NiZnCe复合氧化物的制备及其催化氧化正丁烷脱氢性能

doi:10.11949/0438-1157.20201041

化工学报 ›› 2021, Vol. 72 ›› Issue (1): 534-542.DOI: 10.11949/0438-1157.20201041

• 催化、动力学与反应器 • 上一篇下一篇

NiZnCe复合氧化物的制备及其催化氧化正丁烷脱氢性能

王炼^1,²(),万超^1,^3,⁴,程党国^1,²(),陈丰秋^1,²,詹晓力^1,²

^1.浙江大学化学工程与生物工程学院，浙江省化工高效制造技术重点实验室，浙江杭州 310029
^2.浙江大学衢州研究院，浙江衢州 324000
^3.安徽工业大学化学与化工学院，安徽马鞍山 243000
^4.安徽海德化工科技有限公司，安徽马鞍山 243000

收稿日期:2020-08-04 修回日期:2020-10-03 出版日期:2021-01-05 发布日期:2021-01-05
通讯作者: 程党国
作者简介:王炼（1995—），女，硕士研究生，wwanglian@163.com
基金资助:
国家重点研发计划项目(2016YFA0202900);国家自然科学基金项目(21622606);浙江省自然科学基金杰出青年科学基金项目(LR18B060001);安徽省科技重大专项(201903a05020055)

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

WANG Lian^1,²(),WAN Chao^1,^3,⁴,CHENG Dangguo^1,²(),CHEN Fengqiu^1,²,ZHAN Xiaoli^1,²

^1.Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310029, Zhejiang, China
^2.Institute of Zhejiang University-Quzhou, Quzhou 324000, Zhejiang, China
^3.School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma’anshan 243000, Anhui, China
^4.Anhui Haide Chemical Technology Co. , Ltd. , Ma’anshan 243000, Anhui, China

Received:2020-08-04 Revised:2020-10-03 Online:2021-01-05 Published:2021-01-05
Contact: CHENG Dangguo

摘要/Abstract

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

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

中图分类号:

TQ 426.8

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.

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.

图/表 9

表1 NiZnx及NiZn0.5Cey氧化物催化剂上正丁烷转化率以及产物选择性

Table 1 n-Butane conversion and products selectivity over NiZnx and NiZn0.5Cey oxide catalyst

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

图1 NiZnx(a)和NiZn0.5Cey(b)催化剂的XRD谱图

Fig.1 XRD patterns of NiZnx(a), and NiZn0.5Cey (b) catalysts

表2 NiZnx及NiZn0.5Cey氧化物催化剂的元素组成、比表面积和孔容

Table 2 Atomic ratio, BET surface area, total pore volume of NiZnx and NiZn0.5Cey oxide catalysts

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

图2 不同铈含量的NiZn0.5Cey氧化物催化剂的H2-TPR图

Fig.2 H2-TPR profiles of NiZn0.5Cey with different cerium contents

图3 NiZn0.5Cey氧化物催化剂的 TPRO 图

Fig.3 TPRO profiles of NiZn0.5Cey oxide catalysts

图4 NiZn0.5Ce0.3氧化物催化剂的 TPRO-MS 信号图

Fig.4 MS signals of TPRO of NiZn0.5Ce0.3 oxide catalyst[m/z =32 (?O2), 44(?CO2) were recorded during TPRO analysis]

图5 NiZn0.5Cey氧化物催化剂的O1s谱

Fig.5 The O1s spectrum of NiZn0.5Cey oxide catalysts

图6 NiZn0.5Cey氧化物催化剂的Ni2p3/2谱

Fig.6 The Ni2p3/2 spectra of NiZn0.5Cey oxide catalysts

图7 NiZn0.5Ce0.3氧化物催化剂的反应机理和氧迁移机理

Fig.7 Reaction mechanism and oxygen migration mechanism of NiZn0.5Ce0.3 oxide catalysts

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NiZnCe复合氧化物的制备及其催化氧化正丁烷脱氢性能

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

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