace under typical oxy-fuel combustion conditions represented by high concentrations of CO2 and SO2 formed by gas recirculation to control furnace combustion temperature. The effects of the operating parameters including the reaction temperature, CO2 concentration, SO2 concentration, Ca/S ratio and humidity on SO2 removal efficiency were investigated experimentally. SO2 removal efficiency increased with reaction temperature up to 1,200 due to promoted calcination of limestone reagent particles. And SO2 removal efficiency increased with SO2 concentrations and the humidity of the bulk gas. The increase of SO2 removal efficiency with CO2 concentrations showed that SO2 removal by limestone was mainly done by the direct sulfation reaction under oxy-fuel combustion conditions. From the impact assessment of operation parameters, it was shown that these parameters have an effects on the desulfurization reaction by the order of the Ca/S ratio > residence time > O2 concentration > reaction temperature > SO2 concentration > CO2 concentration > water vapor. The semi-empirical model equation for to evaluate the effect of the operating parameters on the performance of in-furnace desulfurization for oxy-fuel combustion was established.
DTF를 이용한 순산소연소 조건에서 탈황반응과 CaSO₄ 분해 특성
최욱(Wook Choi),조항대(Hang Dae Jo),최원길(Won Kil Choi),박영성(Yeong Sung Park),길상인(Sang In Keel),이형근(Hyung Keun Lee) 大韓環境工學會 2011 대한환경공학회지 Vol.33 No.6
순산소연소 조건하의 로내 탈황공정에서 황화반응 생성물인 CaSO₄의 재분해가 탈황반응에 미치는 영향이 크다. 본 연구에서는 DTF (Drop Tube Furnace)를 이용하여 반응온도, CO₂, O₂, SO₂ 농도 등을 포함한 다양한 실험 변수들이 CaSO₄ 탈황반응에 미치는 영향을 파악하기 위하여 분해반응의 전환율을 측정하고 반응속도를 계산하였다. 반응온도가 상승함에 따라 CaSO₄ 분해반응의 전환율과 반응속도가 증가하였고 O₂가 존재하는 조건에서 CO₂ 농도의 영향은 크지 않았다. 동일한 조건에서 CaSO₄ 분해속도는 O₂ 농도가 감소함에 따라 증가하였으나 SO₂ 농도가 증가함에 따라 감소되었다. In general, the decomposition of CaSO₄ formed by sulfation reaction in the in-furnace desulfurization process using limestone has strong effect on the desulfurization reaction under the oxy-fuel combustion condition. In this study, the conversion rates were measured and reaction rates were calculated in order to investigate the effects of the experimental variables such as temperature and the concentrations of CO₂, O₂, SO₂, on the CaSO₄ decomposition reaction using DTF (Drop Tube Furnace) in the desulfurization reaction. The conversion rate and the reaction rate of CaSO₄ decomposition reaction were increased with reaction temperature. CO₂ concentration has little effect on CaSO₄ decomposition reaction in the presence of O₂. Under the same experimental conditions, the decomposition rate of CaSO₄ was enhanced with the decreasing the O₂ concentration, but vice versa with the increasing of SO₂ concentration.
류호정 ( Ho Jung Ryu ),박상수 ( Sang Soo Park ),이동호 ( Dong Ho Lee ),최원길 ( Won Kil Choi ),이영우 ( Young Woo Rhee ) 한국화학공학회 2012 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.50 No.5
When we use NiO based particle as an oxygen carrier in a chemical looping combustion system, the fuel conversion and the CO2 selectivity decreased with increasing reaction temperature within high temperature range (>900˚C) due to the increment of exhaust CO concentration from reduction reactor. To improve reduction reactivity at high temperature, the applicable metal oxide component was selected by calculation of the equilibrium CO concentration of metal oxide components. After that, feasibility of reduction reactivity improvement at high temperature was checked by using solid mixture of the selected metal oxide particle and NiO based oxygen carrier. The reactivity was measured and investigated using batch type fluidized bed. The solid mixture of Co3O4/CoAl2O4 (10%) and OCN706- 1100(90%) showed higher fuel conversion, higher CO2 selectivity and lower CO concentration than OCN706-1100 (100%) cases. Consequently, we could conclude that improvement of reduction reactivity at high temperature range by adding some Co3O4 based oxygen carrier was feasible.
Layer-by-Layer 나노코팅법을 이용한 수분회수용 폴리에테르술폰 중공사막의 표면개질
박소정(So Jung Park),윤상희(Sang Hee Yun),최원길(Won Kil Choi),조성근(Seong-Keun Cho),이형근(Hyung Keun Lee),허강무(Kang Moo Huh) 한국고분자학회 2015 폴리머 Vol.39 No.5
본 연구에서는 폴리에테르술폰(PES) 중공사막을 수분 회수용 분리막으로 응용하고자 layer-by-layer(LbL) 코팅법에 의한 표면개질을 통하여 PES 중공사막의 수분회수능을 향상시키고자 하였다. PES의 술폰화를 통해 음이온성 sulfonated PES(SPES)를 합성하였고, 양이온성 고분자인 polyallylamine hydrochloride(PAH)와 함께 LbL 코팅수용액 제조에 사용하였다. 표면개질된 PES 중공사막의 특성 변화를 접촉각, ζ-potential, XPS, SEM 분석 등을 통해 관찰하였고, 수분투과도 및 선택도에 대한 성능평가를 실시하였다. LbL 코팅된 PES 중공사막은 50~80 nm 두께의 LbL 나노코팅층을 형성하였으며, 상대적으로 낮은 접촉각과 높은 수분투과도를 보였다. 본 결과를 통해 LbL 코팅법을 이용한 PES 중공사막의 표면개질은 표면 친수성 및 분리막 수분투과도 향상에 효과적임을 확인하였다. Polyethersulfone (PES) hollow fiber membrane was surface-modified for application as a separation membrane to recover water vapor from the flue gas. Hydrophilic sulfonated PES (SPES) was prepared by introducing a sulfonic acid group in PES structure and was used for the layer-by-layer (LbL) coating solution with polyallyamine hydrochloride (PAH). The surface characteristics of the modified PES membranes were observed by XPS, SEM, ζ-potential and contact angle measurements. The formation of hydrophilic nano-coating layer with 50~80 nm in thickness on the surface of PES hollow fiber membranes by the LbL coating method led to relatively lower contact angle and higher water vapor permeance. As a result, the LbL coating method could be considered as a useful method for surface-modification of PES hollow fiber membrane to enhance their surface hydrophilicity and water vapor permeance.