Li Gang, Xiao Penny, Webley Paul
Cooperative Research Centre for Greenhouse Gas Technologies, Department of Chemical Engineering, Monash University, Wellington Road, Clayton, Victoria 3168, Australia.
Langmuir. 2009 Sep 15;25(18):10666-75. doi: 10.1021/la901107s.
Adsorption equilibria of a CO2/H2O binary mixture on activated alumina F-200 were measured at several temperatures and over a wide range of concentrations from 4% to around 90% of the saturated water vapor pressure. In comparison with the single-component data, the loading of CO2 was not reduced in the presence of H2O, whereas at low relative humidity the adsorption of H2O was depressed. The binary system was described by a competitive/cooperative adsorption model where the readily adsorbed water layers acted as secondary sites for further CO2 adsorption via hydrogen bonding or hydration reaction. The combination of kinetic models, namely, a Langmuir isotherm for characterizing pure CO2 adsorption and a BET isotherm for H2O, was extended to derive a binary adsorption equilibrium model for the CO2/H2O mixture. Models based on the ideal adsorbed solution theory of Myers and Prausnitz failed to characterize the data over the whole composition range, and a large deviation of binary CO2/H2O equilibrium from ideal solution behavior was observed. The extended Langmuir-BET (LBET) isotherm, analogous to the extended Langmuir equation, drastically underestimated the CO2 loading. By incorporating the interactions between CO2 and H2O molecules on the adsorbent surface and taking into account the effect of nonideality, the realistic interactive LBET (R-LBET) model was found to be in very good agreement with the experimental data. The derived binary isosteric heat of adsorption showed that the heat was reduced by competitive adsorption but promoted by cooperative adsorption.
在几个温度下以及4%至约90%饱和水蒸气压的宽浓度范围内,测量了CO₂/H₂O二元混合物在活性氧化铝F - 200上的吸附平衡。与单组分数据相比,在有水存在的情况下,CO₂的负载量并未降低,而在低相对湿度下,水的吸附受到抑制。该二元体系由竞争/协同吸附模型描述,其中易于吸附的水层通过氢键或水合反应作为进一步吸附CO₂的次级位点。动力学模型的组合,即用于表征纯CO₂吸附的朗缪尔等温线和用于水的BET等温线,被扩展以推导CO₂/H₂O混合物的二元吸附平衡模型。基于迈尔斯和普劳斯尼茨理想吸附溶液理论的模型未能在整个组成范围内表征数据,并且观察到二元CO₂/H₂O平衡与理想溶液行为有很大偏差。扩展的朗缪尔 - BET(LBET)等温线类似于扩展的朗缪尔方程,极大地低估了CO₂负载量。通过考虑吸附剂表面上CO₂和H₂O分子之间的相互作用并考虑非理想性的影响,发现实际的交互式LBET(R - LBET)模型与实验数据非常吻合。推导得到的二元等量吸附热表明,竞争吸附降低了热量,但协同吸附促进了热量。