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摘要: 以γ-Al2O3为原料采用原位合成法制备CuAl2O4催化材料,通过XRF、XRD、BET和H2-TPR等手段对催化材料进行表征,考察铜铝物质的量比对CuAl2O4催化材料结构、性质及其催化甲醇水蒸气重整制氢性能的影响。结果表明,不同铜铝物质的量比主要影响了铜物种的还原性能,从而影响了其催化甲醇水蒸气重整制氢的性能。当铜铝物质的量比为1:2时,CuAl2O4催化材料的催化性能较好,在反应温度为260℃,水醇物质的量比为1.2,甲醇气体空速为800 h-1时,甲醇转化率为100%,产氢速率为895 mL/(kg·s)。Abstract: The CuAl2O4 catalytic material was in-situ synthesized using γ-Al2O3 as raw material. The catalytic material was characterized by XRF, XRD, BET and H2-TPR. The effect of the copper-aluminum molar ratios on the structure and properties of CuAl2O4 spinel catalytic material and its performance in hydrogen production from methanol steam reforming were investigated. The results show that the copper-aluminum molar ratios affects reduction performance of copper species, which affects its performance in catalyzing methanol steam reforming to produce hydrogen. When the copper-aluminum molar ratios is 1:2, CuAl2O4 catalytic material has better catalytic performance. When the reaction temperature is 260℃, with a water-methanol molar ratio of 1.2 and methanol gas hourly space velocity of 800 h-1, the methanol conversion reaches 100%, the hydrogen production rate is 895 mL/(kg·s).
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Key words:
- CuAl2O4 /
- methanol steam reforming /
- hydrogen /
- in-situ synthesis
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表 1 CuAl2O4-t催化材料的元素含量
Table 1 Elemental content of CuAl2O4-t catalytic materials
Catalyst Content of element w/% Al /Cu
(mol ratio)Cua Cub Ala Alb Oa Ob CuAl2O4-1 45.9 48.9 21.6 20.6 32.5 30.5 0.99 CuAl2O4-2 34.7 35.1 28.3 29.7 37.0 35.2 1.99 CuAl2O4-4 21.7 22.5 38.6 38.0 39.7 39.5 3.97 CuAl2O4-16 6.7 7.1 48.5 48.2 44.8 44.7 15.97 a: theoretical content;b: actual content 表 2 CuAl2O4-t催化材料和γ-Al2O3的比表面积及孔结构参数
Table 2 Specific surface area and pore structure parameters of CuAl2O4-t catalytic materials and γ -Al2O3
Catalyst ABET /(m2·g-1) Bore diameter d/nm CuAl2O4-1 18.6 3.42 CuAl2O4-2 26.2 3.04 CuAl2O4-4 57.6 18.14 CuAl2O4-16 89.9 18.15 γ-Al2O3 145.6 17.89 表 3 CuAl2O4-t催化材料还原峰面积及峰面积占比
Table 3 Reduction peak area and area content of CuAl2O4-t catalytic materials
Catalyst Peak area A/(a.u.) Area /% peak α peak β peak γ peak α peak β peak γ CuAl2O4-1 43242 18474 4562 65 28 7 CuAl2O4-2 6430 25594 1737 19 76 5 CuAl2O4-4 6170 9583 3125 33 51 16 CuAl2O4-16 3934 1209 325 72 22 6 表 4 催化材料的产氢速率对比
Table 4 Hydrogen production rate compare of catalytic materials
Catalyst Reaction temperature t/℃ Water/methanol wmol/% GHSV /h-1 H2 production rateb w/(mL·kg-1·s-1) CuAl2O4-1 260 1.2:1 800 633 CuAl2O4-2 260 1.2:1 800 895 CuAl2O4-4 260 1.2:1 800 820 CuO/CeO2-R[18] 240 1.2:1 800 378 CuO/CeO2[20] 280 1.2:1 800 380 CuZnCeZr[21] 240 1.2:1 1200 510 Zn0.5Ce1Zr9Ox[22] 450 1.4:1 1500 808 GHSV: methanol gas hourly space velocity -
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