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매체 순환식 수소제조공정에 적합한 Fe2O3/ZrO2 산소전달입자에 구리 산화물 첨가가 미치는 영향에 관한 연구
이준규 ( Jun Kyu Lee ),김초균 ( Cho Gyun Kim ),배기광 ( Ki Kwang Bae ),박주식 ( Chu Sik Park ),강경수 ( Kyoung Soo Kang ),정성욱 ( Seong Uk Jeong ),김영호 ( Young Ho Kim ),주종훈 ( Jong Hoon Joo ),조원철 ( Won Chul Cho ) 한국화학공학회 2016 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.54 No.3
매체 순환식 수소제조공정은 직접 고순도의 수소를 생산하는 동시에 CO2 포집 비용을 최소화할 수 있는 고효율/친환경적인 공정이다. 본 공정은 레독스 반응을 통하여 산소를 전달하고 이때 철 산화물계 산소전달입자를 이용하게 된다. 구리 산화물이 첨가된 철-구리 산화물계 산소전달입자는 반응성 향상이 보고되어 왔으나 철 산화물과 구리 산화물간 상호작용에 대한 이해가 부족한 실정이다. 본 연구에서는 여러 기기 분석법(SEM/EDX, XRD, BET, TPR, XPS, TGA)을 통하여 철-구리 산화물계 산소전달입자의 레독스 반응성 향상을 지배하는 주요인을 연구하였다. 첨가된 구리산화물은 철 산화물 성장 억제제 역할 뿐만 아니라 화학적 환경 변화를 일으키는 화학적 촉매제(chemical promoter)역할도 하는 것이 발견되었다. 철-구리 산화물계 산소전달입자의 우수한 환원 반응성은 구리 산화물의 도입으로 Fe2+농도 증가 및 표면 특성 변화 때문이며, 우수한 물분해 특성은 산화 과정에서 일어나는 철 산화물의 응집을 구리 산화물이 억제시킨 것으로 판단되었다. H2 production by chemical looping is an efficient method to convert hydrocarbon fuel into hydrogen with the simultaneous capture of concentrated CO2. This process involves the use of an iron based oxygen carrier that transfers pure oxygen from oxidizing gases to fuels by alternating reduction and oxidation (redox) reactions. The enhanced reactivities of copper oxide doped iron-based oxygen carrier were reported, however, the fundamental understandings on the interaction between Fe2O3 and CuO are still lacking. In this study, we studied the effect of dopant of CuO to Fe2O3/ ZrO2 particle on the morphological changes and the associated reactivity using various methods such as SEM/EDX, XRD, BET, TPR, XPS, and TGA. It was found that copper oxide acted as a chemical promoter that change chemical environment in the iron based oxygen carrier as well as a structural promoter which inhibit the agglomeration. The enhanced reduction reactivity was mainly ascribed to the increase in concentration of Fe2+ on the surface, resulting in formation of charge imbalance and oxygen vacancies. The CuO doped Fe2O3/ZrO2 particle also showed the improved reactivity in the steam oxidation compared to Fe2O3/ZrO2 particle probably due to acting as a structural promoter inhibiting the agglomeration of iron species.
지하다공질(地下多孔質) 매체(媒體)속에서의 오염물질이동(汚染物質移動) 해석(解析)을 위한 지하수(地下水)흐름 모형(模型)
조원철,Cho, Won Cheal 대한토목학회 1989 대한토목학회논문집 Vol.9 No.3
This paper is on the modeling of two-dimensional groundwater flow, which is the first step of the development of Dynamic System Model for groundwater flow and pollutant transport in subsurface porous media. The particular features of the model are its versatility and flexibility to deal with as many real-world problems as possible. Points as well as distributed sources/sinks are included to represent recharges/pumping and rainfall infiltrations. All sources/sinks can be transient or steady state. Prescribed hydraulic head on the Dirichlet boundaries and fluxes on Neumann or Cauchy boundaries can be time-dependent or constant. Sources/sinks strength over each element and node, hydraulic head at each Dirichlet boundary node and flux at each boundary segment can vary independently of each other. Either completely confined or completely unconfined aquifers, or partially confined and partially unconfined aquifers can be dealt with effectively. Discretization of a compound region with very irregular curved boundaries is made easy by including both quadrilateral and triangular elements in the formulation. Large-field problems can be solved efficiently by including a pointwise iterative solution strategy as an optional alternative to the direct elimination solution methed for the matrix equation approximating the partial differential equation of groundwater flow. The model also includes transient flow through confining leaky aquifers lying above and/or below the aquifer of interest. The model is verified against three simple cases to which analytical solutions are available. The groundwater flow model shall be combined with the model of pollutant transport in subsurface porous media. Then the combined model, with the applications of the Eigenvalue technique and the Dynamic system theory, shall be improved to the Dynamic System Model which can simulate the real groundwater flow and the pollutant transport accurately and effectively for the analyses and predictions. 본(本) 연구(硏究)는 유한요소법(有限要素法)(FEM)을 이용(利用)하여 2차원(次元) 지하수(地下水) 흐름모형(模型)을 확립(確立)한 것으로 지하수계(地下水界)에서의 오염물질이동(汚染物質移動)에 관한 종합적(綜合的)인 동적(動的)시스템 모형(模型)을 개발(開發)하는 연구(硏究)의 첫 단계(段階)이다. 이 흐름모형(模型)은 보다 많은 실재문제(實在問題)를 다를 수 있는 융통성(融通性)과 유연성(柔軟性)을 가지도록 하고 있다. 시간(時間)의 함수(函數)로 나타나는 Sources/Sinks, Dirichlet 형(形)의 경계조건(境界條件), Neumann 형(形) 혹은 Cauchy 형(形)의 유동(流動) 경계조건(境界條件), 누수성피압상(漏水性被壓床) (leaky confining beds) 등(等)의 조건(條件)을 가진 지하수(地下水)흐름을 모의발생(模擬發生 수 있으며, 또 복잡(複雜)한 경계조건(境界條件)을 잘 나타내기 위하여 삼각형요소(三角形要素)와 사각형요소(四角形要素)를 혼합(混合)하여 쓸 수 있는 지하수(地下水)흐름 FEM 모형(模型)을 확립(確立)한 것이다.