分會(huì)

第十九分會(huì)：綠色煉油化工與氫能

摘要

花狀NiCu/SiO2雙金屬催化劑的構(gòu)筑及其石油樹脂加氫性能研究 孫洪明，楊江濤，袁珮* 福州大學(xué)石油化工學(xué)院，福建 福州，350108 *Email: yuanpei@fzu.edu.cn 石油樹脂（PR）是一種由石腦油裂解制乙烯副產(chǎn)的C5或C9餾分油聚合而成的熱塑性聚合物[1]。由于傳統(tǒng)石油樹脂中存在著不飽和烯烴基團(tuán)以及S，Cl和不溶性溶膠等雜質(zhì)，使得石油樹脂表現(xiàn)出較差的熱穩(wěn)定性，耐老化性以及耐候性，極大地限制了其在高端領(lǐng)域的應(yīng)用。催化加氫無疑是提高石油樹脂品質(zhì)的有效方法[2]。氫化石油樹脂（HPR）呈水白色，具有良好的熱穩(wěn)定性，耐老化性以及耐候性，被用于壓敏膠，一次性衛(wèi)生用品以及許多高附加值的產(chǎn)品中。對(duì)于石油樹脂加氫，鎳基催化劑因其價(jià)格低廉，抗毒和適宜的加氫活性而受到廣泛關(guān)注。但是，開發(fā)一種具有小顆粒尺寸的，金屬高度分散的以及金屬與載體之間具有強(qiáng)相互作用的新型鎳基催化劑仍然充滿挑戰(zhàn)。 基于反應(yīng)浸漬策略，本研究利用SiO2在堿性環(huán)境中被OH-逐漸刻蝕形成硅酸根離子，可與Ni2+、Cu2+反應(yīng)形成化合物(Ni,Cu)3Si2O5(OH)4的原理，構(gòu)筑高度分散的NiCu/SiO2雙金屬催化劑并將其用于PR的催化加氫研究；系統(tǒng)了研究了NiCu合金效應(yīng)以及催化劑形貌對(duì)PR加氫的影響。結(jié)果表明，花狀結(jié)構(gòu)的NiCu/SiO2雙金屬催化劑具有優(yōu)異的加氫活性和穩(wěn)定性。C5PR和C9PR的加氫度分別為95.0%和96.4%，明顯優(yōu)于通過浸漬法制備的NiCu/SiO2催化劑以及花狀結(jié)構(gòu)的Ni/SiO2單金屬催化劑，這可歸因于：1) 催化劑表面的大開孔會(huì)降低PR的擴(kuò)散阻力，有利于PR/HPR分子轉(zhuǎn)移；2) 具有小顆粒和高度分散的活性組分更易于與反應(yīng)物接觸；3) NiCu合金的形成促進(jìn)了電子從Cu到Ni的轉(zhuǎn)移，富電子的Ni活性位有利于氫氣的解離以及PR中缺電子的烯烴雙鍵的吸附；4) 通過原位還原硅酸鎳銅前驅(qū)體，活性金屬錨固在載體上，減輕了金屬顆粒的遷移和聚集。 Figure 1. Schematic illustration of the fabrication procedure of NiCu/SiO2 catalyst and catalytic conversion mechanism of C5PR to HC5PR. 關(guān)鍵詞：花狀催化劑；NiCu合金；催化加氫；石油樹脂 參考文獻(xiàn) [1] 朱明慧, 蒲延芳. 石油化工動(dòng)態(tài), 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. 石油化工動(dòng)態(tài), 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.

關(guān)鍵詞

花狀催化劑;NiCu合金;催化加氫;石油樹脂

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