粒径均一碳微球材料的制备与改性及其对油品吸附脱氮性能的研究

The spray drying technology developed by our group will be used in our proposed project to generate functional caronaceous microspheres with uniform size, large surface area and developed pore structure, which was the wonderful building block for the developing of high capacity adsorbent.The surface of carbonaceous microshperes will be modified by oxidation and heat treatment to get a series of samples with different amount and kinds of oxygen groups.Furthermore, the surface initiated living free radical polymerization technique was proposed to further modify the surface of carbonaceous microshperes. The chain length and amount of functional groups in the polymer chain can be tuned with such technique. After the modification, the materials was used as the adsorbent for the application in denirogenation of liquid hydrocarbon steams. The adsorption ability of these samples will be characterized in batch adsorption in order to find the relationship between the properties of the adsorbent and their adsorption ability for different nitrogen compounds.The mechnism will be disscussed on the basis of the structure-performance correlation and the molecular simulation.The structure of the material will be optimzed based on the results to improve both the capacity and selectivity for nitrogen compounds in liquid hydrocarbon steams.The advance of current proposal can be addressed on the following two points: 1) by using the spray drying technology to prepare caronaceous microshpere with uniform size and developed pore structure, which will show benefit for accelerating mass transportation and reduce resistence in flow reactor; 2) under the direction of function groups with adsorption capacity and selectivity, uniformly modify the caronaceous microshpere with pre-controlled structure and amount of polymer chain by using surface initiated living free radical polymerization. Such technique will be benificial for the developing high selectively, high capacity adsorbent for denitrogenation of liquid hydrocarbon steams.

本项目拟通过均一液滴微流体喷雾干燥技术制备粒径均一、比表面积高的多孔碳微球材料，并通过氧化活化和接枝具有氮化物选择性吸附功能的聚合物链段进行改性，制备高效的聚合物-多孔碳球吸附材料。喷雾干燥法制备的碳微球具备粒径均一、高比表面、颗粒尺度较大及孔结构发达等优势，是一种优越的且适用于固定床的吸附剂基底材料。通过氧化处理及惰性气体剪裁含氧基团的种类及浓度，制备一系列物化性质不同的吸附剂。通过考察所制备材料的物化性质与其吸附行为的关系，研究不同含氧基团对氮化物的吸附能力，进一步结合量化计算考察吸附脱氮机理。结合实验结果，利用活性自由基聚合技术在碳微球表面接枝利于氮化物吸附的功能性基团，通过调节聚合参数，控制接枝聚合物的厚度和链段长度等，实现其孔道内的均匀涂布，降低氮化物在吸附剂里的扩散阻力，提高对氮化物的吸附量和选择性。将所制备的吸附剂用于汽柴油及煤液化油中氮化物的脱除，可望大幅度降低氮化物含量。

通过本项目的研究探索，成功利用均一液滴微流体喷雾干燥技术制备了一系列粒径相对均一、比表面积较大的多孔碳基吸附材料。进一步利用如氧化处理、接枝对氮化物具有选择性吸附功能的小分子或聚合物链段及惰性气体高温处理剪裁功能性基团等方法，对碳基吸附材料表面化学和物理性能进行改性，获得了具有不同表面性质的吸附材料。利用所得吸附材料，考察其物化性质与在模拟油以及汽油中的对中性氮化物和碱性氮化物的吸附能力的关系，并在此基础上进一步研究了对于油品中含氮化合物的吸附机理。进一步的利用反应性试剂开展了聚合物修饰和改性的研究。本项目的研究结果有益于今后研发高吸附量，高选择性的油品脱氮吸附剂。在项目基金资助下，共发表SCI收录论文3篇，待发表论文3篇，培养硕士生2名，本科生3名，参加国际会议2次，国内会议1次，完成了项目的预期成果。