Ce改性CuZnAl催化剂上仲丁醇脱氢制备甲乙酮

李英; 马会霞; 周峰; 苑兴洲; 张磊; 张健

doi:10.19906/j.cnki.JFCT.2021005

Ce改性CuZnAl催化剂上仲丁醇脱氢制备甲乙酮

doi: 10.19906/j.cnki.JFCT.2021005

李英¹,
马会霞²,
周峰²,
苑兴洲¹,
张磊¹,
张健^1, ,

1.
辽宁石油化工大学，辽宁抚顺 113001
2.
中国石油化工股份有限公司大连石油化工研究院，辽宁大连 116000

详细信息

通讯作者:
E-mail: zhangjian_lnpu@163.com

中图分类号: O643
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出版历程
- 收稿日期: 2020-08-24
- 修回日期: 2020-10-01
- 刊出日期: 2021-01-29

Performance of Ce-modified CuZnAl catalyst in the dehydrogenation of sec-butanol to methyl ethyl ketone

1.
Liaoning Petrochemical University, Fushun 113001, China
2.
Dalian Research Institute of Petroleum and Petrochemicals, Dalian 116000, China

摘要

摘要: 采用共沉淀法制备了CuZnAl催化剂，并通过浸渍法将不同含量Ce引入到CuZnAl催化剂中，将其用于仲丁醇（SBA）脱氢制甲乙酮（MEK），研究了Ce改性对其催化性能的影响。结果表明，Ce的引入可以促使CuZnAl催化剂中Zn物种和Al物种发生反应，生成尖晶石（CuAl₂O₄）结构，有利于提高其催化稳定性；同时引入Ce能降低催化剂晶粒尺寸、提高CuO和ZnO的分散度，并使催化剂中Cu²⁺含量提高、还原温度降低、还原后催化剂中活性组分Cu⁰含量增加。Ce改性后的8%-Ce-CuZnAl催化剂对仲丁醇脱氢具有良好的活性，在240 °C、质量空速为5 h⁻¹的条件下，SBA转化率达91.4%，MEK收率为87.74%；而且在100 h内催化活性稳定，SBA转化率保持在92%左右、MEK收率保持在88%左右。
- CuZnAl催化剂 /
- 脱氢 /
- 仲丁醇 /
- 甲乙酮 /
- Ce改性
Abstract: The CuZnAl catalyst prepared by co-precipitation was further modified with different contents of Ce through impregnation and used in the dehydrogenation of sec-butanol (SBA) to methyl ethyl ketone (MEK); the effect of Ce modification on the performance of CuZnAl catalyst was investigated. The results illustrate that the introduction of Ce in CuZnAl can promote the formation of CuAl₂O₄ spinel and thus improve the stability of Ce-modified CuZnAl catalyst; meanwhile, Ce is also conducive to reducing the grain size, enhancing the dispersion of CuO and ZnO, lowering the reduction temperature, and increasing the content of Cu²⁺ and consequently the content of active Cu⁰ species upon reduction. Over the Ce-modified 8%-Ce-CuZnAl catalyst, the conversion of SBA reaches 91.4% under 240 °C and a mass space velocity of 5 h⁻¹, with a selectivity of 96% to MEK; during the 100 h reaction test, the SBA conversion keeps at about 92%, with the selectivity to MEK at about 96%, demonstrating excellent stability of the Ce-modified CuZnAl catalyst.
- CuZnAl catalyst /
- dehydrogenation /
- sec-butanol /
- methyl ethyl ketone /
- Ce modification

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图 1 CuZnAl基体和不同Ce含量Ce-CuZnAl催化剂的XRD谱图

Figure 1 XRD patterns of the CuZnAl matrix and Ce-CuZnAl catalysts with different Ce contents

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图 2 CuZnAl催化剂和Ce-CuZnAl催化剂的H₂-TPR谱图

Figure 2 H₂-TPR profiles of the CuZnAl and 8%-Ce-CuZnAl catalysts

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图 3 CuZnAl和Ce-CuZnAl催化剂N₂吸附-脱附等温线

Figure 3 N₂ adsorption-desorption isotherms of the CuZnAl and Ce-CuZnAl catalysts

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图 4 CuZnAl和Ce-CuZnAl催化剂的XPS谱图

Figure 4 XPS spectra of the CuZnAl and Ce-CuZnAl catalysts

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图 5 不同Ce含量的Ce-CuZnAl催化剂催化SBA脱氢制MEK的性能曲线

Figure 5 Performance of the Ce-CuZnAl catalysts with different Ce contents in the dehydrogenation of SBA to MEKa: MEK selectivity; b: SBA conversion; c: MEK yield reaction conditions: atmospheric pressure, 240 °C, LHSV = 5 h⁻¹

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图 6 不同温度对SBA脱氢制MEK的影响柱状图

Figure 6 Influence of reaction temperature on the dehydrogenation of SBA to MEK reaction conditions: atmospheric pressure, LHSV = 5 h⁻¹

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图 7 不同质量空速对SBA脱氢制MEK的影响

Figure 7 Influence of mass space velocity on the dehydrogenation of SBA to MEK a: MEK selectivity; b: SBA conversion; c: MEK yield reaction conditions: atmospheric pressure, 240 °C, LHSV = 2.5–15 h⁻¹

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图 8 SBA脱氢制MEK的稳定性

Figure 8 Stability of the 8%-Ce-CuZnAl catalyst in the dehydrogenation of SBA to MEK a: MEK selectivity; b: SBA conversion; c: MEK yield reaction conditions: atmospheric presuure, 240 °C, LHSV = 5 h⁻¹

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表 1 CuZnAl and 8%-Ce-CuZnAl催化剂的结构参数

Table 1 Structural parameters of CuZnAl and 8%-Ce-CuZnAl catalysts

Sample Pore diameter
d/nm Pore volume
v/(cm³·g⁻¹) A_BET/
(m²·g⁻¹)

CuZnAl 7 0.200 66
8%-Ce-CuZnAl 12 0.241 79

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表 2 CuZnAl和Ce-CuZnAl催化剂的表面元素组成

Table 2 Surface element composition of the CuZnAl and Ce-CuZnAl catalysts

Catalyst Element composition w/%
Cu Zn Al

CuZnAl 7.65 6.32 23.11
8%-Ce-CuZnAl 7.12 5.86 22.46

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