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通过用钠改性的铁锆催化剂上的费托合成将合成气直接转化为轻质烯烃

Direct Conversion of Syngas to Light Olefins through Fischer-Tropsch Synthesis over Fe-Zr Catalysts Modified with Sodium.

作者信息

Ma Zhunzhun, Ma Hongfang, Zhang Haitao, Wu Xian, Qian Weixin, Sun Qiwen, Ying Weiyong

机构信息

Engineering Research Centre of Large Scale Reactor Engineering and Technology, Ministry of Education, State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China.

State Key Laboratory of Coal Liquefaction and Coal Chemical Technology, Shanghai 201203, China.

出版信息

ACS Omega. 2021 Feb 8;6(7):4968-4976. doi: 10.1021/acsomega.0c06008. eCollection 2021 Feb 23.

Abstract

Fe-Zr-Na catalysts synthesized by coprecipitation and impregnation methods were implemented to investigate the promoting effects of Na and Zr on the iron-based catalyst for high-temperature Fischer-Tropsch synthesis (HTFT). The catalysts were characterized by Ar adsorption-desorption, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, CO temperature-programmed desorption, H temperature-programmed desorption, X-ray photoelectron spectroscopy, and Mössbauer spectroscopy (MES). The results indicated that Na changed the active sites on the catalyst surface for the CO and hydrogen adsorption, owing to the electron migration from Na to Fe atoms, which resulted in an enhanced CO dissociative adsorption and a decrease in hydrogen adsorption on the metallic Fe surface. The decreased H/C ratio on the catalyst surface accounted for the increased chain propagation and weakened hydrogenation of light olefins. Besides, Na could also facilitate the carbonization of catalysts and protect the iron carbide against oxidation, which provides more active sites for HTFT reaction and is beneficial to the C-C coupling. Zr could decrease the hematite crystallite size and stabilize the active phase to improve the HTFT activity. At an optimal Na loading of 1.0 wt %, the Fe-Zr-1.0Na catalyst exhibited the highest light olefin selectivity of 35.8% in the hydrocarbon distribution at a CO conversion of 95.2%.

摘要

采用共沉淀法和浸渍法合成了Fe-Zr-Na催化剂,用于研究Na和Zr对高温费托合成(HTFT)铁基催化剂的促进作用。通过氩气吸附-脱附、X射线衍射、扫描电子显微镜、透射电子显微镜、CO程序升温脱附、H程序升温脱附、X射线光电子能谱和穆斯堡尔光谱(MES)对催化剂进行了表征。结果表明,由于电子从Na迁移到Fe原子,Na改变了催化剂表面CO和氢吸附的活性位点,导致CO解离吸附增强,金属Fe表面氢吸附减少。催化剂表面H/C比降低,导致链增长增加,轻烯烃加氢减弱。此外,Na还可以促进催化剂的碳化,并保护碳化铁不被氧化,为HTFT反应提供更多活性位点,有利于C-C偶联。Zr可以减小赤铁矿微晶尺寸并稳定活性相,从而提高HTFT活性。在Na负载量为1.0 wt%的最佳条件下,Fe-Zr-1.0Na催化剂在CO转化率为95.2%时,在烃类分布中表现出最高的轻烯烃选择性,为35.8%。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5b02/7905929/ce3cc98a8048/ao0c06008_0002.jpg

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