新型改性海泡石负载型镍基多金属催化剂构筑及催化己二腈加氢性能研究

The production rate of ε-caprolactam is faster than its market demand, which leads to intense competition on the market and requirement for researchers to improve its production technology. Producing ε-caprolactam from Butadiene/Adiponitrile hydrogenation methods has the advantages of cheaper butadiene material, low energy consumption and simple process. But the key step of adiponitrile hydrogenation in the process is less than ideal and needs improvement..Based on the combination of the molecular simulation calculations and experiments, this project designs the modified sepiolite supported nickel based multi-metal catalysts, investigates the influence of modification on the pore structure of the support, active and adsorption centers, and morphology and dispersion of active component . With the investigation of electron interaction mechanism of active components and auxiliary metal, and of its influence on the surface morphology and electronic structure of catalysts and the further study of the synergistic catalytic effects between supports, active components and auxiliary metals, the optimal modification conditions are achieved, and the novel catalyst with synergistic catalysis will be prepared, which could catalyze adiponitrile hydrogenation to form 6-aminocapronitrile and hexamethylendiamine with high conversion and selectivity under mild conditions without addition of aqueous ammonia or alkali metal hydroxide solution. .Using the online FT-IR, the reaction mechanism and kinetics will be studied, and the results of this work could provide effective guidance for the industrial application and reactor design, and provide a reference for hydrogenation catalyst preparation of nitrile compounds and nitrogen compounds synthesis processes. The results of this work would also simplify and improve the present technology of ε-caprolactam production and is of great scientific value and application prospects.

由于己内酰胺产能增速快于需求量增速，其市场竞争愈发激烈，因此需要加大技术研发。丁二烯/己二腈法采用来源丰富、价格低廉的丁二烯，物耗能耗低，工艺简单，但需突破关键步骤己二腈加氢过程。本项目采用分子模拟计算和实验结合的方法，设计制备改性海泡石负载型镍基多金属催化剂，研究修饰改性对载体孔结构、表面活性吸附中心及对活性组分形貌结构、分散度等的影响。通过研究活性组分与助剂金属的电子相互作用及对表面形貌、电子结构等的影响规律，进而研究载体、活性组分和助剂金属间协同催化效应，获得最优修饰改性方法和条件，构筑具有协同催化作用的新型催化剂用于己二腈加氢，实现在温和条件，不加氨水或碱溶液体系中，高转化和高选择性制备6-氨基己腈和己二胺。应用在线反应红外技术研究反应机理和动力学，为工业化应用提供指导，为腈基、含氮化合物加氢催化剂研制提供借鉴，项目成果有望简化和改进己内酰胺生产工艺，有重要学术价值和很好应用前景。

本项目设计与制备具有多金属协同催化效应的新型催化材料，应用于己二腈高选择性制备6-氨基己腈和己二胺，有望提升丁二烯/己二腈法合成己内酰胺及己二胺生产技术，具有重要的理论价值和很好的应用前景。考察K、La共掺杂的镍基海泡石催化剂的制备及其加氢性能研究，发现助剂K、La修饰有利于活性组分镍的分散，同时提供了碱性位点，进而提高了催化活性及产物选择性；考察改性海泡石负载K掺杂镍基催化剂的制备及其加氢性能研究，发现无机酸对海泡石的形貌、表面基团、酸碱性有很大影响，进而影响活性组分镍的吸附、分散、颗粒大小、还原活化能以及金属价态，揭示了催化剂微观结构和催化性能的“构-效”关系；考察K、Fe共掺杂的镍基活性炭催化剂及Cu、Mg共掺杂的镍基碳纳米管催化剂的制备及其加氢性能研究，研究不同助剂金属对活性金属Ni颗粒粒径大小、分散度、载体表面Ni0+含量、NiO还原活化能以及助剂金属与活性金属的协同作用对催化己二腈液相加氢性能的影响，揭示了催化剂表面性质和结构与催化性能之间的“构-效”关系；考察功能化碳纳米管负载镍基催化剂的制备及其在碱性离子液体[Bmim]OH体系下加氢性能的研究，通过化学修饰（-NH2、-COOH、-OH）以及高温氮掺杂对碳纳米管进行修饰改性，然后以功能化碳纳米管为载体负载镍基催化剂。研究功能化碳管的修饰对催化剂表面的酸碱性及活性金属Ni粒子粒径大小、分散度、载体表面Ni0+含量、NiO还原活化能的影响以及载体与活性金属的协同作用对催化己二腈液相加氢性能的影响，揭示催化剂表面性质和结构与催化性能之间的“构-效”关系。同时，研究发现碱性离子液体[Bmim]OH可调控反应体系产物分布，并通过DFT计算进一步揭示了相应的反应过程机理。项目发表相关SCI论文14篇，申请国家发明专利15项，授权6项。