摘要: This work aims to investigate the structural evolution of the char during gasification under a single or mixed atmosphere of H2O and/or CO2 with the synchronized investigation of the effect of the varying char structure on the gasification reactivity. The experimental char was prepared from a bituminous coal at 1000℃. The changes of the char structure along with the progress of the carbon conversion during gasification were characterized using N2 adsorption, SEM, and Raman spectroscopy. The results revealed that H2O showed a more dramatically change on the char structure than CO2 and two reactants had different reaction pathways. The different pathways of reactants affected the evolution manners of the char structure and different gasification reactivity of char was related to structural evolution. The specific reaction rate between the char and CO2 decreased monotonously with increasing carbon conversion. However, the opposite trends are observed when H2O exist, either H2O alone or the mixtures of H2O and CO2. The char gasification reactivity was under the common effect of physical and chemical structure. In terms of the mixture of H2O and CO2, the significant specific surface area caused by H2O provided more active sites for CO2. The interactions between H2O and CO2 promoted reaction between C and CO2 (C + CO2 → CO) in mixtures of H2O and CO2, leading to higher amount of CO and higher specific reaction rate than calculated.
摘要: Y-Co3O4 catalysts with Y/Co molar ratio of 0.03 were prepared by several methods, such as one-step hydrothermal, two-step hydrothermal, and impregnation methods, to catalyze the decomposition of N2O. Among these catalysts, the one prepared by one-step hydrothermal method exhibited the highest activity, and then the Y-Co3O4 catalysts with various molar ratios of Y/Co were synthesized by one-step hydrothermal method. Subsequently, the optimized 0.03Y-Co3O4 was impregnated by K2CO3 solution to prepare K-modified catalyst and named as 0.02K/0.03Y-Co3O4. These catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, hydrogen temperature-programmed reduction (H2-TPR), oxygen temperature-programmed desorption (O2-TPD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques. The results show that both Co3O4 and Y-Co3O4 exhibit spinel structure, however Y-doped Co3O4 catalysts are more active than bare Co3O4. After further modified by potassium, the 0.02K/0.03Y-Co3O4 reveals higher activity due to the more active sites (Co2+) and easier desorption of surface oxygen species than un-modified 0.03Y-Co3O4. In detail, the temperatures of N2O full conversion over 0.02K/0.03Y-Co3O4 catalyst are 325, 350, 375℃, under the reaction atmospheres of 1%N2O+Ar, 1%N2O+2%O2+Ar, 1%N2O+2%O2+8.2%H2O+Ar, respectively. In addition, over 90% conversion of N2O can be maintained at 350℃ after continuous reaction for 50 h in the co-presence of oxygen and steam on K-modified Y-Co3O4 catalyst. There is a dynamic compensation effect between apparent activation energy (Ea) and pre-exponential factor (A) in N2O decomposition over Y-Co3O4 and K-modified catalysts.
