Effects of Promoters of Cobalt-Based Catalysts on the Yield of Diesel-Range Hydrocarbons in Fischer–Tropsch Synthesis

IF 1.1 4区 工程技术 Q3 CHEMISTRY, ORGANIC
O. L. Eliseev, E. M. Smirnova, K. M. Mazurova, R. V. Kazantsev, I. N. Zubkov, R. E. Yakovenko, N. R. Demikhova, A. P. Glotov, A. V. Stavitskaya
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Abstract

The paper investigates the effects of lanthanum and manganese promotion (3 wt %) on the physicochemical properties and catalytic performance of a supported 15%Co/Al2O3 catalyst in the synthesis of hydrocarbons from Co and H2. The catalysts were prepared by impregnating the support with relevant metal nitrate solutions followed by drying, calcination, and hydrogen activation. The samples were characterized by X-ray diffraction analysis (XRD), low-temperature nitrogen adsorption, temperature-programmed reduction (TPR), and transmission electron microscopy (TEM). The catalytic performance was tested in fixed-bed flow-type reactors at 240°C, 2 MPa, and CO/H2 = 1 : 2 with the feed GHSV being varied. At a CO conversion of about 50%, the promoted catalysts exhibited an increase in the C5+ selectivity and a drop in the methane selectivity in the order of Co < Co–La < Co–Mn. The Mn promotion increased the hydrocarbon chain growth probability up to 0.89, thus enhancing the yield of the most valuable products such as diesel-range and solid hydrocarbons. In the presence of 15Co3.15Mn/Al2O3, a C5+ selectivity of 45.3% was achieved at 86% CO conversion. Under high CO conversion conditions (80–86%), the selectivity towards higher hydrocarbons markedly declined, apparently due to the intensification of the water gas shift reaction. Nonetheless, even under these conditions, the Co–Mn catalyst provided the highest relative content of diesel-range hydrocarbons in the products. For 15Co3.15Mn/Al2O3, the C11–C18 selectivity reached 56.7 at 51.4% CO conversion and 41.2 at 86% CO conversion. The C11–C18 selectivity values provided by 15Co/Al2O3 were 10–20% lower (51.8 and 35.0%, respectively).

Abstract Image

钴基催化剂促进剂对费托合成柴油系烃产率的影响
研究了镧和锰促进剂(3wt %)对负载型15%Co/Al2O3催化剂的理化性质和催化性能的影响。催化剂的制备方法是在载体上浸渍相应的硝酸金属溶液,然后干燥、煅烧、氢活化。采用x射线衍射分析(XRD)、低温氮吸附、程序升温还原(TPR)和透射电镜(TEM)对样品进行了表征。在固定床流动式反应器中,在240℃、2 MPa、CO/H2 = 1:2条件下,改变进料GHSV,测试了催化性能。在CO转化率约为50%时,催化剂的C5+选择性提高,甲烷选择性降低,其顺序为CO <; CO - la < CO - mn。Mn的促进作用使烃链生长概率提高到0.89,从而提高了柴油和固体烃等最有价值产品的产率。在15Co3.15Mn/Al2O3存在下,C5+选择性为45.3%,CO转化率为86%。在高CO转化率条件下(80 ~ 86%),对高碳氢化合物的选择性明显下降,这可能是由于水气转换反应的加剧。尽管如此,即使在这些条件下,Co-Mn催化剂在产品中提供了最高的柴油范围碳氢化合物的相对含量。对于15Co3.15Mn/Al2O3,当CO转化率为51.4%时,C11-C18选择性为56.7,当CO转化率为86%时,C11-C18选择性为41.2。15Co/Al2O3提供的C11-C18选择性值降低了10-20%(分别为51.8%和35.0%)。
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来源期刊
Petroleum Chemistry
Petroleum Chemistry 工程技术-工程:化工
CiteScore
2.50
自引率
21.40%
发文量
102
审稿时长
6-12 weeks
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.
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