Cu-Al spinel as a sustained release catalyst for H2 production from methanol steam reforming:Effects of different copper sources
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摘要: 以拟薄水铝石为铝源，氢氧化铜、乙酸铜和硝酸铜等为铜源，采用固相法合成Cu-Al尖晶石催化剂。采用TG-MS、XRD、H2-TPR、BET和XANES等表征技术，对合成过程、产物的物相、还原性质及表层结构进行研究，并考察了甲醇重整制氢的缓释催化性能。结果表明，三种铜源都得到尖晶石固溶体，其晶粒粒径相差不大，但其比表面积（25.4-65.9 m2/g）、孔容（0.213-0.434 cm3/g）、表面结构（Cu的分布）以及还原性能有明显的差别，从而导致不同的缓释催化行为。在甲醇重整反应过程中，铜铝缓释催化剂通过反应条件下还原释放活性铜物种而起催化作用。以氢氧化铜合成的催化剂活性高，反应稳定性好，反应后生成的Cu粒子最小（6.6 nm），其表现出优异的催化性能。Abstract: Cu-Al spinel catalysts were synthesized by the solid-state reaction method using pseudo-boehmite as the Al source and hydroxides, acetates and nitrates of copper as the Cu source. Several techniques such as TG-MS, XRD, H2-TPR, BET and XANES were employed for the exploration of the synthetic process, phase composition, reduction behaviors and surface structure of the catalysts. Moreover, the catalytic properties for methanol steam reforming (MSR) of these catalysts were evaluated. The obtained results showed that spinel solid solution can be successfully synthesized with the three different Cu sources. The synthesized spinels showed little difference in crystalline size, but their specific surface area (25.4-65.9 m2/g), pore volume (0.213-0.434 cm3/g), surface structure (distribution of Cu) and reduction properties were quite different, which led to different catalytic behavior and performance. During the methanol steam reforming reaction, active Cu species can be released from Cu-Al spinel structure. The catalyst synthesized from copper(Ⅱ) hydroxide shows excellent catalytic performance for MSR as it generates the smallest Cu particles (6.6 nm).
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Key words:
- solid-state reaction method /
- solid solution /
- methanol steam reforming
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图 1 前驱体的TG-MS谱图
Figure 1 Thermogravimetric mass spectrometry (TG-MS) profiles of the precursors
图 5 不同铜源制备的铜铝尖晶石催化剂的H2-TPR谱图
Figure 5 H2-TPR patterns of the Cu-Al spinel catalysts from different Cu sources
图 6 催化剂的还原度随反应温度的变化
Figure 6 Reduction degree of catalysts with the change of reduction temperature
图 7 不同催化剂上甲醇转化率随反应时间的变化
Figure 7 Change of methanol conversion vs time for three different catalyst
图 8 反应后催化剂的XRD谱图
Figure 8 XRD patterns of tested catalysts
a: CuHAl-950-t; b: CuAAl-950-t; c: CuNAl-950-t
表 1 催化剂的特征参数
Table 1 Characteristic parameter of fresh and tested catalysts
Fresh catalyst CuHAl-950 CuAAl-950 CuNAl-950 Cu source Cu(OH)2 Cu(CH3COO)2·H2O Cu(NO3)2·3H2O dspinel/ nm[a] 12.7 12.4 11.3 BET surface area A/ (m2·g-1) 65.9 33.8 25.4 Pore volume v/(cm3·g-1) 0.434 0.213 0.289 X spinel / %[b] 81.3 79.1 93.7 x in Cu1-3xVxAl2+2xO4 0.129 0.134 0.104 After MSR CuHAl-950-t CuAAl-950-t CuNAl-950-t dCu-after MSR / nm[c] 6.6 9.2 20.2 Cu0 surface area A/(m2 ·g-1)[d] 183.9 146.1 94.7 RD/%[e] 88.7 85.9 66.8 [a]: the crystallite size of spinel was calculated by the Scherrer equation with the XRD patterns (Figure 2);
[b]: the molar ratio of Cu in the Cu-Al spinel phase to total Cu as derived from H2-TPR (Figure 5);
[c]: Cu crystalline size of tested catalyst was calculated by the Scherrer equation with XRD patterns (Figure 8);
[d]: Cu surface area of tested catalyst was measured by N2O chemisorption method;
[e]: the releasing degree (RD) of Cu from spinel after catalytic testing was calculated by using H2-TPR data of tested samples
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