An Experimental Study of the Performance of Isomorphically Zirconium-Substituted Mesoporous Alumina Supported Cobalt Catalysts in Fischer-Tropsch Synthesis

S. Simanungkalit, Mingming Zhu, G. Pham, Zhezi Zhang, Dongke Zhang
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Abstract

A series of mesoporous alumina (MA) supported cobalt (Co/MA) catalysts with MA isomorphically substituted by zirconium (Zr) were synthesised and evaluated for their performance in the Fischer-Tropsch synthesis. The Zr/(Zr + Al) atomic ratios varied from 1% - 15%. A zirconium-impregnated Co/MA catalyst prepared by wet impregnation with a Zr/(Zr + Al) atomic ratio of 5% was also evaluated to examine Zr incorporation’s effect method. The catalysts synthesised were characterised using N 2 adsorption-desorption, X-ray Powder Diffraction (XRD), Transmission Electron Microscopy (TEM), and X-Ray Photoelectron Spectroscopy (XPS). It was found that Zr 4+ ions were incorporated into the framework of MA and kept intact up to a Zr/(Zr + Al) atomic ratio of 5%. The cobalt dispersion and reducibility were improved as the Zr/(Zr + Al) atomic ratio increased to 50%. The performance of these catalysts for Fischer-Tropsch synthesis was evaluated using a fixed bed reactor at temperature and pressure of 493 K and 20 bar, respectively. The feed syngas had an H 2 /CO ratio of 2, diluted with 10% Ar. For isomorphically Zr-substituted Co/MA, the CO conversion and selectivity of diesel (C 10 - C 20 ) increased first and then decreased with increasing the Zr/(Zr + Al) atomic ratio. The maxi-mum 38.9% CO conversion and 34.6% diesel (C 10 - C 20 ) selectivity were obtained at Zr/(Zr + Al) atomic ratio of 5%. The isomorphic substitution method was better than the wet impregnation method in CO conversion and diesel selectivity.
同形锆取代介孔氧化铝负载钴催化剂费托合成性能的实验研究
合成了一系列介孔氧化铝(MA)负载钴(Co/MA)催化剂,并在费托合成中对其性能进行了评价。Zr/(Zr + Al)原子比在1% ~ 15%之间变化。采用湿浸渍法制备了Zr/(Zr + Al)原子比为5%的锆浸渍Co/MA催化剂,考察了Zr掺入的影响方法。采用n2吸附-解吸、x射线粉末衍射(XRD)、透射电镜(TEM)和x射线光电子能谱(XPS)对合成的催化剂进行了表征。发现zr4 +离子被吸收到MA的骨架中,并在Zr/(Zr + Al)原子比为5%时保持完整。当Zr/(Zr + Al)原子比增加到50%时,钴的分散性和还原性得到改善。在固定床反应器上,分别在493 K和20 bar的温度和压力下,对这些催化剂的费托合成性能进行了评价。以10% Ar稀释的原料合成气h2 /CO比为2。对于同形Zr取代的CO /MA,随着Zr/(Zr + Al)原子比的增加,柴油(c10 ~ c20) CO转化率和选择性先升高后降低。Zr/(Zr + Al)原子比为5%时,CO转化率为38.9%,柴油(c10 ~ c20)选择性为34.6%。同构取代法在CO转化率和柴油选择性方面优于湿浸渍法。
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