Carbon monoxide hydrogenation on cobalt/alumina and cobalt/NaX catalysts

Wei-Jye Wang, Yu-Wen Chen *
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引用次数: 27

Abstract

The synthesis of hydrocarbons from catalytic hydrogenation of carbon monoxide was investigated over Co/Al2O3 and Co/NaX catalysts at 1 atm, 493–553 K, H2/CO = 2, and gas hourly space velocity (GHSV) = 1200. These catalysts were characterized by hydrogen chemisorption. X-ray diffraction (XRD), and temperature-programmed reduction. The type of support had pronounced effects on the activity and selectivity of cobalt. The results indicated that the cobalt oxide supported on alumina is easier to reduce than that on zeolite X. This is essentially due to strong acidity of the HX and the high dispersion of cobalt. This would result in less active sites for the chemisorption of hydrogen, and would result in a decrease in activity and an increase in the selectivity to alkenes. Significant amounts of 2-butene are observed on Co/NaX catalyst, indicating that the predominant secondary reaction is isomerization rather than oligomerization and cracking reactions. The presence of water in the zeolite may cause a change in the catalytic behavior of the Co/NaX catalyst. The kinetic order of the reaction for Co/Al2O3 is negative to the carbon monoxide partial pressure and positive to the hydrogen partial pressure. The reaction rates for the Co/NaX catalysts are independent of the carbon monoxide partial pressure and become more strongly dependent on the hydrogen partial pressure with positive order. The different kinetics seem to be due to different reaction mechanisms operative on the cobalt surface with different degrees of reduction.

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钴/氧化铝和钴/NaX催化剂上的一氧化碳加氢反应
以Co/Al2O3和Co/NaX为催化剂,在1atm, 493 ~ 553 K, H2/ Co = 2,气体时空速(GHSV) = 1200的条件下,对一氧化碳催化加氢合成烃类进行了研究。对催化剂进行了氢化学吸附表征。x射线衍射(XRD)和程序升温还原。载体类型对钴的活性和选择性有显著影响。结果表明,负载在氧化铝上的氧化钴比负载在沸石x上的氧化钴更容易还原,这主要是由于HX的强酸性和钴的高分散性。这将导致氢的化学吸附活性位点减少,并导致活性降低和对烯烃的选择性增加。在Co/NaX催化剂上观察到大量的2-丁烯,表明主要的二级反应是异构化而不是寡聚化和裂解反应。沸石中水的存在会引起Co/NaX催化剂催化行为的改变。Co/Al2O3反应的动力学级数对一氧化碳分压为负,对氢气分压为正。Co/NaX催化剂的反应速率与一氧化碳分压无关,而与氢分压的正序依赖性更强。不同的动力学似乎是由于不同的反应机制作用于不同还原程度的钴表面。
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