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Selective Ethylene Oligomerization with Chromium-based Metal-Organic Framework MIL-100 Evacuated under Different Temperatures
HAN Yang 1,ZHANG Ying 1 *,LIU Suyan 2,FENG Guangliang 1,GAO Fei 1,WANG Hui 1
1.The State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing, 102249
2.College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, Hebei, 066004
*Correspondence author
#Submitted by
Subject:
Funding: Specialized Research Fund for the Doctoral Program of Higher Education of China （No.No. 20130007110008）, National Natural Science Foundation of China （No.No. 51072230, No. 21676296, No. U1162118 and No. 21606193）, the Beijing Young Talents Plan （No.No. YEPT0687)）
Opened online:14 October 2016
Accepted by: none
Citation: HAN Yang,ZHANG Ying,LIU Suyan.Selective Ethylene Oligomerization with Chromium-based Metal-Organic Framework MIL-100 Evacuated under Different Temperatures[OL]. [14 October 2016] http://en.paper.edu.cn/en_releasepaper/content/4706439
 
 
MIL-100(Cr) was synthesized and evacuated under different temperatures to generate a series of Cr-based heterogeneous catalysts for ethylene slurry oligomerization. Their crystal structures, pore properties and metal oxidation states were characterized by XRD, N-adsorption/desorption and XPS techniques. These catalysts showed moderate catalytic activities for ethylene oligomerization but high selectivities to low carbon olefins C6, C8 and C10. Moreover, the oligomer distributions were different depending on the evacuation temperatures. The XPS results showed that the increase of evacuation temperature below 350 oC caused the reduction of some CrIII active sites in the MIL-100(Cr) structure to CrII active sites, which made the catalytic behavior switch from oligomerization to oligomerization plus polymerization activities. The MIL-100(Cr)-250 catalyst evacuated at 250 oC exhibited the largest BET surface area of 2348 m2og-1 and the highest oligomerization and polymerization activities up to 9.27×105 g/(molCroh) and 0.99×105 g/(molCroh) respectively. The main oligomerization products were low carbon olefins C6, C8 and C10. The by-product polymer from MIL-100(Cr)-250 was also characterized in detail by various techniques. It was found that the polymer belonged to linear polyethylene with ultrahigh molecular weight and broad molecular weight distributions. This work demonstrated that MOFs containing coordinatively unsaturated metal sites might be a promising selective catalyst for ethylene slurry oligomerization.
Keywords:Ethylene oligomerization; MIL-100(Cr); Evacution temperature
 
 
 

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