Citation: WANG Feng, YAN Shu-Jun, YONG Xiao-Jing, LUO Chun-Tao, ZHANG Qing, WEN Peng-Yu, NG Yan-Jun, DOU Tao. Effects of Na⁺ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts[J]. Acta Physico-Chimica Sinica, ;2013, 29(02): 358-364. doi: 10.3866/PKU.WHXB201211143 shu

Effects of Na⁺ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts

1.
1 Research and Development Division, Shenhua Ningxia Coal Industry Group Co. Ltd., Yinchuan 750411, P. R. China;
2 The Key Laboratory of Catalysis of CNPC, China University of Petroleum-Beijing, Beijing 102249, P. R. China

Received Date: 12 September 2012
Available Online: 14 November 2012
Fund Project: 国际科技与交流专项(2010DFB40440) (2010DFB40440) 宁夏回族自治区科技攻关计划(年产50 万吨煤基聚丙烯装置工业运行及下游产业关键技术研究)资助项目 (年产50 万吨煤基聚丙烯装置工业运行及下游产业关键技术研究)

The effects of Na⁺ in dilution steam and coke deposition on the physicochemical properties andcatalytic performance of ZSM-5 catalysts for the methanol-to-propylene (MTP) reaction were investigated.The deactivated and regenerated catalysts were characterized by means of X-ray diffraction (XRD),scanning electron microscopy (SEM), X-ray fluorescence (XRF) spectrum, nitrogen adsorption/desorption,temperature-programmed desorption of ammonia (NH₃-TPD), and thermogravimetry (TG). Their catalyticperformance for MTP reaction was tested in a continuous flow fixed-bed micro-reactor at 470℃, 101325Pa, and with methanol weight hourly space velocity (WHSV) in the range of 1.0-3.0 h^-1. The resultsindicated that the catalyst crystal structure and morphology was not significantly altered after 970 h onstream. In the MTP reaction, Na⁺ in the dilution steam can easily enter the pore channels of the catalyst,and partially replace H protons, thereby gradually decreasing the amount of acidity and acid strength of thecatalyst, which eventually causes deactivation. In addition, coke deposits on the catalyst surface blocking its micropores are the main reason for deactivation of the MTP catalyst. Coke deposits are mostlyeliminated through the burning charcoal regeneration process. The effect of framework dealumination fromthe catalyst by steam in the MTP process is slow but more serious. Through regeneration and ionexchange process, the catalytic activity of the deactivated catalyst can be fully restored. The conversion ofmethanol is consistently above 99%, and propylene selectivity is greater than 46% even after 470 h onstream. With increasing reaction time, the propylene selectivity gradually increases, while ethyleneselectivity gradually decreases.
- Methanol-to-propylene catalyst,
- Coke deposition,
- Regeneration,
- Dilution steam
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沈阳化工大学材料科学与工程学院沈阳 110142

Effects of Na+ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts

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通讯作者: 陈斌, bchen63@163.com

Effects of Na⁺ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts