Influence of cerium sources on CuO/CeO2 catalysts for hydrogen production from steam reforming of methanol
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摘要: 采用沉淀法合成了CeO2载体，再经浸渍法负载活性组分得到CuO/CeO2催化材料，探究了铈源（Ce（NO3）3·6H2O、CeCl3·6H2O、Ce（NH4）2（NO3）6、Ce（SO4）2·4H2O）对CuO/CeO2催化性能的影响。通过采用XRD、SEM、N2O滴定、BET和H2-TPR等表征手段对催化材料的结构和性质研究发现，四种铈源合成的CuO/CeO2催化材料在Cu比表面积、还原性能以及活性组分和载体间的相互作用方面存在着明显差别。其中，由Ce（NO3）3·6H2O合成的CuO/CeO2催化材料的Cu比表面积较大，CuO还原温度较低，CeO2载体与CuO之间相互作用较强，在甲醇水蒸气重整反应过程中，表现出较佳的催化活性，在反应温度为553 K，水醇比n（H2O）/n（MeOH）为1.2，甲醇水蒸气气体空速（GHSV）为1760 h-1时，甲醇的转化率为100%，重整气中CO摩尔含量为0.84%。Abstract: CeO2 support was synthesized by precipitation method and used to prepare CuO/CeO2 catalyst using impregnation method. The effects of cerium sources (Ce(NO3)3·6H2O, CeCl3·6H2O, Ce(NH4)2(NO3)6 and Ce(SO4)2·4H2O) on the catalytic performance of CuO/CeO2 catalyst were investigated. XRD, SEM, N2O titration, BET and H2-TPR were used to study the structure and properties of the catalysts. The CuO/CeO2 catalysts with different cerium sources have obvious differences in Cu specific surface area, reduction performance and interaction between active component and support. Moreover, CuO/CeO2 catalyst prepared with Ce(NO3)3·6H2O has large Cu specific surface area, low reduction temperature and strong interaction between CeO2 support and CuO and shows better catalytic activity in methanol steam reforming. The methanol conversion is 100% at reaction temperature of 553 K, water/methanol ratio in feed of 1.2 and methanol water gas hourly space velocity of 1760 h-1. Besides, the CO molar content in reformed gas is 0.84%.
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Key words:
- method of precipitation /
- cerium source /
- methanol steam reforming /
- hydrogen
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图 1 CeO2-A纳米材料的SEM照片和表面粒径直方图
Figure 1 Surface particle size histogram and SEM image of the CeO2-A nano-materials
图 2 CeO2-B纳米材料的SEM照片和表面粒径直方图
Figure 2 Surface particle size histogram and SEM image of the CeO2-B nano-materials
图 3 CeO2-C纳米材料的SEM照片和表面粒径直方图
Figure 3 Surface particle size histogram and SEM image of the CeO2-C nano-materials
图 4 CeO2-D纳米材料的SEM照片和表面粒径直方图
Figure 4 Surface particle size histogram and SEM image of the CeO2-D nano-materials
图 5 CeO2-X纳米材料的XRD谱图
Figure 5 XRD patterns of the CeO2-X nano-materials
a: CeO2-A; b: CeO2-B; c: CeO2-C; d: CeO2-D
图 6 不同铈源合成催化剂的XRD谱图
Figure 6 XRD patterns of the catalysts synthesized from different cerium sources
a: Cu-Ce-A; b: Cu-Ce-B; c: Cu-Ce-C; d: Cu-Ce-D
图 7 不同铈源合成催化剂的H2-TPR谱图
Figure 7 H2-TPR profiles of the catalysts synthesized from different cerium sources
a: Cu-Ce-A; b: Cu-Ce-B; c: Cu-Ce-C; d: Cu-Ce-D
图 8 催化活性与重整温度的关系
Figure 8 Relationship between catalytic activity and reforming temperature
(reaction conditions: n(H2O)/n(MeOH)=1.2:1, GHSV=1760h-1)
a: Cu-Ce-A; b: Cu-Ce-B; c: Cu-Ce-C; d: Cu-Ce-D; e: equil
图 9 不同温度下重整气中的CO摩尔含量
Figure 9 CO molar content in reformed gas at different temperatures
(reaction conditions: n(H2O)/n(MeOH)=1.2:1, GHSV=1760h-1)
a: Cu-Ce-A; b: Cu-Ce-B; c: Cu-Ce-C; d: Cu-Ce-D; e: equil表 1 催化剂表面的物化性质和产氢速率
Table 1 Physical properties of the synthesized catalysts and hydrogen production rate in methanol steam reforming
Catalyst ABET
/(m2·g-1)Pore volume
v/(cm3·g-1)Cu dispersion /% Cu surface area
A /(m2·g-1)H2 production ratea
/(μmol·kg-1·s-1)CeO2-A 37.4 0.10 - - - CeO2-B 59.1 0.15 - - - CeO2-C 96.9 0.04 - - - CeO2-D 110.3 0.05 - - - Cu-Ce-A 21.9 0.09 15 8.8 16941 Cu-Ce-B 54.6 0.14 13 7.2 14753 Cu-Ce-C 81.6 0.03 8 4.4 9329 Cu-Ce-D 83.1 0.04 2 1.2 7874 aH2 production rate was calculated when temperature is 553K, n(H2O)/n(MeOH)=1.2:1, GHSV=1760h-1 
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表 2 催化剂还原峰位置
Table 2 Reduction peak position of the catalysts
Catalyst Peak position t/℃ peak 1 peak 2 Cu-Ce-A 178 222 Cu-Ce-B 182 253 Cu-Ce-C 195 227 Cu-Ce-D 200 223
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