【作者】 李雪梅；

【导师】 李忠；

【作者基本信息】 华南理工大学 ， 化学工程， 2013， 硕士

【摘要】 MIL-100（Fe）是金属有机骨架材料MOFs中的一种，因其环境友好、含部分金属位不饱和等优势，在对CO的吸附分离应用方面具有广阔的前景。本文主要针对现有合成工艺使用氢氟酸不环保且产品收率低的问题，开展新工艺研究；此外还研究MIL-100（Fe）对CO和水蒸气的吸附/脱附性能，为此材料在CO吸附方面的应用提供依据。本文首先研制出一种不使用氢氟酸又可获得高收率的MIL-100（Fe）晶体材料合成新工艺。研究表明：120分钟、160℃为最佳微波反应时间和温度，在添加12mmol助剂的情况下（Fe:BTC:H₂O:助剂: HNO₃=1:0.67:278:2:2.6），晶体中的铁转化率为55.03%，明显高于传统工艺的收率，不仅合成工艺更加环保，又可降低成本、节约资源能源。研究了CO在MIL-100（Fe）晶体材料中的吸附相平衡和动力学。结果表明：CO在MIL-100（Fe）上的吸附主要为微孔物理吸附，在T=298K、p=10bar时，MIL-100（Fe）对CO的吸附容量为2.56mmol/g （71.68mg/g）；等量吸附热变化范围为28.31³8.43kJ/mol；在298K、0.5¹.1bar范围内，扩散系数处于1.1×10^-15和3.9×10^-15cm²/s之间。TPD实验表明：CO在MIL-100（Fe）晶体上存在两种吸附位，对应脱附活化能分别为53.38kJ/mol和109.5kJ/mol。固定床吸附实验表明：对含5%（v/v） CO的混合气体，MIL-100（Fe）对CO的工作吸附量为9.95mg/g，明显高于活性炭和分子筛的工作吸附容量。本文还研究了水蒸气在MIL-100（Fe）晶体材料中的吸附相平衡和动力学。结果表明：水蒸气在MIL-100（Fe）上的吸附等温线为Ⅴ型；当RH=90%、T=298K时，MIL-100（Fe）对水蒸气的吸附量为0.61g/g；当RH=40%，温度处于298K和313K之间时，水蒸气在MIL-100（Fe）中的扩散系数处于2.735×10-16和5.603×10-16cm²/s之间，吸附活化能为38.41kJ/mol。TPD实验表明：水蒸气在MIL-100（Fe）上的脱附活化能为60.53kJ/mol。固定床吸附实验表明：对RH=40%的混合气体，MIL-100（Fe）晶体材料对水蒸气的工作吸附量为0.11g/g。最后，本文研究了MIL-100（Fe）固定床对CO/H₂O（g）混合气体的吸附。结果表明：进料气体中存在水蒸气对固定床吸附CO会产生负面影响，由于水蒸气的竞争吸附，使MIL-100（Fe）对CO的工作吸附容量下降，当相对湿度为40%时，MIL-100（Fe）对CO的工作吸附量为9.11mg/g（0.325mmol/g）。更多还原

【Abstract】 MIL-100（Fe）, featured by its environmetal friendship and accessible partial unsaturatedmetal sites, is one of the most eye-catching nanomaterials among MOFs. The presentresearches concerning the product yield, the adsorption and desorption of carbonmonoxide,the hygroscopic property of MIL-100（Fe）are relatively insufficient, which restricts the furtherdevelopment of this material. In order to solve these problems, it is necessary to do thefollowing works.A new method of process improvement on the synthesis of MIL-100（Fe） was advanced.The optimalsynthesis time and temperature are120min and160℃respectively.By adding12mmol additive （Fe:BTC:H₂O:Additive:HNO₃=1:0.67:278:2:2.6）,the yield of MIL-100（Fe） canreach55.03%, and thisresult is more than20%higher than the yield of MIL-100（Fe）synthesized following traditional synthesizing process. The improving of yield helps to saveresource and energy as well as provide technical support for furthering application ofMIL-100（Fe）.Adsorption equilibrium and kinetics, TPD desorption and breakthrough property of COon the MIL-100（Fe） crystal was studied. Resultsshowed thatthe amount adsorbed of CO onthe MIL-100（Fe） was up to2.56mmol/g at298K and10bar. The isosteric adsorptionheatchanged slightly with the amounts adsorbed of CO, indicating the uniformity of surfacestructure and adsorption energy.The diffusivity coefficients of CO within MIL-100（Fe） crystalwas between1.1×10^-15and3.9×10^-15cm²/s. MIL-100（Fe） had two kinds of adsorption sites,with desorptionactivation energy53.38kJ/mol and109.5kJ/mol respectively; the workingadsorption amount of CO on MIL-100（Fe） was9.95mg/g，for5%（v/v） carbonmonoxidemixed gases.Adsorption equilibrium and kinetics, TPD desorption and breakthrough property of watervaporon the MIL-100（Fe） crystal was studied. The result indicated that the adsorptionisotherm of water vapor on MIL-100（Fe） was Type Ⅴ. The amount adsorbed of water vaporon MIL-100（Fe） was up to0.61g/g whenT=298K RH=90%.The diffusivity coefficients ofwater vapor was between2.735×10-16and5.603×10-16cm²/s within MIL-100（Fe） crystal,andactivation adsorption energy was38.41kJ/mol. Desorptionactivation energy was 60.53kJ/mol. The working adsorption amount of water vapor on MIL-100（Fe） was0.11g/g,for RH=40%mixed gases.Finally, adsoption property of CO/H₂O（g）mixed gases within MIL-100（Fe） fixed bed wasinvestigated. Results showed that competitive adsorption of water vapor was existed,decreased the working adsorption amount of carbonmonoxide on MIL-100（Fe） to9.11mg/g（0.325mmol/g）..更多还原