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采用钠促进的铁锌催化剂生产线性α-烯烃 费托合成。

Linear α-olefin production with Na-promoted Fe-Zn catalysts Fischer-Tropsch synthesis.

作者信息

Yang Sunkyu, Lee Sungwoo, Kang Seok Chang, Han Seung Ju, Jun Ki-Won, Lee Kwan-Young, Kim Yong Tae

机构信息

Carbon Resources Institute, Korea Research Institute of Chemical Technology Daejeon 34114 Republic of Korea

Department of Chemical and Biological Engineering, Korea University 145 Anam-ro Seoul 02841 Republic of Korea

出版信息

RSC Adv. 2019 May 7;9(25):14176-14187. doi: 10.1039/c9ra02471a.

Abstract

The production of linear alpha-olefins (α-olefins) is a practical way to increase the economic potential of the Fischer-Tropsch synthesis (FTS) because of their importance as chemical intermediates. Our study aimed to optimize Na-promoted FeZnO catalysts such that they selectively converted syngas to linear α-olefins FTS at 340 °C and 2.0 MPa. The FeZnO catalysts were calcined at different temperatures from 350 to 700 °C before Na anchoring. The increase in the size of the ZnFeO crystals comprising the catalyst had a negative effect on the reducibility of Fe oxides and the particle size of FeC during the reaction. The Na species in the catalyst restrained the reduction of FeZnO but facilitated the formation of FeC. When pure FeZnO was calcined at 400 °C, the corresponding catalyst (, Na/FeZnO (400)) exhibited higher catalytic activity and stability than the other catalysts for a 50 h reaction. Compared to the other catalysts, Na/FeZnO (400) enabled a higher number of active Fe carbides (FeC) to intimately interact with the Na species, even though the catalyst had a lower total surface basicity based on surface area. The Na/FeZnO (400) showed a maximum hydrocarbon yield of 49.7% with a maximum olefin selectivity of 61.3% in the C1-C32 range. Examination of the reaction product mixture revealed that the Na/FeZnO catalysts converted α-olefins to branched paraffins (13.9-19.5%) a series of isomerization, skeletal isomerization, and hydrogenation reactions. The Na/FeZnO (400) catalyst had a relatively low consumption rate of internal olefins compared to other catalysts, resulting in the lowest selectivity for branched paraffins. The Na/FeZnO (400) showed a maximum α-olefin yield (26.6%) in the range C2-C32, which was 27.9-50.0% higher than that of other catalysts. The α-olefin selectivity in the C5-C12 range for the Na/FeZnO (400) was 37.5% relative to the total α-olefins.

摘要

线性α-烯烃(α-烯烃)的生产是提高费托合成(FTS)经济潜力的一种切实可行的方法,因为它们作为化学中间体具有重要意义。我们的研究旨在优化钠促进的FeZnO催化剂,使其在340℃和2.0MPa条件下将合成气选择性转化为线性α-烯烃进行费托合成。在钠锚固之前,将FeZnO催化剂在350至700℃的不同温度下煅烧。构成催化剂的ZnFeO晶体尺寸的增加对反应过程中Fe氧化物的还原度和FeC的粒径有负面影响。催化剂中的钠物种抑制了FeZnO的还原,但促进了FeC的形成。当纯FeZnO在400℃煅烧时,相应的催化剂(Na/FeZnO(400))在50小时的反应中表现出比其他催化剂更高的催化活性和稳定性。与其他催化剂相比,Na/FeZnO(400)能使更多的活性碳化铁(FeC)与钠物种紧密相互作用,尽管基于表面积该催化剂的总表面碱度较低。Na/FeZnO(400)在C1-C32范围内显示出最大烃产率为49.7%,最大烯烃选择性为61.3%。对反应产物混合物的检查表明,Na/FeZnO催化剂通过一系列异构化、骨架异构化和氢化反应将α-烯烃转化为支链石蜡(13.9-19.5%)。与其他催化剂相比,Na/FeZnO(400)催化剂的内烯烃消耗率相对较低,导致支链石蜡的选择性最低。Na/FeZnO(400)在C2-C32范围内显示出最大α-烯烃产率(26.6%),比其他催化剂高27.9-50.0%。相对于总α-烯烃,Na/FeZnO(400)在C5-C12范围内的α-烯烃选择性为37.5%。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a76c/9064040/8d2b8d68e5fb/c9ra02471a-f1.jpg

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