Effect of Mg content in Ni/MgAl2O4 catalysts on catalytic performance during methane dry reforming reaction
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摘要: 甲烷干重整反应是CO2和CH4综合利用的有效途径，但此反应温度高，催化剂易因积碳和烧结而失活。本研究采用溶剂蒸发自组装法制备了不同Mg含量的镁铝尖晶石（MgAl2O4）载体，随后负载了金属Ni，并将该催化剂（Ni/x-MAO）应用于甲烷干重整制合成气反应。结合X射线衍射、氮气物理吸脱附和透射电镜等表征对催化剂的结构性质进行了分析，发现适量Mg的加入（10-15%）有利于提高载体的比表面积，并形成耐高温的有序介孔结构。该结构可以将Ni颗粒限域在孔道内，有利于形成高分散、小晶粒的活性物种，其在高温反应下不易烧结。同时，H2-TPR和XPS结果表明，10-15%的Mg含量有利于增强Ni与MgAl2O4的金属-载体相互作用，可以有效抑制Ni烧结，且其表面的活性氧物种可以有效抑制积碳生成。在性能评价中，10-15%的Mg含量的Ni/MgAl2O4催化剂呈现出优异的CH4和CO2转化率，在180 h的长周期活性评价期间，Ni/15-MAO催化剂的CH4转化率和CO2转化率分别保持在92.6%和92.5%左右，同时积碳量仅为0.89%，且反应后的Ni颗粒尺寸变化不大。
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关键词:
- 甲烷干重整反应 /
- 有序介孔MgAl2O4 /
- 镍基催化剂
Abstract: Methane dry reforming reaction is a promising route for the valorization of both CO2 and CH4. However, the catalysts usually suffered from the coking deactivation and the sintering of active phase under the harsh reaction conditions. In this paper, the Mg-Al spinel support with different Mg content prepared by the solvent evaporation-induced self-assembly method was investigated. With this support, Ni/MgAl2O4 was used as the catalyst for methane dry reforming to syngas. XRD, BET and TEM results showed that the addition of appropriate amount of magnesium (10-15%) was beneficial to the formation of highly stable ordered mesoporous magnesia spinel support with large specific surface area, which can confine the Ni particles in the pore structure and thus enhance the nickel dispersion and improve the resistance of coke formation under high temperature. H2-TPR and XPS analysis indicated the addition of 10-15% magnesium can promote the interaction between Ni and MgAl2O4, inhibiting the agglomeration of Ni and the coke formation with the active surface-adsorbed oxygen species. Detailed activity tests showed that Ni/MgAl2O4 catalysts with 10-15% magnesium content has high CH4 and CO2 conversion. During the long-term test for 180 h, the Ni/15-MAO catalyst exihibited the CH4 and CO2 conversions of 92.6% and 92.5%, respectively. The coke deposition percentage was only 0.89% and the grain size of Ni was maintained after reaction.1) # 共同第一作者 -
图 1 新鲜催化剂的（a）XRD谱图；（b）小角XRD谱图；（c）氮气物理吸脱附曲线和（d）孔径分布
Figure 1 (a) XRD patterns; (b) small-angel XRD patterns; (c) N2 adsorption-desorption isotherms and (d) pore size distributions of the fresh catalysts
图 3 还原催化剂的TEM图及其相应的金属颗粒尺寸分布：（a）Ni/10-MAO；（b）Ni/15-MAO；（c） Ni/20-MAO；（d）Ni/25-MAO
Figure 3 TEM images of the reduced catalysts and the relevant metal size distribution: (a) Ni/10-MAO; (b) Ni/15-MAO; (c) Ni/20-MAO; (d) Ni/25-MAO
图 4 还原催化剂的XPS谱图：（a）Ni 2p 和（b）O 1s
Figure 4 XPS spectra of the reduced catalysts: (a) Ni 2p and (b) O 1s
图 5 不同反应温度下的催化性能曲线：（a） CH4转化率；（b）CO2转化率和（c）H2/CO比；反应条件：CH4/CO2=1, GHSV=120000 mL·g−1·h−1, 1 atm.
Figure 5 The catalytic performance curves of the (a) CH4 conversion; (b) CO2 conversion and (c) H2/CO ratio at various reaction temperatures; Reaction conditions: CH4/CO2=1, GHSV=120000 mL·g−1·h−1, 1 atm.
图 6 反应后催化剂的TEM图及其相应的金属颗粒尺寸分布：（a）Ni/10-MAO；（b）Ni/15-MAO；（c）Ni/20-MAO；（d）Ni/25-MAO.
Figure 6 TEM images of the spent catalysts and the relevant metal size distribution: (a) Ni/10-MAO; (b) Ni/15-MAO; (c) Ni/20-MAO; (d) Ni/25-MAO
图 7 （a）Ni/15-MAO催化剂的稳定性测试；（b）反应后Ni/15-MAO催化剂的TEM图及其相应的金属颗粒尺寸分布
Figure 7 (a) Stability test of the Ni/15-MAO catalyst; (b) TEM image of the spent Ni/15-MAO catalyst and the relevant metal size distribution
表 1 新鲜催化剂的孔结构参数
Table 1 Pore structure parameters of the fresh catalysts
Catalyst BET surface area S/(m2·g−1) Total pore volume v/(cm3·g−1) Average pore size d/nm Ni/10-MAO 247.3 0.628 10.2 Ni/15-MAO 203.1 0.471 9.3 Ni/20-MAO 181.2 0.424 9.4 Ni/25-MAO 177.1 0.394 8.9 
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表 2 还原催化剂的XPS分析数据
Table 2 XPS analysis results of the reduced catalysts
Catalyst Ni 2p O 1s Ni content (%)a Ni0/(Ni0 + Ni2 + ) (%) Oα (%) Oβ (%) Ni/10-MAO 1.56 19.6 46.5 53.5 Ni/15-MAO 1.80 13.1 45.3 54.8 Ni/20-MAO 5.44 N.D. 56.9 43.1 Ni/25-MAO 5.73 N.D. 54.5 45.5 a 催化剂表面Ni含量
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