非晶态Ni-P合金柱撑膨润土的组装、结构特征及其催化性能

Using a non-precious metal instead of precious metal in the progress of catalytic hydrogenation is the trend in industrial applications. According to the characteristics of Ni-based non-precious metal catalysts and combining bentonite, which is a characteristics resources in Guangxi, amorphous Ni-P alloy, which was the active component, was embedded into the bentonite layer and form the sandwich structure, which improve the stability and dispersion of the amorphous Ni-P alloy, this new intercalation catalyst was studied. The present project mainly focus on the molecular design and preparation of the amorphous Ni-P pillared bentonite catalyst, and the relations between the structure of amorphous Ni-P pillared bentonite and its catalytic hydrogenation performance was investigated. Because the amorphous alloy catalysts are easy deactivation, the stability, deactivation and regeneration methods of the amorphous Ni-P pillared bentonite catalysts were also investigated. Finally, from the microscopic structure of the catalyst, the changes of reactive intermediates in the reaction process, the reaction kinetics and the other aspects, the reaction mechanism of the hydrogenation of nitrobenzene to aniline over the amorphous Ni-P-pillared bentonite was discussed, and the scientific law of bentonite assembled in the solid catalyst and in the catalytic reaction was revealed, which lay the foundation for bentonite in heterogeneous catalytic reactions.

在催化加氢过程采用非贵金属代替贵金属是工业应用的趋势。根据Ni基非贵金属的催化剂的特点，结合广西的特色资源——膨润土，研究一种将活性组分非晶态Ni-P合金嵌入膨润土层间，构成夹层结构，提高非晶态Ni-P合金稳定性及分散度的新型插层催化剂。项目主要对非晶态Ni-P柱撑膨润土层柱状催化剂的进行分子设计及制备，研究非晶态Ni-P柱撑膨润土层柱状催化剂的结构特征与其催化加氢性能的关系。针对非晶态合金催化剂易失活等问题，对非晶态Ni-P合金柱撑膨润土的稳定性、失活原因与再生方法等进行研究，最后从催化剂的微观结构、反应过程中活性中间体的变化及反应动力学等方面对非晶态Ni-P柱撑膨润土层柱状催化剂上硝基苯加氢为苯胺的反应机理进行探讨，揭示膨润土在固体催化剂插层组装及催化反应中的科学规律，为膨润土在多相催化反应中的应用奠定基础。

项目利用非晶态催化剂的高催化活性和优良的抗毒性，以改性后的膨润土作为载体，制备了非晶态Ni-P合金柱撑膨润土催化剂，并应用于硝基苯加氢制苯胺反应，研究其组装、结构特征及其催化性能，关联硝基苯加氢制苯胺反应的活性，稳定性等，研究了加氢催化剂微观结构对催化硝基苯加氢制苯胺的影响。研究表明焙烧、酸化、Al柱撑改性后的膨润土能够作为载体制备Ni-P非晶态合金/改性膨润土催化剂，并可用于催化硝基苯加氢为苯胺反应。与普通Ni金属催化剂相比，Ni-P非晶态合金/Al柱撑膨润土催化剂可使硝基苯转换率和苯胺选择性增强。采用微波干燥辅助化学还原法制备Ni-P非晶态合金/酸化膨润土催化剂能够提高硝基苯加氢催化活性，改善催化剂稳定性。采用B对Ni基催化剂进行掺杂改性，可提高催化剂的抗积碳性能，从而延长催化剂寿命。另外，Ni/膨润土催化剂同样能够应用于CO2催化甲烷化过程中，表现出良好的催化活性。该项目立足于广西丰富的膨润土资源，设计制备非晶态Ni-P合金柱撑膨润土，推动膨润土开发利用向深度和广度发展，为广西非金属矿产业链的延长，提高广西非金属矿产业的科技创新水平提供基础支撑。研究结果既可以为膨润土在催化剂组装中的应用提供基础数据和科学规律，也为非晶态合金催化剂的改性提供新方法。因项目基于实际工业过程开展研究，项目除发表论文8篇外，还申请了6件专利，其中3件获授权。