摘要：以活性碳为载体，制备出用于甲醇水蒸气重整制氢的新型高效Cu/Zr/C，Cu/Ce/C，Cu/La/C催化剂，并详细比较Zr，Ce，La元素对催化性能的影响。结果表明，添加适量的Zr，Ce，La可显著提高催化活性和制氢选择性，同时有效降低产物中CO的含量。采用XRD图谱及TPR图谱分析方法证实添加适量稀土元素La、Ce对催化剂的微结构性质可产生重要的调控作用，从而大大提高催化活性和制氢选择性,其中Ce的催化活性和制氢选择性优于其它稀土元素。采用XPS谱图表明加入Zr可使铜系催化剂的活性提高，但催化活性的提高仅仅保持在小范围内。另外TPR结果表明催化剂的还原行为和ZrO2含量存在很大的关系。5276
关键词: 制氢；甲醇重整；Cu/Zr/C催化剂；Cu/Ce/C催化剂；Cu/La/C催化剂
The promoting role of ZrO2 and La2O3 on Cu catalysts for Methanol Steam Reforming
Abstract: The catalysts of Cu/Zr/C,Cu/Ce/C,Cu/La/C with high catalytic activities for hydrogen production by methanol steam reforming were prepared with the active carbon as supporters, and the promoting roles of Zr, Ce, La promoters to catalytic performance were compared in detail. The results displayed that the proper loadings of Zr,Ce,La can improve the catalytic activity and selectivity of H2, and depress the production of CO effectively. The results of XRD and TPR illustrated the high activity and selectivity of catalysts with Ce and La are accounted for the structure modification of rare earth promoters. The catalysts promoted by Ce are superior to other ones in catalytic activity and selectivity of hydrogen. The results of XPS confirmed that the introduction of Zr can make copper catalyst activity increased, but only keep on a small scale. In addition the TPR results showed that the reduction behavior of catalyst depends much on the content of ZrO2.
KeyWords: Hydrogen Production; Steam Reforming of Methanol; Cu/ Zr/ C;
Cu/ Ce/C ; Cu/ La/C
目 录
1 引言 1
1.1前言 1
1.2甲醇水蒸气重整反应机理 2
1.3甲醇水蒸气重整反应热力学及动力学分析 2
1.3.1热力学分析 2
1.3.2动力学分析 2
1.4甲醇水蒸气重整反应影响因素 3
1.5甲醇水蒸气重整制氢反应催化剂 3
1.5.1镍系催化剂 3
1.5.2铂钯系催化剂 3
1.5.3铜基催化剂 4
1.6稀土元素在Cu/C催化里面的作用 5
1.7 Zr元素在Cu/C催化里面的作用 6
1.8选题意义和目的 6
2 实验方法和仪器 8
2.1 催化剂的制备 8
2.1.1传统草酸盐共沉淀方法 8
2.1.2传统碳酸盐共沉淀方法 8
2.1.3 Cu/C以及Cu-Ce/C制备 8
2.2 催化剂的活性测试 8
2.3 催化剂的表征 8
2.3.1程序升温还原（TPR） 8
2.3.2 X光粉末衍射（XRD） 9
2.3.3原位漫反射（FT-IR） 9
2.4 实验材料和仪器 9
3 结果与讨论 10
3.1稀土催化剂 10
3.1.1不同含量的稀土催化剂SRM性能的研究 10
3.1.2添加次序不同的稀土催化剂SRM性能的研究 10
3.1.3催化剂在XRD图谱中的分析结果 11
3.1.4催化剂在TPR图谱中的分析结果 13
3.1.5原位红外表征结果 14
3.2 ZrO2助剂 16
3.2.1 ZrO2对催化剂基本性能的影响 16 ZrO2和La2O3助剂对Cu催化剂甲醇水蒸气重整反应的促进作用:http://www.751com.cn/huaxue/lunwen_2245.html