分会

第十九分会：绿色炼油化工与氢能

摘要

花状NiCu/SiO2双金属催化剂的构筑及其石油树脂加氢性能研究 孙洪明，杨江涛，袁珮* 福州大学石油化工学院，福建 福州，350108 *Email: yuanpei@fzu.edu.cn 石油树脂（PR）是一种由石脑油裂解制乙烯副产的C5或C9馏分油聚合而成的热塑性聚合物[1]。由于传统石油树脂中存在着不饱和烯烃基团以及S，Cl和不溶性溶胶等杂质，使得石油树脂表现出较差的热稳定性，耐老化性以及耐候性，极大地限制了其在高端领域的应用。催化加氢无疑是提高石油树脂品质的有效方法[2]。氢化石油树脂（HPR）呈水白色，具有良好的热稳定性，耐老化性以及耐候性，被用于压敏胶，一次性卫生用品以及许多高附加值的产品中。对于石油树脂加氢，镍基催化剂因其价格低廉，抗毒和适宜的加氢活性而受到广泛关注。但是，开发一种具有小颗粒尺寸的，金属高度分散的以及金属与载体之间具有强相互作用的新型镍基催化剂仍然充满挑战。 基于反应浸渍策略，本研究利用SiO2在碱性环境中被OH-逐渐刻蚀形成硅酸根离子，可与Ni2+、Cu2+反应形成化合物(Ni,Cu)3Si2O5(OH)4的原理，构筑高度分散的NiCu/SiO2双金属催化剂并将其用于PR的催化加氢研究；系统了研究了NiCu合金效应以及催化剂形貌对PR加氢的影响。结果表明，花状结构的NiCu/SiO2双金属催化剂具有优异的加氢活性和稳定性。C5PR和C9PR的加氢度分别为95.0%和96.4%，明显优于通过浸渍法制备的NiCu/SiO2催化剂以及花状结构的Ni/SiO2单金属催化剂，这可归因于：1) 催化剂表面的大开孔会降低PR的扩散阻力，有利于PR/HPR分子转移；2) 具有小颗粒和高度分散的活性组分更易于与反应物接触；3) NiCu合金的形成促进了电子从Cu到Ni的转移，富电子的Ni活性位有利于氢气的解离以及PR中缺电子的烯烃双键的吸附；4) 通过原位还原硅酸镍铜前驱体，活性金属锚固在载体上，减轻了金属颗粒的迁移和聚集。 Figure 1. Schematic illustration of the fabrication procedure of NiCu/SiO2 catalyst and catalytic conversion mechanism of C5PR to HC5PR. 关键词：花状催化剂；NiCu合金；催化加氢；石油树脂 参考文献 [1] 朱明慧, 蒲延芳. 石油化工动态, 1996, 4(9): 18. [2] Z.G. Bai, X. Chen, C. Li, W.X. Guan, P. Chen, C.H. Liang*. Molecular Catalysis. 2020, 484: 110728.   Hierarchical flower-like NiCu/SiO2 bimetallic catalysts with enhanced catalytic activity and stability for petroleum resin hydrogenation Hongming Sun, Jiangtao Yang, Pei Yuan* College of Chemical Engineering, Fuzhou University, Fujian, Fuzhou, 350108 *Email: yuanpei@fzu.edu.cn Petroleum resin (PR) is a kind of thermoplastic polymer made from the polymerization of the C5 or C9 fraction which are by-products of the cracking of naphtha to ethylene[1]. Due to the presence of unsaturated olefinic groups and impurities such as S, Cl and insoluble sol in the conventional PR, it exhibits poor thermal stability, poor aging resistance and poor weather resistance, which greatly limits its applications in high-end fields. Catalytic hydrogenation has been proved to be an effective process to improve the quality of PR[2]. The hydrogenated PR (HPR) has watery white color, high thermal stability and good aging and weather resistance, which can be utilized as pressure sensitive adhesives, disposable hygiene products and many other high value-added products. Ni-based catalysts have attracted significant attention because of its lower price, resistance to poison and moderate hydrogenation activity for PR hydrogenation. However, the development of novel catalysts with reduced Ni particle size, increased metal dispersion and strong interactions between metals and supports is still a huge challenge. In this work, based on the reactive impregnation strategy, SiO2 is gradually etched by OH- in an alkaline environment to form Si2O5(OH)43-, then reacted with Ni2+ and Cu2+ to form (Ni, Cu)3Si2O5(OH)4. Finally, highly dispersed NiCu/SiO2 bimetallic catalyst was constructed and applied for PR hydrogenation. The results indicated that compared with the NiCu/SiO2 catalyst prepared prepared via an impregnation method and flower-like Ni/SiO2 monometallic catalysts, the flower-like NiCu/SiO2 bimetallic catalyst show a superior catalytic activity and outstanding stability for PR hydrogenation. The hydrogenation degrees for C5PR and C9PR could reach up to 95.0% and 96.4%, respectively. The excellent catalytic performance of flower-like NiCu/SiO2 may be attributed to: 1) The large open pores on the surface will reduce the diffusion resistance of PR, making the PR/HPR molecules easily transfer in the pores; 2) The active components with small particle size and high metal dispersion are deposited on the surface of SiO2 nanoplatelets, which will improve the number of active sites and make them more accessible to the reactants; 3) The formation of NiCu alloy promotes the electrons transfer from Cu to Ni, and the electron-rich Ni active sites are beneficial for the disassociation of hydrogen and adsorption of electron-deficient olefin double bonds in PR for hydrogenation; 4) The active metals are firmly anchored on the supports through in situ reduction of the hierarchical (Ni,Cu)3Si2O5(OH)4 precursor, which will alleviate the migration and aggregation of metal particles, thereby significantly improving the catalytic stability of catalysts. Keywords: flower-like catalyst; NiCu alloy; catalytic hydrogenation; petroleum resin References [1] 朱明慧, 蒲延芳. 石油化工动态, 1996,4(9): 18. [2] Z.G. Bai, X. Chen, C. Li, W.X. Guan, P. Chen, C.H. Liang*. Molecular Catalysis. 2020, 484: 110728.

关键词

花状催化剂;NiCu合金;催化加氢;石油树脂

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