Catalytic Properties of Unsupported Catalysts Based on Transition Metal Phosphides in Hydrotreating of Pyrolysis Products of Chlorinated Polymer Wastes
E. G. Dzhabarov, N. N. Petrukhina, E. M. Zakharyan
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引用次数: 0
Abstract
Nickel, cobalt, molybdenum, tungsten, and iron phosphides were prepared in situ from oil-soluble precursors and red phosphorus in the presence of a chlorinated substrate, 1,4-dichlorobenzene. Their catalytic activity was studied in competing processes of the hydrogenolysis of model feedstock containing a chlorinated derivative (1,4-dichlorobenzene) and heteroatomic compounds (benzothiophene, guaiacol, terephthalic acid, quinoline). Analysis of the phase composition of the catalysts by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) confirmed the formation of the phases of the metal phosphides, chlorides, and phosphates. The activity of the phosphides in the 1,4-dichlorobenzene hydrodechlorination increases in the order Mo < Fe < W < Co < Ni, and that in the joint process of 1,4-dichlorobenzene hydrodechlorination and benzothiophene hydrodesulfurization, in the order Co < W < Fe ≈ Ni < Mo. In the hydrodechlorination of 1,4-dichlorobenzene in a mixture with guaiacol, the activity of all the phosphides except iron phosphide decreases as compared to the 1,4-dichlorobenzene hydrodechlorination in the single-component system. Iron phosphide shows promise as a protective bed catalyst in the hydrotreating of polymer waste pyrolysis products, and nickel phosphide, as a catalyst for the hydrotreating of products formed by pyrolysis of polyvinyl chloride in polymer waste mixtures.
在氯化底物1,4-二氯苯的存在下,用油溶性前体和红磷原位制备镍、钴、钼、钨和铁磷化物。在含有氯化衍生物(1,4-二氯苯)和杂原子化合物(苯并噻吩、愈创木酚、对苯二甲酸、喹啉)的模型原料的氢解竞争过程中研究了它们的催化活性。用x射线光电子能谱(XPS)和x射线衍射(XRD)分析催化剂的相组成,证实了金属磷化物、氯化物和磷酸盐的形成。在1,4-二氯苯加氢脱氯过程中,磷化物的活性按Mo <; Fe < W < Co <; Ni的顺序增大;在1,4-二氯苯加氢脱氯与苯并噻吩加氢脱硫联合过程中,磷化物的活性按Co <; W < Fe≈Ni <; Mo的顺序增大。与单组分体系中1,4-二氯苯加氢脱氯相比,除磷化铁外,所有磷化物的活性均降低。磷化铁在聚合物废热解产物加氢处理中具有良好的应用前景,磷化镍在聚合物废混合物中聚氯乙烯热解产物加氢处理中具有良好的应用前景。
期刊介绍:
Petroleum Chemistry (Neftekhimiya), founded in 1961, offers original papers on and reviews of theoretical and experimental studies concerned with current problems of petroleum chemistry and processing such as chemical composition of crude oils and natural gas liquids; petroleum refining (cracking, hydrocracking, and catalytic reforming); catalysts for petrochemical processes (hydrogenation, isomerization, oxidation, hydroformylation, etc.); activation and catalytic transformation of hydrocarbons and other components of petroleum, natural gas, and other complex organic mixtures; new petrochemicals including lubricants and additives; environmental problems; and information on scientific meetings relevant to these areas.
Petroleum Chemistry publishes articles on these topics from members of the scientific community of the former Soviet Union.