球状介孔锆铝复合氧化物甲醇催化剂载体的制备及性能

Preparation and Performance of Spherical Mesoporous Zr-Al Composite Oxides as Supporter of Methanol Catalyst

以Zr(NO 3)4·5H 2 O和Al(NO 3)3·9H 2 O为原料,采用葡萄糖水热法制备了一系列球状介孔复合氧化物(ZrO 2)x-Al 2 O 3(x=0、0.18、0.42、0.76和1.26),其结构和性能经扫描电子显微镜、低温N 2吸脱附、NH 3吸脱附表征。以(ZrO 2)x-Al 2 O 3为载体,制备了铜锌基甲醇催化剂,其结构经X-射线衍射和N 2 O化学滴定表征,并考察了催化剂在合成气合成甲醇反应中的催化性能。结果表明:当n(ZrO 2)/n(Al 2 O 3)=0.42时,复合氧化物ZA2具有较大的孔径和较弱的表面酸强度,以其作为载体合成的铜锌基甲醇催化剂CZn/ZA2的活性铜比表面积较高。在5 MPa、250℃反应条件下,甲醇的时空收率达到1.44 g·mL-1·h-1,活性比传统C307甲醇合成催化剂提高约2.1%。

Several spherical mesoporous composite oxides of(ZrO 2)x-Al 2 O 3(x=0,0.18,0.42,0.76 and 1.26)were prepared using Zr(NO 3)4·5H 2 O and Al(NO 3)3·9H 2 O as raw material by glucose hydrothermal method.The structure and properties of these oxides were characterized by SEM,N 2-sorption and NH 3-TPD.The Cu-Zn based catalysts were prepared using these oxide as supporters.The structures were characterized by XRD and N 2 O titration.The performance of the catalysts were investigated in the reaction of methanol synthesis from synthesis gas.The results showed that the oxide of ZA2 with the ZrO 2/Al 2 O 3 molar ratio of 0.42 had larger pore size and weaker acid strength.The space-time yield can reach 1.44 g·mL-1·h-1 over the CZn/ZA2 methanol catalyst using ZA2 as supporter under the reaction condition of 5 MPa and 250℃.The activity of CZn/ZA2 was 2.1%higher than traditional C307 methanol catalyst.