负载型铜在萘的α-硝基化反应中的催化性能

doi:10.16085/j.issn.1000-6613.2021-0814

化工进展 ›› 2022, Vol. 41 ›› Issue (4): 1894-1899.DOI: 10.16085/j.issn.1000-6613.2021-0814

负载型铜在萘的α-硝基化反应中的催化性能

洪乾¹^,²(), 白瑞¹, 彭欣华¹, 孙鸣¹^,², 刘珊珊³, 焦林郁¹^,²(), 马晓迅¹^,²

^1.西北大学化工学院，陕西西安 710069
^2.国家碳氢资源清洁利用国际科技合作基地，陕北能源先进化工利用技术教育部工程研究中心，陕西省洁净煤转化工程技术中心，陕北能源化工产业发展协同创新中心，陕西西安 710069
^3.陕西科技大学化学与化工学院，陕西省轻化工助剂重点实验室，陕西西安 710021

收稿日期:2021-04-18 修回日期:2021-06-13 出版日期:2022-04-23 发布日期:2022-04-25
通讯作者: 焦林郁
作者简介:洪乾（1992—），男，硕士研究生，研究方向为反应工艺优化。E-mail：1102270482@qq.com。
基金资助:
国家重点研发计划(2018YFB0604603);陕西省自然科学基金(2019JQ-787)

Studies on the catalytic performance of supported copper in the α-nitration of naphthalene

HONG Qian¹^,²(), BAI Rui¹, PENG Xinhua¹, SUN Ming¹^,², LIU Shanshan³, JIAO Linyu¹^,²(), MA Xiaoxun¹^,²

^1.School of Chemical Engineering, Northwest University, Xi’an 710069, Shaanxi, China
^2.International Scientific and Technological Cooperation Base for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advance Use Technology of Shaanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaboration Innovation Center for Development of Energy and Chemical Industry in Northern Shaanxi, Xi’an 710069, Shaanxi, China
^3.Shaanxi Key Laboratory of Chemical Additives for Industry, College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi’an 710021, Shaanxi, China

Received:2021-04-18 Revised:2021-06-13 Online:2022-04-23 Published:2022-04-25
Contact: JIAO Linyu

摘要/Abstract

摘要：

目前工业上合成 α-硝基萘仍然采用传统的混酸硝化法，然而该方法存在区域选择性不高、官能团耐受性差、产生过量酸性废液以及后处理费用高等诸多局限性，导致环境污染以及生产成本的提高，不符合绿色化学的理念。鉴于 α-硝基萘的应用前景，本文通过浸渍-焙烧-还原等步骤设计合成一系列负载型铜催化剂，实现了萘向 α-硝基萘的高效、经济、绿色的催化转化。其中，以ZSM-5等为载体合成的催化剂Cu/ZSM-5催化效果最好，以较高的分离产率（高达95%）和优异的区域选择性[(α-∶β-)>(98∶2)]得到了目标产物α-硝基萘，而且在重复使用4次后依然保持较高的催化活性和结构稳定性。

关键词: 分子筛, 化学反应, 多相反应, 选择性, 负载型铜催化剂, 硝化, 萘, α-硝基萘

Abstract:

At present, the traditional nitrification method with mixed acids is still often used in the synthesis of α-nitronaphthalene in chemical industry. However, the method has many limitations such as low regional selectivity, poor functional group tolerance, excessive acid waste generated, as well as high cost of post-treatment, which lead to environmental pollution and increase of production cost. This is not in line with the concept of green chemistry. In view of the application prospect of α-nitronaphthalene, a series of supported copper catalysts were designed and synthesized through the steps of impregnation, roasting and reduction, which realized the efficient, economical and green catalytic conversion of naphthalene to α-nitronaphthalene. Among them, the catalyst Cu/ZSM-5 with ZSM-5 as the carrier had the best catalytic performance. The target product α-nitronaphthalene was obtained with high yield (up to 95%) and excellent regioselectivity [(α-∶β-)>(98∶2)]. The catalyst still maintained high catalytic activity and structural stability after recycled for 4 times.

Key words: molecular sieves, chemical reaction, multiphase reaction, selectivity, supported copper catalyst, nitration, naphthalene, α-nitronaphthalene

中图分类号:

TQ246.1

洪乾, 白瑞, 彭欣华, 孙鸣, 刘珊珊, 焦林郁, 马晓迅. 负载型铜在萘的α-硝基化反应中的催化性能[J]. 化工进展, 2022, 41(4): 1894-1899.

HONG Qian, BAI Rui, PENG Xinhua, SUN Ming, LIU Shanshan, JIAO Linyu, MA Xiaoxun. Studies on the catalytic performance of supported copper in the α-nitration of naphthalene[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1894-1899.

图/表 12

表1 负载型铜催化剂对选择性硝基化反应的催化性能

编号	催化剂	转化率/%	反应时间/h	分离产率/%
1	Cu/SiO₂	100	2	97
2	Cu/TiO₂	100	0.5	93
3	Cu/Al₂O₃	100	1	94
4	Cu/ZrO₂	100	2	92
5	Cu/ZSM-5	100	0.5	95
6	Cu/SSZ-13	100	1	85
7	Cu/KF/ZnO	97	6	92
8	Cu/ZnO	97	6	96
9	Cu/KF/MgO	90	6	74
10	Cu/MgO	92	6	80
11	Cu/SBA-15	95	6	89
12	Cu/USY	95	3	86

图1 负载型催化剂Cu/Al2O3的循环催化性能

图2 负载型催化剂Cu/ZSM-5的循环催化性能

图3 负载型铜催化剂的XRD图谱

图4 负载型催化剂Cu/SiO2的SEM图谱

图5 负载型催化剂Cu/ZSM-5的SEM图谱

图6 负载型催化剂Cu/Al2O3的SEM图谱

图7 负载型催化剂Cu/Al2O3的TEM图谱

图8 负载型催化剂Cu/SiO2的TEM图谱

图9 负载型催化剂Cu/ZSM-5的TEM图谱

图10 负载型铜催化剂的H2-TPR图谱

表2 负载型铜催化剂BET表征

编号	催化剂	比表面积 /m²·g^-1	总孔体积 /cm³·g^-1	α-硝基萘产率 /%
1	Cu/SSZ-13	408.7	0.360	85
2	Cu/ZSM-5	302.8	0.177	95
3	Cu/SiO₂	122.0	0.660	97
4	Cu/Al₂O₃	116.4	0.643	94
5	Cu/KF/MgO	31.8	0.353	74
6	Cu/ZrO₂	6.5	0.063	92
7	Cu/ZnO	1.9	0.010	96

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负载型铜在萘的α-硝基化反应中的催化性能

Studies on the catalytic performance of supported copper in the α-nitration of naphthalene

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