Preparation of NiZnCe composite oxide and its catalytic performance for dehydrogenation of n-butane

doi:10.11949/0438-1157.20201041

Abstract

Abstract:

The nickel zinc cerium (NiZnCe) composite oxide catalyst was prepared by the sol-gel method, and the effects of Zn and Ce content in the NiZnCe composite oxide catalyst on the performance of n-butane oxidative dehydrogenation were investigated. The research results showed that the conversion rate and olefin selectivity of NiZn_0.5Ce_0.3 catalyst were higher. A series of characterization methods, such as H₂-TPR, XPS and TPRO, were used to reveal the influence of different steps of the oxygen movement cycle in the catalyst on the performance of the catalyst. The results showed that the introduction of Ce element had a greater impact on the oxygen mobility of the catalyst, and the catalyst performance was positively correlated with the oxygen capacity (the amount of oxygen in the catalyst participating in the reaction). In addition, the interaction between Ni and Ce led to an increase in the cation valence and acceptable electron capacity of Ni. Active Ni became easier to adsorb active oxygen species, and the cyclic reciprocating reaction between metal and oxygen was more active.

Key words: nickel zinc cerium, catalyst, oxidation, selectivity, n-butane, oxygen mobility, oxygen capacity

摘要：

采用溶胶凝胶法制镍锌铈（NiZnCe）复合氧化物催化剂，分别考察了NiZnCe复合氧化物催化剂中Zn和Ce含量对正丁烷氧化脱氢性能的影响。研究结果表明，NiZn_0.5Ce_0.3催化剂的转化率和烯烃选择性较高。采用H₂-TPR、XPS及TPRO的表征方法来揭示催化剂中氧移动循环的不同步骤对催化剂性能的影响。表征结果显示，Ce元素的引入对催化剂的氧移动性产生较大的影响，且催化剂性能与氧容量（参与反应的催化剂中的氧量）呈正相关。此外，Ni与Ce的相互作用导致了Ni阳离子化合价和可接受电子能力的提高，活性Ni更容易吸附活性氧物种，金属与氧气的循环往复反应更活泼。

关键词: 镍锌铈, 催化剂, 氧化, 选择性, 正丁烷, 氧移动性, 氧容量

CLC Number:

TQ 426.8

WANG Lian, WAN Chao, CHENG Dangguo, CHEN Fengqiu, ZHAN Xiaoli. Preparation of NiZnCe composite oxide and its catalytic performance for dehydrogenation of n-butane[J]. CIESC Journal, 2021, 72(1): 534-542.

王炼, 万超, 程党国, 陈丰秋, 詹晓力. NiZnCe复合氧化物的制备及其催化氧化正丁烷脱氢性能[J]. 化工学报, 2021, 72(1): 534-542.

Figures/Tables 9

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催化剂	正丁烷转化率/%	选择性/%
催化剂	正丁烷转化率/%	二氧化物	C₁~C₃	反-2-丁烯	顺-2-丁烯	1-丁烯	异丁烯	1,3-丁二烯
NiO	0	0	0	0	0	0	0	0
NiZn₁	10.5	74.0	4.5	5.0	4.0	10.4	0.2	1.9
NiZn₃	10.4	62.2	18.4	4.9	3.4	8.7	0.2	2.2
NiZn₅	7.7	51.4	24.8	6.4	4.3	11.7	0.3	1.1
NiZn_0.5	11.8	57.0	16.4	6.2	4.5	11.1	0.2	4.6
NiZn_0.5Ce_0.2	22.0	66.1	2.7	5.4	4.7	12.7	0.08	8.3
NiZn_0.5Ce_0.3	23.9	64.3	3.1	4.1	3.3	8.5	0.07	16.6
NiZn_0.5Ce_0.5	19.2	59.0	8.7	5.3	3.4	6.9	0.1	16.6
NiZn_0.5Ce₁	18.3	61.5	9.4	5.3	3.3	6.2	0.1	14.2

催化剂	正丁烷转化率/%	选择性/%
催化剂	正丁烷转化率/%	二氧化物	C₁~C₃	反-2-丁烯	顺-2-丁烯	1-丁烯	异丁烯	1,3-丁二烯
NiO	0	0	0	0	0	0	0	0
NiZn₁	10.5	74.0	4.5	5.0	4.0	10.4	0.2	1.9
NiZn₃	10.4	62.2	18.4	4.9	3.4	8.7	0.2	2.2
NiZn₅	7.7	51.4	24.8	6.4	4.3	11.7	0.3	1.1
NiZn_0.5	11.8	57.0	16.4	6.2	4.5	11.1	0.2	4.6
NiZn_0.5Ce_0.2	22.0	66.1	2.7	5.4	4.7	12.7	0.08	8.3
NiZn_0.5Ce_0.3	23.9	64.3	3.1	4.1	3.3	8.5	0.07	16.6
NiZn_0.5Ce_0.5	19.2	59.0	8.7	5.3	3.4	6.9	0.1	16.6
NiZn_0.5Ce₁	18.3	61.5	9.4	5.3	3.3	6.2	0.1	14.2

催化剂	原子比^①			S_BET/(m²·g^-1)	孔容/(cm³·g^-1)
催化剂	Ni	Zn	Ce	S_BET/(m²·g^-1)	孔容/(cm³·g^-1)
NiO	1	0	0	2.7	0.008
NiZn₁	1	0.97	0	2.4	0.009
NiZn₃	1	3.19	0	2.9	0.011
NiZn₅	1	5.09	0	3.1	0.010
NiZn_0.5	1	0.54	0	3.3	0.013
NiZn_0.5Ce_0.2	1	0.56	0.15	8.5	0.041
NiZn_0.5Ce_0.3	1	0.55	0.28	6.7	0.028
NiZn_0.5Ce_0.5	1	0.53	0.47	7.8	0.046
NiZn_0.5Ce₁	1	0.52	0.83	9.1	0.049

催化剂	原子比^①			S_BET/(m²·g^-1)	孔容/(cm³·g^-1)
催化剂	Ni	Zn	Ce	S_BET/(m²·g^-1)	孔容/(cm³·g^-1)
NiO	1	0	0	2.7	0.008
NiZn₁	1	0.97	0	2.4	0.009
NiZn₃	1	3.19	0	2.9	0.011
NiZn₅	1	5.09	0	3.1	0.010
NiZn_0.5	1	0.54	0	3.3	0.013
NiZn_0.5Ce_0.2	1	0.56	0.15	8.5	0.041
NiZn_0.5Ce_0.3	1	0.55	0.28	6.7	0.028
NiZn_0.5Ce_0.5	1	0.53	0.47	7.8	0.046
NiZn_0.5Ce₁	1	0.52	0.83	9.1	0.049

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