液体镓-铟共晶活化铝-钴和铝-镍合金与叔丁基氯的相互作用,形成催化金属-铝-氯配合物

A. B. Arbuzov, V. Drozdov, D. A. Shlyapin, A. Lavrenov
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引用次数: 2

摘要

众所周知,铝和铁族金属(钴、镍)的二元合金在与液态共晶镓铟激活后,通过去除“钝化”氧化层,急剧增加了对有机氯的反应性。相应的反应形成金属-铝-氯络合物作为无机产物,在烃类液相转化的许多实际重要催化反应中都很活跃,如:烷基化、异构化、寡聚化。这种方法是由作者先前为多晶铝开发的,对金属络合物催化很感兴趣,因为催化氯化铝和/或金属-氯化铝络合物的形成可以直接在反应介质中进行,即在原位。本文采用扫描电镜和x射线能谱分析方法,研究了液态镓铟共晶活化铝钴合金和铝镍合金表层的局部组成、结构和形貌,确定了它们在室温下与叔丁基氯相互作用动力学的物理化学规律。采用原位ATR-FT-IR方法研究了“活化合金-氯化叔丁酯”相间区金属氯配合物的形成。结果表明,在相互作用过程中形成了由钴和镍离子稳定的单核和双核氯化铝阴离子。假定在低温下形成的离子络合物对是烃类液相转化反应的活性中心。与氯化铝催化剂相比,这些结构导致了催化过程选择性的显著变化。引用本文:Arbuzov A.B., Drozdov V.A., Shlyapin D.A., Lavrenov a .。液体镓-铟共晶与叔丁基氯活化铝-钴和铝-镍合金的相互作用形成催化金属-铝-氯配合物。Izv。Vyssh。Uchebn。Zaved。Khim。Khim。Tekhnol》2018。v . 61。N 9。p . 64 - 69
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INTERACTION OF ALUMINUM-COBALT AND ALUMINUM-NICKEL ALLOYS ACTIVATED BY LIQUID GALLIUM-INDIUM EUTECTIC WITH TERT-BUTYL CHLORIDE FOR FORMATION OF CATALYTIC METAL - ALUMO-CHLORIDE COMPLEXES
It is known that binary alloys of aluminum and metals of the iron group (cobalt, nickel) after their activation with the liquid eutectic gallium-indium by the removal of “passivating” oxide layers sharply increase the reactivity with respect to organochlorines. Corresponding reactions lead to the formation    of metal – alumo - chloride complexes as inorganic products, which are active in many practically important catalytic reactions of liquid-phase conversion of hydrocarbons such as: alkylation, isomerization, oligomerization. This approach which was previously developed by the authors for the polycrystalline aluminum, is of interest in metal-complex catalysis since the formation of catalytic alumo-chloride and/or metal-alumo-chloride complexes can be carried out directly in the reaction medium, i.e. in situ. In this work, the local composition, structure and morphology of surface layers of aluminum-cobalt and aluminum-nickel alloys activated with liquid gallium-indium eutectic were studied using the methods of scanning electron microscopy and X-ray energy-dispersive spectrometry to determine the physicochemical regularities of the dynamics of their interaction with tert-butyl chloride at room temperatures. The formation of metal chloride complexes in the interphase area “activated alloy - tert-butyl chloride” was studied by ATR-FT-IR method in situ. The results obtained indicate that mono- and bi- nuclear alumo-chloride anions stabilized by cobalt and nickel cations are formed during the interaction. It is assumed that the ionic complex pairs formed are the active centers in liquid-phase reactions of hydrocarbons transformation at low temperatures. These structures are responsible for significantly change in the selectivity of catalytic processes compared to aluminum chloride catalyst. For citation: Arbuzov A.B., Drozdov V.A., Shlyapin D.A., Lavrenov A.V. Interaction of aluminum-cobalt and aluminum-nickel alloys activated by liquid gallium-indium eutectic with tert-butyl chloride for formation of catalytic metal - alumo-chloride complexes. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 9-10. P. 64-69
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