氨分解制氢棒状La x Ce1-x O y 负载Ru催化剂

doi:10.16085/j.issn.1000-6613.2022-0392

摘要/Abstract

摘要：

氨分解得到的H₂不含CO _x 、SO _x 、NO _x 等有害物质，是其他所有含碳资源为原料制氢所不能比拟的。本文采用无模板水热法制备了一系列棒状载体，并采用沉积沉淀法制备了Ru/La _x Ce_1-_x O _y 催化剂，考察了制备方法、催化剂组成对性能的影响，并通过扫描电镜（SEM）、X射线衍射（XRD）、BET、H₂-程序升温还原（TPR）和CO₂-程序升温脱附（TPD）进行了表征。结果表明，La₂O₃掺杂量为40%的Ru/La_0.4Ce_0.6O_1.8催化剂在常压、7800h^-1、450℃下氨分解转化率为98%。该催化剂活性高归因于部分还原的CeO_2-_x 对Ru的供电子性能和Ru/La_0.4Ce_0.6O_1.8催化剂表面的强碱性增加了对Ru活性位的给电子能力。同时考察了K₂O含量的影响，最优的催化剂为Ru-2%K/La_0.4Ce_0.6O_1.8，在400℃、7800h^-1氨气转化率可以达到93%。结果表明Ru-2%K/La_0.4Ce_0.6O_1.8可以作为一种新型高效氨分解催化剂，为工业化应用提供了可能，具有良好的发展前景。

关键词: Ru催化剂, 制氢, 载体, 复合材料, 活性, 固定床

Abstract:

The hydrogen by ammonia decomposition does not contain CO _x, SO _x, NO _x and other harmful substances, which is advantageous to other carbon-containing hydrogen production methods. In this paper, a series of rod-like supports were prepared by a template-free hydrothermal method, and Ru/La _x Ce_1-_x O _y catalysts were prepared by a deposition precipitation method. The effects of preparation method and catalyst composition on the decomposition performance were investigated and the catalysts were characterized by SEM, XRD, BET, H₂-TPR and CO₂-TPD. The results showed that the ammonia decomposition rate of Ru/La_0.4Ce_0.6O_1.8 catalyst with 40% La₂O₃ doping was 98% at normal pressure, 7800h^-1and 450℃. The high activity was attributed to the electro donating to metal Ru by the partially reduced CeO_2-_x and the strong basicity of the Ru/La_0.4Ce_0.6O_1.8 catalyst surface. At the same time, the influence of K₂O was investigated, and the optimal catalyst was Ru-2%K/La_0.4Ce_0.6O_1.8, which gave an ammonia conversion of 93% at 400℃, 7800h^-1, allowing it to be used as a promising new type high-efficiency ammonia decomposition catalyst in industry.

Key words: Ru catalyst, hydrogen production, support, composites, reactivity, fixed-bed

中图分类号:

O643.36

张姗, 刘化章. 氨分解制氢棒状La _x Ce_1-_x O _y 负载Ru催化剂[J]. 化工进展, 2022, 41(12): 6350-6357.

ZHANG Shan, LIU Huazhang. Rod La _x Ce_1-_x O _y supported Ru catalyst for hydrogen production by ammonia decomposition[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6350-6357.

图/表 12

表1 合成不同La2O3掺杂载体所需反应物的用量[Ce(NO3)3·6H2O固定1.736g]

La₂O₃掺杂量/%	La(NO₃)₃·6H₂O质量/g
0	0
10	0.192
30	0.742
40	1.154
50	1.732

图1 Ru/La x Ce1-x O y 催化剂的氨分解转化率和400℃下，Ru//La x Ce1-x O y 催化剂氨分解转化率与La2O3含量的关系

图2 载体的SEM图

图3 Ru//La x Ce1-x O y 催化剂的XRD图谱和Ru//La x Ce1-x O y 在28.6°左右放大的XRD图谱

表2 Ru/La x Ce1-x O y 催化剂的平均粒径

La₂O₃掺杂量/%	平均粒径/nm
0	7.8
10	7.4
30	5.2
40	3.7
50	2.1

表3 Ru/La x Ce1-x O y 催化剂的物理结构参数

样品	比表面积/m²·g^-1	总孔容/cm³·g^-1	平均孔径/nm
Ru/CeO₂	112.12	0.25	8.40
Ru/La_0.1Ce_0.9O_1.95	101.79	0.63	22.78
Ru/La_0.3Ce_0.7O_1.85	90.88	0.58	19.53
Ru/La_0.4Ce_0.6O_1.8	85.90	0.28	11.25
Ru/La_0.5Ce_0.5O_1.75	80.54	0.28	11.14

图4 不同催化剂的N2吸附脱附等温线和孔径分布曲线

图5 Ru/La x Ce1-x O y 催化剂的H2-TPR

图6 Ru/La x Ce1-x O y 催化剂的CO2-TPD图

表4 K2O含量对Ru/La0.4Ce0.6O1.8催化剂氨分解活性的影响

K₂O含量/%	350℃	400℃	450℃	500℃
0	24.48	71.05	98.77	99.41
2	50.26	93.81	99.23	99.34
4	48.09	93.19	99.38	99.68
6	48.49	92.61	99.37	99.56
10	40.18	84.44	99.11	99.39

图7 Ru-2%K/La0.4Ce0.6O1.8催化剂在450℃ NH3转化率随时间的变化

图8 空速对Ru-2%K/La0.4Ce0.6O1.8催化剂NH3分解性能的影响

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