Chain-like ZSM-5 zeolite coupled with Cu-Fe3O4 for CO2 hydrogenation to light aromatics
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摘要: 近年来,二氧化碳(CO2)的捕获与利用受到广泛关注,尤其CO2加氢直接制轻质芳烃(如苯、甲苯和二甲苯等)已被当作一条具有潜力的化学品生产路线,但有效调控芳烃产物分布及提高目标芳烃选择性仍是一个巨大的挑战。在此,本研究提供了一种由铜改性铁基催化剂耦合链状ZSM-5分子筛组成的双功能催化剂用于CO2加氢一步高效制备轻质芳烃。采用了XRD、SEM、TEM、ICP-AES、Py-FTIR和N2吸附-脱附等表征手段对双功能催化剂组分进行了分析,研究了分子筛酸密度和长径比(即b轴/a轴)对芳烃选择性及分布的影响。结果表明,具有高酸密度及适当长径比的链状ZSM-5分子筛能促进产物的C−C偶联并抑制CH4的生成,从而有效提高芳烃的选择性及甲苯的时空收率(STY)。Abstract: The capture and utilization of carbon dioxide (CO2) have attracted much attention in recent years; in particular, the direct hydrogenation of CO2 to light aromatics has been considered as a potential route to produce high value-added chemicals. However, it is still a big challenge to adjust the aromatic distribution and achieve a high selectivity to the targeted products. In this work, a bifunctional catalyst that combines the Cu-modified Fe3O4 and the chain-like ZSM-5 zeolite is used for the hydrogenation of CO2 to light aromatics. The catalyst components were characterized by XRD, SEM, TEM, ICP-AES, Py-IR and N2 adsorption-desorption; the effect of acid density and length-to-diameter ratio (b-axis/ a-axis) of zeolite moiety on the selectivity and distribution of aromatic products was then investigated. The results indicate that the chain-like ZSM-5 zeolite moiety with high acid density and appropriate length-to-diameter ratio can promote the C–C coupling for CO2 hydrogenation and inhibit the formation of CH4, which can improve the selectivity to aromatics and the space time yield (STY) of toluene.
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Key words:
- carbon dioxide hydrogenation /
- aromatics /
- ZSM-5 zeolite /
- Cu-Fe3O4 /
- bifunctional catalyst
1) 共同第一作者 -
表 1 CZ5样品物理化学性质
Table 1 Physicochemical properties of various CZ5 zeolite samples
Catalyst Si/Al* Lewis acidity/(μmol·g−1) Brønsted acidity/(μmol·g−1) Total acidity/
(μmol·g−1)SBET
/(m2·g−1)CZ5-0.6-41.8 165 9.1 32.7 41.8 − CZ5-0.6-44.7 83 5.2 39.5 44.7 398.8 CZ5-0.6-61.0 61 8.8 52.2 61.0 − CZ5-1.7-52.4 88 4.3 48.1 52.4 377.6 CZ5-2.9-59.5 85 3.1 56.4 59.5 376.3 CZ5-3.7-28.7 90 2.3 26.5 28.7 369.7 *Calculated from ICP-AES -
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