研究气体循环比对费托合成生产 C5-C18 烯烃的影响

I. Zubkov, O. D. Denisov, M. A. Timokhina, A. Savost’yanov, R. Yakovenko
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摘要

在温度为 250 °C、压力为 2.0 MPa、GHSV 为 1000 h-1 的条件下,在源气中 H2 /CO 的比例为 1.70,循环比为 4、8 和 16 的情况下,研究了含沸石催化剂 Сo-Al2O3 /SiO2 /ZSM-5/Al2O3 在流动和流动-循环操作模式下生产 C5+ 碳氢化合物(包括不饱和碳氢化合物)的工艺。结果表明,循环比为 8 时,工艺指标(C5+ 产品的选择性和生产率)达到最大值。与流动合成模式相比,使用气体循环可以调节产品的成分。循环比在 4-16 之间时,烃链长度为 5-20 个碳原子的烯烃比例从 53.9% 增加到 65.7%。与 Co-Al2O3 /SiO2 催化剂相比,使用含沸石催化剂可将 C8-C12 烯烃的生成量提高 3.3 倍--在循环比、压力和源气体中 H2 /CO 的比例 = 1.70 的相似值条件下,其含量从 13.5 wt.% 提高到 44.2 wt.%。研究发现,随着循环比的增加,含沸石催化剂的失活率降低,这可能是由于反应体积中水的分压降低所致。
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Study of the influence of the gas circulation ratio on the production of C5–C18 alkenes in the Fischer–Tropsch synthesis
The process of producing C5+ hydrocarbons, including unsaturated ones, on a zeolite-containing catalyst Сo-Al2O3 /SiO2 /ZSM-5/Al2O3 in flow and flow-circulation modes of operation at a temperature of 250 °C, a pressure of 2.0 MPa, GHSV 1000 h–1 has been studied , H2 /CO ratio = 1.70 in the source gas and circulation ratios of 4, 8 and 16. It was determined that the process indicators (selectivity and productivity for C5+ products) pass through a maximum at a circulation ratio of 8. The use of gas circulation in comparison with flow synthesis mode allows you to regulate the composition of products. An increase in the circulation ratio in the range of 4–16 leads to an increase in the proportion of formed olefins with a hydrocarbon chain length containing 5–20 carbon atoms, from 53.9 wt.% up to 65.7 wt.%. The use of a zeolite-containing catalyst intensifies the formation of C8–C12 alkenes in comparison with the Co-Al2O3 /SiO2 catalyst by 3,3 times – the content increases from 13,5 wt.% up to 44.2 wt.% at similar values of circulation ratio, pressure and H2 /CO ratio = 1.70 in the source gas. It was found that as the circulation ratio increases, the rate of deactivation of the zeolite-containing catalyst decreases, which may be caused by a decrease in the partial pressure of water in the reaction volume.
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