甲酸为氢源硝基苯转移加氢合成对氨基苯酚

doi:10.16085/j.issn.1000-6613.2023-1200

化工进展 ›› 2024, Vol. 43 ›› Issue (8): 4421-4431.DOI: 10.16085/j.issn.1000-6613.2023-1200

• 工业催化 • 上一篇

甲酸为氢源硝基苯转移加氢合成对氨基苯酚

王雨菲¹(), 贾宇¹, 张议升¹, 薛伟¹^,², 李芳¹^,²(), 王延吉¹^,²^,³

^1.河北工业大学化工学院河北省绿色化工与高效节能重点实验室，天津 300400
^2.天津市本质安全化工技术重点实验室，天津 300400
^3.河北省绿色化学工业产业研究院，河北沧州 061000

收稿日期:2023-07-14 修回日期:2023-12-10 出版日期:2024-08-15 发布日期:2024-09-02
通讯作者: 李芳
作者简介:王雨菲（1999—），女，硕士研究生，研究方向为绿色化工。E-mail：961283910@qq.com。
基金资助:
国家自然科学基金(U21A20306);河北省自然科学基金(B2022202077)

Synthesis of p-aminophenol by transfer hydrogenation of nitrobenzene using formic acid as hydrogen source

WANG Yufei¹(), JIA Yu¹, ZHANG Yisheng¹, XUE Wei¹^,², LI Fang¹^,²(), WANG Yanji¹^,²^,³

^1.Hebei Provincial Key Laboratory of Green Chemical Technology and High Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300400, China
^2.Tianjin Key Laboratory of Chemical Process Safety, Tianjin 300400, China
^3.Hebei Industrial Technology Research Institute of Green Chemical Industry, Cangzhou 061000, Hebei, China

Received:2023-07-14 Revised:2023-12-10 Online:2024-08-15 Published:2024-09-02
Contact: LI Fang

摘要/Abstract

摘要：

以UiO-66为前体，在N₂气氛下焙烧制备了ZrO₂@C，以其为载体，利用浸渍法制备了Pd/ZrO₂@C催化剂。以Pd/ZrO₂@C+SO₄^2-/ZrO₂为催化剂，对以甲酸（FA）为氢源、硝基苯（NB）转移加氢合成对氨基苯酚（PAP）的反应进行了研究。通过表征发现，Pd/ZrO₂@C载体中的ZrO₂为四方相ZrO₂，包埋在无定形C中。随着ZrO₂@C在空气中焙烧温度的升高和焙烧时间的增加，其C含量和比表面积随之下降，同时Pd颗粒尺寸变大。Pd/ZrO₂@C催化剂中Pd以Pd⁰和Pd²⁺两种形式存在，且随着C含量的减少，Pd⁰含量增加，Pd²⁺含量减少；当Pd⁰含量明显高于Pd²⁺，其对PAP的选择性明显下降。在140℃、反应6h的条件下，Pd/ZrO₂@C-200-4+SO₄^2-/ZrO₂具有较好的催化性能，NB转化率为63.7%，PAP选择性为42.3%。

关键词: 催化, 加氢, 载体, 对氨基苯酚, 甲酸, 硝基苯

Abstract:

With UiO-66 as the precursor, ZrO₂@C was prepared by calcination in N₂ atmosphere. Then, Pd/ZrO₂@C was prepared by impregnation method. In this paper, the catalytic transfer hydrogenation of nitrobenzene (NB) to p-aminophenol (PAP) over Pd/ZrO₂@C+SO₄^2-/ZrO₂ was studied with formic acid (FA) as hydrogen source. Characterization results showed that tetragonal ZrO₂ was present in ZrO₂@C and was embedded in amorphous C. With the increase of calcination temperature and time in the air, the C content and specific surface area of ZrO₂@C decreased accordingly, while the Pd particle size became larger. Pd in the Pd/ZrO₂@C catalyst was in the form of Pd⁰ and Pd²⁺. The content of Pd²⁺ decreased with C content, While the content of Pd⁰ increased. When the content of Pd⁰ was higher than that of Pd²⁺, PAP selectivity decreased obviously. Pd/ZrO₂@C-200-4+SO₄^2-/ZrO₂ exhibited good catalytic activity at 140℃ for 6h. The conversion of NB was 63.7% and the selectivity of PAP was 42.3%.

Key words: catalysis, hydrogenation, support, p-aminophenol, formic acid, nitrobenzene

中图分类号:

TQ246.35

王雨菲, 贾宇, 张议升, 薛伟, 李芳, 王延吉. 甲酸为氢源硝基苯转移加氢合成对氨基苯酚[J]. 化工进展, 2024, 43(8): 4421-4431.

WANG Yufei, JIA Yu, ZHANG Yisheng, XUE Wei, LI Fang, WANG Yanji. Synthesis of p-aminophenol by transfer hydrogenation of nitrobenzene using formic acid as hydrogen source[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4421-4431.

图/表 15

参考文献 33

1	WU Shutao, HUANG Xun, ZHANG Hongliang, et al. Efficient electrochemical hydrogenation of nitroaromatics into arylamines on a CuCo₂O₄ spinel cathode in an alkaline electrolyte[J]. ACS Catalysis, 2022, 12(1): 58-65.
2	ABDELHAMID Hani Nasser. High performance and ultrafast reduction of 4-nitrophenol using metal-organic frameworks[J]. Journal of Environmental Chemical Engineering, 2021, 9(1): 104404.
3	ATTIA Yasser A, MOHAMED Yasser M A. Silicon-grafted Ag/AgX/rGO nanomaterials (X = Cl or Br) as dip-photocatalysts for highly efficient p-nitrophenol reduction and paracetamol production[J]. Applied Organometallic Chemistry, 2019, 33(3): 1-11.
4	YU Yeonhwa, JUNG Euiyoung, KIM Hyun Jin, et al. Protein particles decorated with Pd nanoparticles for the catalytic reduction of p-nitrophenol to p-aminophenol[J]. ACS Applied Nano Materials, 2020, 3(10): 10487-10496.
5	ZHANG Tingting, JIANG Jingyang, WANG Yanhua. Green route for the preparation of p-aminophenol from nitrobenzene by catalytic hydrogenation in pressurized CO₂/H₂O system[J]. Organic Process Research & Development, 2015, 19(12): 2050-2054.
6	ZOU Luyao, CUI Yuanyuan, DAI Weilin. Highly efficient Au/TiO₂ catalyst for one-pot conversion of nitrobenzene to p-aminophenol in water media[J]. Chinese Journal of Chemistry, 2014, 32(3): 257-262.
7	DONG Zhen, WANG Tao, ZHAO Jie, et al. Ni-Silicides nanoparticles as substitute for noble metals for hydrogenation of nitrobenzene to p-aminophenol in sulfuric acid[J]. Applied Catalysis A: General, 2016, 520: 151-156.
8	RODE Chandrashekhar V, VAIDYA Manisha J, CHAUDHARI Raghunath V. Synthesis of p-aminophenol by catalytic hydrogenation of nitrobenzene[J]. Organic Process Research & Development, 1999, 3(6): 465-470.
9	王淑芳, 高杨, 王延吉, 等. 负载型纳米Pt催化剂的制备及其催化合成对氨基苯酚[J]. 石油化工, 2009, 38(4): 361-366.
	WANG Shufang, GAO Yang, WANG Yanji, et al. Preparation of supported nano-Pt catalyst for synthesis of p-aminophenol[J]. Petrochemical Technology, 2009, 38(4): 361-366.
10	王淑芳, 王延吉, 高杨, 等. SAPO-5分子筛的制备及其催化合成对氨基苯酚[J]. 催化学报, 2010, 31(6): 637-644.
	WANG Shufang, WANG Yanji, GAO Yang, et al. Preparation of SAPO-5 and its catalytic synthesis of p-aminophenol[J]. Chinese Journal of Catalysis, 2010, 31(6): 637-644.
11	WANG Shufang, JIN Yadan, HE Beibei, et al. Synthesis of bifunctional Pt/MgAPO-5 catalysts and their catalytic performance in the hydrogenation of nitrobenzene to p-aminophenol[J]. Science China Chemistry, 2010, 53(7): 1514-1519.
12	宋丽娟, 王利, 张晓彤, 等. 一种非酸介质中硝基苯选择加氢制对氨基苯酚的催化剂：CN102600891A[P]. 2012-07-25.
	SONG Lijuan, WANG Li, ZHANG Xiaotong, et al. A catalyst for selective hydrogenation of nitrobenzene to p-aminophenol in a non-acid medium：CN102600891A[P]. 2012-07-25.
13	Jeeva RATNAM K, Sudarshan REDDY R, SEKHAR N S, et al. Bamberger rearrangement on solid acids[J]. Applied Catalysis A: General, 2008, 348(1): 26-29.
14	DESHPANDE Abhay, FIGUERAS F, LAKSHMI KANTAM M, et al. Environmentally friendly hydrogenation of nitrobenzene to p-aminophenol using heterogeneous catalysts[J]. Journal of Catalysis, 2010, 275(2): 250-256.
15	黄伟, 储政, 任磊, 等. 碳基固体酸在硝基苯加氢制备对氨基苯酚中的应用[J]. 化工进展, 2023, 42(1): 272-281.
	HUANG Wei, CHU Zheng, REN Lei, et al. Application of carbon-based solid acid in hydrogenation of nitrobenzene to p-aminophenol[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 272-281.
16	刘迎新, 刘晓爽, 曾茂, 等. 硝基苯催化加氢合成对氨基苯酚的研究进展[J]. 石油化工, 2018, 47(1): 79-85.
	LIU Yingxin, LIU Xiaoshuang, ZENG Mao, et al. Progress in synthesis of p-aminophenol by catalytic hydrogenation of nitrobenzene[J]. Petrochemical Technology, 2018, 47(1): 79-85.
17	GU Jing, ZHANG Zhiyang, DING Liping, et al. Platinum nanoparticles encapsulated in HZSM-5 crystals as an efficient catalyst for green production of p-aminophenol[J]. Catalysis Communications, 2017, 97: 98-101.
18	蒋文艳, 魏光涛, 刘子涵, 等. 催化转移加氢及其强化研究进展[J]. 现代化工, 2019, 39(3): 26-30.
	JIANG Wenyan, WEI Guangtao, LIU Zihan, et al. Research progress in catalytic transfer hydrogenation and its intensification[J]. Modern Chemical Industry, 2019, 39(3): 26-30.
19	郑纯智, 张继炎, 王日杰. 催化转移加氢及其在有机合成中的应用[J]. 工业催化, 2004， 12(3): 29-35.
	ZHENG Chunzhi, ZHANG Jiyan, WANG Rijie. Catalytic transfer hydrogenation and its application in organic synthesis[J]. Industrial Catalysis, 2004， 12(3): 29-35.
20	MENG Qinglei, YANG Xiaolong, WANG Xian, et al. Preparation strategy using pre-nucleation coupled with in situ reduction for a high-performance catalyst towards selective hydrogen production from formic acid[J]. Catalysts, 2022, 12(3): 325.
21	王显. 甲酸氢能转换过程中抗中毒催化剂的理性设计与精准制备[D]. 合肥: 中国科学技术大学, 2021.
	WANG Xian. Rational design and precise preparation of anti-poisoning catalyst in the conversion of formic acid to hydrogen energy[D]. Hefei: University of Science and Technology of China, 2021.
22	JIA Yu, LI Fang, ZHANG Yisheng, et al. A novel process for the synthesis of p-aminophenol by transfer hydrogenation of nitrobenzene using formic acid as hydrogen source[J]. Asia-Pacific Journal of Chemical Engineering, 2022, 17(5): 1-10.
23	DHAKSHINAMOORTHY Amarajothi, GARCIA Hermenegildo. Metal-organic frameworks as solid catalysts for the synthesis of nitrogen-containing heterocycles[J]. Chemical Society Reviews, 2014, 43(16): 5750-5765.
24	Raja DAS, PACHFULE Pradip, BANERJEE Rahul, et al. Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): Finding the border of metal and metal oxides[J]. Nanoscale, 2012, 4(2): 591-599.
25	SHEN Kui, CHEN Xiaodong, CHEN Junying, et al. Development of MOF-derived carbon-based nanomaterials for efficient catalysis[J]. ACS Catalysis, 2016, 6(9): 5887-5903.
26	CAO Wenxiu, LUO Wenhao, GE Hongguang, et al. UiO-66 derived Ru/ZrO₂@C as a highly stable catalyst for hydrogenation of levulinic acid to γ-valerolactone[J]. Green Chemistry, 2017, 19(9): 2201-2211.
27	ZHANG Weina, LU Guang, CUI Chenlong, et al. A family of metal-organic frameworks exhibiting size-selective catalysis with encapsulated noble-metal nanoparticles[J]. Advanced Materials, 2014, 26(24): 4056-4060.
28	ZHANG Xue, QIAO Jing, LIU Chang, et al. A MOF-derived ZrO₂/C nanocomposite for efficient electromagnetic wave absorption[J]. Inorganic Chemistry Frontiers, 2020, 7(2): 385-393.
29	RAHMAN Md Anisur, ROUT S, THOMAS Joseph P, et al. Defect-rich dopant-free ZrO₂ nanostructures with superior dilute ferromagnetic semiconductor properties[J]. Journal of the American Chemical Society, 2016, 138(36): 11896-11906.
30	QIAO Jing, ZHANG Xue, XU Dongmei, et al. Design and synthesis of TiO₂/Co/carbon nanofibers with tunable and efficient electromagnetic absorption[J]. Chemical Engineering Journal, 2020, 380: 122591.
31	FENG Wei, WANG Yaming, CHEN Junchen, et al. Reduced graphene oxide decorated with in-situ growing ZnO nanocrystals: Facile synthesis and enhanced microwave absorption properties[J]. Carbon, 2016, 108: 52-60.
32	Qing LYU, MENG Qinglei, LIU Weiwei, et al. Pd-PdO interface as active site for HCOOH selective dehydrogenation at ambient condition[J]. The Journal of Physical Chemistry C, 2018, 122(4): 2081-2088.
33	WEI Qinhong, MA Qingxiang, ZUO Pingping, et al. Hollow structure and electron promotion effect of mesoporous Pd/CeO₂ catalyst for enhanced catalytic hydrogenation[J]. ChemCatChem, 2018, 10(5): 1019-1026.

样品	C质量分数/%	比表面积 /m²·g^-1	孔容积 /cm³·g^-1	孔径/nm
ZrO₂@C	24.38	240.95	0.23	3.82
ZrO₂@C-200-4	22.74	246.94	0.25	4.01
ZrO₂@C-300-1.5	7.56	206.56	0.20	3.92
ZrO₂@C-300-4	2.77	173.74	0.26	6.02
ZrO₂@C-400-4	0.50	118.44	0.26	8.84

样品	C质量分数/%	比表面积 /m²·g^-1	孔容积 /cm³·g^-1	孔径/nm
ZrO₂@C	24.38	240.95	0.23	3.82
ZrO₂@C-200-4	22.74	246.94	0.25	4.01
ZrO₂@C-300-1.5	7.56	206.56	0.20	3.92
ZrO₂@C-300-4	2.77	173.74	0.26	6.02
ZrO₂@C-400-4	0.50	118.44	0.26	8.84

样品	O 1s/%	Zr 3d/%	O/Zr
ZrO₂@C	30.65	10.88	2.82
ZrO₂@C-200-4	33.67	11.64	2.89
ZrO₂@C-300-1.5	43.74	15.34	2.85
ZrO₂@C-300-4	51.55	18.34	2.81
ZrO₂@C-400-4	59.73	21.97	2.72

样品	O 1s/%	Zr 3d/%	O/Zr
ZrO₂@C	30.65	10.88	2.82
ZrO₂@C-200-4	33.67	11.64	2.89
ZrO₂@C-300-1.5	43.74	15.34	2.85
ZrO₂@C-300-4	51.55	18.34	2.81
ZrO₂@C-400-4	59.73	21.97	2.72

样品	比表面积/m²·g^-1	孔容积/cm³·g^-1	孔径/nm
Pd/ZrO₂@C	234.37	0.26	4.51
Pd/ZrO₂@C-200-4	223.02	0.29	5.15
Pd/ZrO₂@C-300-1.5	168.93	0.24	5.62
Pd/ZrO₂@C-300-4	160.99	0.21	5.10
Pd/ZrO₂@C-400-4	115.89	0.25	8.69

甲酸为氢源硝基苯转移加氢合成对氨基苯酚

Synthesis of p-aminophenol by transfer hydrogenation of nitrobenzene using formic acid as hydrogen source

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 15

参考文献 33

相关文章 15

编辑推荐

Metrics

本文评价

样品	Pd物种分布/%		Pd²⁺/Pd⁰
样品	Pd⁰	Pd²⁺	Pd²⁺/Pd⁰
Pd/ZrO₂@C	57.0	43.0	0.75
Pd/ZrO₂@C-200-4	55.7	44.3	0.80
Pd/ZrO₂@C-300-1.5	80.2	19.8	0.25
Pd/ZrO₂@C-300-4	81.7	18.3	0.22
Pd/ZrO₂@C-400-4	83.3	16.7	0.20

催化剂	TOF/h^-1
Pd/ZrO₂@C	306.4
Pd/ZrO₂@C-200-4	331.1
Pd/ZrO₂@C-300-1.5	252.7
Pd/ZrO₂@C-300-4	182.9
Pd/ZrO₂@C-400-4	160.0

催化剂	S/%	Pd/%	比表面积 /m²·g^-1	孔容 /cm³·g^-1	孔径 /nm
新鲜催化剂	5.90	0.33	81.24	0.31	11.72
循环5次后的催化剂	4.03	0.30	80.15	0.23	8.05

[1]	胡婷霞, 赵立欣, 姚宗路, 霍丽丽, 贾吉秀, 谢腾. 双金属催化剂在生物质焦油催化蒸汽重整领域的研究进展[J]. 化工进展, 2024, 43(8): 4354-4365.
[2]	吴泽亮, 管琦卉, 陈世霞, 王珺. 炔烃选择性加氢制烯烃反应的研究进展[J]. 化工进展, 2024, 43(8): 4366-4381.
[3]	张叶素, 权燕红, 丁欣欣, 任军. 链状MFI型分子筛的合成与应用[J]. 化工进展, 2024, 43(8): 4382-4392.
[4]	王嘉, 李文翠, 吴凡, 高新芊, 陆安慧. NiMo/Al₂O₃催化剂活性组分分布调控及其加氢脱硫应用[J]. 化工进展, 2024, 43(8): 4393-4402.
[5]	付涛, 李立, 高莉宁, 朱富维, 曹炜烨, 陈华鑫. 水泥基硼掺杂石墨相氮化碳降解NO[J]. 化工进展, 2024, 43(8): 4403-4410.
[6]	龙涛, 周锋, 张伟, 吴泓, 王建, 陈霖. CO-CO₂体系制备氘代甲醇催化剂的合成与改性[J]. 化工进展, 2024, 43(8): 4411-4420.
[7]	刘文津, 张玉明, 李家州, 张炜, 陈哲文. 典型石油热加工技术发展现状及展望[J]. 化工进展, 2024, 43(7): 3534-3550.
[8]	张子杭, 王树荣. 生物质热解转化与产物低碳利用研究进展[J]. 化工进展, 2024, 43(7): 3692-3708.
[9]	龚德成, 沈倩, 朱贤青, 黄云, 夏奡, 张敬苗, 朱恂, 廖强. 微藻超临界水气化制取富氢合成气的研究进展[J]. 化工进展, 2024, 43(7): 3709-3728.
[10]	郭鹏, 李红伟, 李贵贤, 季东, 王东亮, 赵新红. 直接甲醇燃料电池阳极催化剂的失活机制及应对策略[J]. 化工进展, 2024, 43(7): 3812-3823.
[11]	王颖杰, 祝新利. 溶胶-凝胶法制备高分散Ni-Cu/SiO₂ 促进间甲酚直接脱氧制甲苯[J]. 化工进展, 2024, 43(7): 3824-3833.
[12]	罗丛佳, 豆义波, 卫敏. 水滑石光催化剂结构调控用于二氧化碳还原的研究进展[J]. 化工进展, 2024, 43(7): 3891-3909.
[13]	龚勇, 潘忠文, 谢纯, 崔瑾, 王鲜. 碳酸钠催化制备纳米碳纤维[J]. 化工进展, 2024, 43(7): 3980-3986.
[14]	张世蕊, 范朕连, 宋慧平, 张丽娜, 高宏宇, 程淑艳, 程芳琴. 粉煤灰负载光催化材料的研究进展[J]. 化工进展, 2024, 43(7): 4043-4058.
[15]	何弈雪, 秦先超, 马伟芳. 过硫酸盐高级氧化原位修复地下水中卤代烃污染研究进展[J]. 化工进展, 2024, 43(7): 4072-4088.