Effect of promoter M(M=Cr, Zn, Y, La) on CuO/CeO2 catalysts for hydrogen production from steam reforming of methanol
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摘要: 采用顺序浸渍法制备了掺杂助剂M（M=Cr、Zn、Y、La）的CuO/CeO2催化剂，并利用XRF、XRD、BET、H2-TPR和XPS等手段对催化剂进行了表征，考察了不同助剂对CuO/CeO2催化剂结构、性质和性能的影响。结果表明，助剂的掺杂主要影响CuO/CeO2催化剂的CuO分散、催化剂的还原性质、CuO与CeO2间的相互作用和催化剂表面氧空穴含量。掺杂助剂Cr和Zn后，提高了CuO在催化剂表面的分散度，使CuO和CeO2间的相互作用加强，表面氧空穴增加，进而使得催化活性提高。而掺杂助剂Y和La后，降低了CuO在催化剂表面的分散度，使CuO和CeO2间的相互作用减弱，表面氧空穴减少，进而使得催化活性降低。其中，掺杂Cr助剂的催化剂催化性能较优，当反应条件为260 ℃，n（CH3OH）：n（H2O）=1：1.2，甲醇水蒸气气体空速为1760 h-1时，最终转化率可达100%，重整尾气中CO含量为0.15%，与CuO/CeO2催化剂相比，转化率提高了10%，重整尾气中CO含量降低了0.34%。Abstract: M/CuO/CeO2 (M=Cr, Zn, Y, La) catalyst was prepared by sequential impregnation method. The catalysts were characterized by XRF, XRD, BET, H2-TPR and XPS. The effects of different promoters on the structure and properties of CuO/CeO2 catalysts were investigated.The results show that the doping of promoters mainly affects the dispersion of CuO, the reduction properties of the catalyst, the interaction between CuO and CeO2, and the oxygen hole content on the surface of the catalyst. After doping additives Cr and Zn, improving the dispersion of CuO on catalysts, and the interaction between CuO and CeO2 strengthens, the surface oxygen holes increase, which in turn increases the catalytic activity. After doping the additives Y and La, decreasing the dispersion of CuO on catalysts, the interaction between CuO and CeO2 is weakened, and the surface oxygen holes are reduced, thus the catalytic activity is reduced. Among them, the catalyst doped with promoter Cr has better catalytic activity. When the reaction conditions are 260℃, n(CH3OH):n(H2O)=1:1.2 and the space velocity of methanol vapor gas is 1760 h-1, the final conversion can reach 100%, the CO content in reforming tail gas is 0.15%. Compared with CuO/CeO2 catalyst, the conversion rate is increased by 10%, and the CO content in reforming tail gas is reduced by 0.34%.
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Key words:
- auxiliaries /
- methanol steam reforming /
- hydrogen /
- carbon monoxide
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图 1 未掺杂助剂和掺杂不同助剂催化剂的XRD谱图
Figure 1 XRD spectra of catalysts undoped promoters and doped with different promoters
a: CuO/CeO2; b: Cr/CuO/CeO2; c: Zn/CuO/CeO2; d: Y/CuO/CeO2; e: La/CuO/CeO2
图 2 未掺杂助剂和掺杂不同助剂催化剂的H2-TPR谱图
Figure 2 H2-TPR spectra of catalysts undoped promoters and doped with different promoters
a: CuO/CeO2; b: Cr/CuO/CeO2; c: Zn/CuO/CeO2; d: Y/CuO/CeO2; e: La/CuO/CeO2
图 3 催化剂的Ce 3d XPS谱图
Figure 3 Ce 3d XPS spectra of catalyst
a: CuO/CeO2; b: Cr/CuO/CeO2; c: Zn/CuO/CeO2; d: Y/CuO/CeO2; e: La/CuO/CeO2
图 4 催化剂的Cu 2p XPS谱图
Figure 4 Cu 2p XPS spectra of catalyst
a: CuO/CeO2; b: Cr/CuO/CeO2; c: Zn/CuO/CeO2; d: Y/CuO/CeO2; e: La/CuO/CeO2
图 5 催化剂Cu LMM XPS谱图
Figure 5 XPS spectra of catalyst Cu LMM
a: CuO/CeO2; b: Cr/CuO/CeO2; c: Zn/CuO/CeO2; d: Y/CuO/CeO2; e: La/CuO/CeO2
图 6 催化剂的O 1s XPS谱图
Figure 6 O 1s XPS spectra of the catalysts
a: CuO/CeO2; b: Cr/CuO/CeO2; c: Zn/CuO/CeO2; d: Y/CuO/CeO2; e: La/CuO/CeO2
图 7 反应温度与催化剂性能的关联
Figure 7 Correlation between reaction temperature and catalyst performance
a: CuO/CeO2; b: Cr/CuO/CeO2; c: Zn/CuO/CeO2; d: Y/CuO/CeO2; e: La/CuO/CeO2; f: equil
图 8 不同反应温度下重整尾气中的摩尔CO含量
Figure 8 Molar CO content in reforming gas at different reaction temperatures
a: CuO/CeO2; b: Cr/CuO/CeO2; c: Zn/CuO/CeO2; d: Y/CuO/CeO2; e: La/CuO/CeO2; f: equil
表 1 不同助剂催化剂的元素含量
Table 1 Element content of catalysts with different auxiliaries
Catalyst Content of element w/% Cu Ce O Cr Zn Y La CuO/CeO2 7.9 73.4 18.7 - - - - Cr/CuO/CeO2 7.3 70.7 19.3 2.7 - - - Zn/CuO/CeO2 7.2 71.4 18.8 - 2.6 - - Y/CuO/CeO2 7.1 71.5 18.8 - - 2.6 - La/CuO/CeO2 7.3 71.4 18.6 - - - 2.7 
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表 2 催化材料的物化性质和产氢速率
Table 2 Physicochemical properties and hydrogen production rate of catalytic materials
Catalyst Specific surface area A/(m2·g-1) Pore volume v/(cm3·g-1) dCuO/nm Cu dispersiona/% Cu surface areaa A/(m2·g-1) H2 production rateb/(cm3·kg-1·s-1) CeO2 37.4 0.10 - - - - CuO/CeO2 21.9 0.09 29.9 15.3 8.8 379.7 Cr/CuO/CeO2 18.6 0.08 20.2 16.8 9.7 631.2 Zn/CuO/CeO2 28.2 0.11 22.5 16.5 9.5 521.8 Y/CuO/CeO2 18.6 0.08 25.4 14.1 8.1 282.5 La/CuO/CeO2 27.5 0.07 23.8 15.1 8.7 334.7 a: determined by N2O experiments; b: reaction conditions: 280 ℃, n(CH3OH):n(H2O)=1.2:1, GHSV=1760 h-1
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表 3 催化剂的还原峰位置
Table 3 Reduction peak position of catalyst
Catalyst Peak position t/ ℃ peak α peak β peak γ CuO/CeO2 178 222 249 Cr/CuO/CeO2 150 205 235 Zn/CuO/CeO2 160 204 217 Y/CuO/CeO2 247 264 285 La/CuO/CeO2 203 252 272
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表 4 催化剂的Ce 3d和Cu LMM XPS曲线拟合结果
Table 4 Fitting results of Cu LMM and Ce 3d XPS curves of catalysts
Catalyst Ce3+/(Ce3++Ce4+)/% Cu+/(Cu++Cu2+)/% CuO/CeO2 18.5 43.9 Cr/CuO/CeO2 34.4 74.9 Zn/CuO/CeO2 31.5 46.4 Y/CuO/CeO2 13.5 31.5 La/CuO/CeO2 15.9 40.2
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