煤热解挥发分在活性炭上的积炭行为及其过程分析

Coke formation on activated carbon during catalytic upgrading of coal pyrolysis volatiles

  • 摘要: 中低温热解煤焦油存在重质组分含量高、焦油品质差等问题,通过引入催化剂原位调控热解挥发分的反应,可有效改善焦油品质,但催化剂易积炭失活,影响其持续使用时间。利用下行床连续热解反应器,研究了挥发分在活性炭催化剂上的积炭行为,通过改变进煤时间(30、60和100 min),考察了挥发分的反应及其在活性炭上形成积炭的过程机制。结果表明,挥发分反应在活性炭上形成了大量积炭,随着进料时间的延长,活性炭上积炭的绝对量增加,但积炭形成的速率降低,因此,对于干基煤积炭的产率减小。随着活性炭上积炭量增加,活性炭的比表面积显著减小,催化裂解活性降低,焦油产率以及其中的沥青产率均有增大。焦油的组成分析表明,随着进料时间的延长,含氧化合物的相对含量增加,C−O弱键的断裂被抑制,这也使得积炭形成速率有所降低。

     

    Abstract: The content of heavy pitch in tar generated from coal pyrolysis is high. To improve the quality of tar, catalysts are applied for adjusting the reaction of volatiles during coal pyrolysis. However, catalysts are easy to deactivate due to coke deposition. In this study, coke amount on activated carbon catalysts during catalytic upgrading of coal pyrolysis volatiles was investigated in the downer-bed reactor. The process of coke formation was studied at different feed time (30, 60 and 100 min) of coal. Results show that a great amount of coke is generated on the activated carbons. With the increase of feed time, the amount of coke on activated carbon increases, while the rate of coke formation decreases, thus decreasing the coke yield based on dry coal. The specific surface area and catalytic cracking activity of the activated carbon decrease with the increase of coke amount. Hence, the yields of tar and pitch increase with the increase of feed time. The relative content of oxygen-containing compounds in the tar increases with the increase of feed time, which indicates that the cleavage of weak chemical bond C−O is suppressed. That may result in a decrease in the rate of coke formation.

     

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