The Preparation of LaAl0.5Ni0.5O3 Perovskite and Its Catalytic Performance in Methane Dry Reforming
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摘要: 采用硬模板法制备比表面积大的介孔LaAl1-xNixO3钙钛矿催化剂，将其用于碳中和甲烷干重整领域，研究不同温度下的反应活性。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)、N2吸附-脱附(BET)、H2程序升温还原(H2-TPR)、热重分析(TGA)对制备的催化剂进行表征。结果表明：LaAl0.5Ni0.5O3催化剂在反应过程中表现出了最优异的活性与稳定性。在反应温度为750 ℃，空速GHSV=36 000 mL/(g·h)的反应条件下, CH4与CO2的转化率分别达到69.8%和81.5%，经25 h稳定性测试后CH4与CO2的转化率仅分别降低2.7%和3.3%。这是由于在H2-Ar混合气还原过程中，LaAl0.5Ni0.5O3催化剂获得了比LaAl0.7Ni0.3O3催化剂更多的Ni活性位点，同时获得了比LaAl0.3Ni0.7O3催化剂更优异的抗烧结、抗积碳性能。Abstract: The hard template method was used to prepare the mesoporous LaAl1-xAlxO3 perovskite catalyst with a large surface area, which was used for carbon-neutral methane dry reforming for reaction activity test at different temperatures. With scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), N2 adsorption and desorption (BET), H2 temperature programmed reduction (H2-TPR), thermogravimetric analysis (TGA) and other methods, the as-prepared catalyst was characterized. The results showed that the LaAl0.5Ni0.5O3 catalyst exhibited the most excellent activity and stability during the reaction, the initial activity of CH4 and CO2 in the LaAl0.5Ni0.5O3 catalyst reached 69.8% and 81.5% respectively under the conditions of reaction temperature of 750 ℃ and space velocity GHSV=36 000 mL/(g·h). And the CH4 and CO2 activity of the LaAl0.5Ni0.5O3 catalyst reduced by 2.7% and 3.3% respectively after the 25 h stability test. The reason was that the LaAl0.5Ni0.5O3 catalyst obtained more Ni active sites than the LaAl0.7Ni0.3O3 catalyst and the LaAl0.5Ni0.5O3 catalyst had more favorable anti-sintering and anti-carbon deposition ability than the LaAl0.3Ni0.7O3 catalyst.
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图 1 LaAl1-xNixO3钙钛矿催化剂的合成路线
Figure 1. The route of LaAl1-xNixO3 perovskite catalyst synthesis
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图 2 新制的LaAlO3-C与LaAlO3钙钛矿SEM图
Figure 2. The SEM images of LaAlO3-C and LaAlO3 perovskite prepared
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图 3 所有新制钙钛矿的N2吸附-脱附等温图
Figure 3. The N2 adsorption-desorption isotherms of all perov-skites prepared
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图 4 新制钙钛矿和还原后LaAl1-xNixO3钙钛矿的XRD图谱
Figure 4. The XRD patterns of the as-prepared and reduced LaAl1-xNixO3 perovskites
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图 5 新制LaAl1-xNixO3催化剂的H2-TPR曲线
Figure 5. The H2-TPR curves of LaAl1-xNixO3 catalysts prepared
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图 6 不同温度下催化剂对CH4和CO2的催化活性
Figure 6. The catalytic activity of each catalyst for CH4 and CO2 at different temperatures
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图 8 催化剂在稳定性测试反应前后的TEM图、XRD图谱及TG曲线
Figure 8. The TEM images, XRD patterns and TG curves of the catalysts before and after stability test
表 1 不同样品的物理性质
Table 1 The physical characteristics of different samples
样品 比表面积/(m2·g-1) 孔容积/(cm3·g-1) 孔径/nm D0/nm D1/nm LaAlO3-C 5.3 0.041 30.5 — — LaAlO3 137.1 0.274 8.0 — — LaAl0.7Ni0.3O3 98.3 0.288 11.7 13.5 — LaAl0.5Ni0.5O3 93.7 0.251 10.7 14.2 15.5 LaAl0.3Ni0.7O3 85.6 0.223 10.4 17.8 21.6 注：D0为LaAl1-xNixO3钙钛矿还原后的Ni粒径; D1为LaAl1-xNixO3钙钛矿稳定性测试后的Ni粒径。 
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表 2 LaAl0.5Ni0.5O3催化剂与各种同类催化剂的性能比较
Table 2 The performance of various catalysts for methane dry reforming
样品 气体组分 GHSV/(mL·g-1·h-1) T/℃ 转化率/% t/h 来源 CH4 CO2 La(Co0.1Ni0.9)0.5Fe0.5O3 V(CH4)∶V(CO2)=1∶1 12 000 750 70 80 30 [25] La0.4Ce0.6Ni0.5O0.5O3 V(CH4)∶V(CO2)=1∶1 12 000 750 62 72 25 [26] 10%NiO/MgO V(CH4)∶V(CO2)=1∶1 30 000 750 63 75 30 [27] Ni-ATP@Ce V(CH4)∶V(CO2)=1∶1 18 000 700 58 74 6 [28] LaAl0.5Ni0.5O3 V(CH4)∶V(CO2)∶V(N2)=25∶25∶10 36 000 750 69 81 25 本文 注：空速(GHSV): 反应气体每小时通过每克催化剂的体积。
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