Cu-ZrO_2/凹凸棒石催化剂在甲醇水蒸气重整制氢反应中的性能

Performances of Cu-ZrO_2/attapulgite catalysts in steam reforming of methanol for hydrogen production

以凹凸棒石(ATP)为载体,采用浸渍法制备了Cu-ZrO_2/ATP系列催化剂,并在连续流动常压固定床微型反应器上对Cu-ZrO_2/ATP催化剂催化甲醇水蒸气重整制氢反应的催化性能进行评价,考察了反应温度、反应时间、Cu和ZrO_2的负载量、水醇摩尔比及重时空速(WHSV)等条件对催化性能的影响。采用XRD、N_2吸附-脱附、H_2-TPR、NH3-TPD、CO_2-TPD、BET等方法对催化剂的结构进行表征。实验结果表明,Cu(20%(w))-ZrO_2(15%(w))/ATP催化剂具有较高的活性和稳定性;在280℃、n(水)∶n(甲醇)=1.2∶1和WHSV=3.6 h^(-1)的条件下,甲醇转化率和氢气选择性均高于99%,CO选择性低于2.5%,且连续反应50 h后,催化剂仍保持较高的活性。表征结果显示,ZrO_2的加入改变了催化剂的孔结构和酸碱性,ZrO_2和Cu之间存在相互作用。

Cu-ZrO2/attapulgite（ATP） catalysts were prepared through impregnation with ATP as the support and characterized by means of XRD,N2 adsorption-desorption,H2-TPR,NH3-TPD, CO2-TPD and BET. Hydrogen production by the steam reforming of methanol over the Cu-ZrO2/ATP catalysts was investigated in a fixed bed micro-reactor under atmospheric pressure. The effects of reaction temperatures,mole ratio of water to methanol and weight hourly space velocity（WHSV） on the performances of the catalysts were researched. The results showed that the catalytic activity of the Cu（20%（w））-ZrO2（15%（w））/ATP catalyst was high, and its activity did not significantly reduce after reaction 50 h. Under the conditions of Cu（20%（w））-ZrO2（15%（w））/ATP as the catalyst,temperature 280℃,mole ratio of water to methanol 1.2∶1 and WHSV 3.6 h-1,both the conversion of methanol and the selectivity to hydrogen were higher than 99%,and the selectivity to CO was less than 2.5%. The characterization results indicated that,the addition of ZrO2 changed the pore structure and acid-alkali properties of the catalysts and there was some interaction between Cu and ZrO2.