Effect of H2O on Cu-based catalyst in one-step slurry phase dimethyl ether synthesis

被引:64
作者
Wang, Dongsheng [1 ,2 ]
Han, Yizhuo [1 ]
Tan, Yisheng [1 ]
Tsubaki, Noritatsu [3 ]
机构
[1] Chinese Acad Sci, Inst Coal Chem, State Key Lab Coal Convers, Taiyuan 030001, Peoples R China
[2] Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China
[3] Toyama Univ, Sch Engn, Dept Appl Chem, Toyama 9308555, Japan
关键词
Dimethyl ether; Hybrid catalyst; Deactivation; Cu-based catalyst; Methanol; Slurry reactor; METHANOL SYNTHESIS; HYBRID CATALYSTS; DEACTIVATION; ZNO; SYNGAS; REGENERATION; PRECURSORS; SUPPORT; DME;
D O I
10.1016/j.fuproc.2008.11.007
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
One-step dimethyl ether (DME) synthesis in slurry phase was catalyzed by a hybrid catalyst composed of a Cu-based methanol synthesis catalyst and a gamma-Al2O3 methanol dehydration catalyst under reaction conditions of 260 degrees C and 5.0 MPa. It was found that instability of the Cu-based catalyst led to rapid deactivation of the hybrid catalyst. The stability of the Cu-based catalyst under DME synthesis conditions was compared with that under methanol synthesis conditions. The results indicated that harmfulness of water, which formed in DME synthesis, caused the Cu-based catalyst to deactivate at a high rate. Surface physical analysis, elemental analysis. XRD and XPS were used to characterize the surface physical properties, components, crystal structures and Surface morphologies of the Cu-based catalysts. it was found that Cu-0 was the active component for methanol synthesis and Cu2O might have less activity for the reaction. Compared with methanol synthesis process, crystallite size of Cu became bigger in DME synthesis process, but carbon deposition was less severe. It was also found that there was distinct metal loss of Zn and Al caused by hydrothermal leaching, impairing the stability of the catalyst. In slurry phase DME synthesis, a part of Cu transformed into Cu-2(OH)(2)CO3, causing a decrease in the number of active sites of the Cu-based catalyst. And some ZnO converted to Zn-5(OH)(6)(CO3)(2), which caused the synergistic effect between Cu and ZnO to become weaker. Crystallite size growth of Cu, carbon deposition, metal loss of Zn and Al, formation of Cu-2(OH)(2)CO3 and Zn-5(OH)(6)(CO3)(2) were important reasons for rapid deactivation of the Cu-based catalyst. (c) 2008 Elsevier B.V. All rights reserved.
引用
收藏
页码:446 / 451
页数:6
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