高黏附性Pd/SiO2/NF整体式催化剂的制备及加氢性能研究

doi:10.11949/0438-1157.20231296

摘要/Abstract

摘要：

旋转填充床反应器（RPB）中液体的高速冲刷和较强的离心力容易导致整体式催化剂的涂层和活性组分从基体表面脱落造成损失，限制了整体式催化剂在RPB反应器中的应用。因此，研究整体式催化剂涂层和活性组分的黏附性，以提升催化剂在RPB反应器中的催化活性和使用寿命具有重要意义。基于此，采用超重力喷涂法在泡沫镍（NF）基体表面负载氧化硅（SiO₂）涂层，制备了具有高黏附性的Pd/SiO₂₍_x₎/NF整体式催化剂，通过超声振荡、BET、XRD、SEM和XPS等对整体式催化剂进行测试和分析。当RPB反应器的转速为1200 r/min时，整体式催化剂具有优异的黏附性能，涂层的脱落率为4%。以对硝基苯甲醚（PNA）催化加氢制备对氨基苯甲醚（PA）为探针反应，RPB反应器中Pd/SiO_2(1200)/NF整体式催化剂具有较好的催化活性，180 min 时PNA转化率为98.9%。本工作可为开发高黏附性的整体式催化剂提供新的途径。

关键词: 旋转填充床反应器, 整体式催化剂, 黏附性, 催化加氢

Abstract:

The high-speed scouring and strong centrifugal force of the liquid in the rotating packed bed reactor (RPB) can easily cause the coating and active components of the monolithic catalyst to fall off the surface of the matrix and cause losses, which limits the application of monolithic catalysts in RPB reactors. Therefore, it is important to investigate the adhesion of coatings and active components to improve the catalytic activity and lifetime of monolithic catalysts in the RPB reactor. In this work, the SiO₂ coating was deposited on nickel foam by the high gravity spraying method to prepare Pd/SiO₂₍_x₎/NF monolithic catalysts. The monolithic catalysts were characterized by ultrasonic oscillation test, BET, XRD, SEM and XPS. When the rotational speed was 1200 r/min, the monolithic catalyst had the excellent adhesion performance, and the mass loss rate of the coating was 4%. The Pd/SiO_2(1200)/NF monolithic catalyst exhibited good catalytic activity in the hydrogenation of p-nitroanisole (PNA) to p-aminoanisole (PA) reaction in the RPB reactor, and the conversion of PNA was 98.9% within 180 min. This work provides a new strategy for the development of stable monolithic catalysts.

Key words: rotating packed bed reactor, monolithic catalyst, adhesion, catalytic hydrogenation

中图分类号:

TQ 021.8

韩宇, 周乐, 张鑫, 罗勇, 孙宝昌, 邹海魁, 陈建峰. 高黏附性Pd/SiO₂/NF整体式催化剂的制备及加氢性能研究[J]. 化工学报, 2024, 75(4): 1533-1542.

Yu HAN, Le ZHOU, Xin ZHANG, Yong LUO, Baochang SUN, Haikui ZOU, Jianfeng CHEN. Preparation of high adhesion Pd/SiO₂/NF monolithic catalyst and its hydrogenation performance[J]. CIESC Journal, 2024, 75(4): 1533-1542.

图/表 14

图1 超重力喷涂法负载SiO2涂层装置

Fig.1 Schematic diagram of loading SiO2 coating by HiGee spraying method

图2 催化反应评价装置示意图1—H2钢瓶;2—N2钢瓶;3—控制器;4—超重力反应器;5—电机;6—排空口;7—压力表;8—取样口;9—转子;10—提升器

Fig.2 Schematic diagram of experimental apparatus for catalytic hydrogenation

图3 酸蚀前后NF的SEM图

Fig.3 SEM images of NF before and after acid etching

表1 整体式催化剂Pd的实际负载量

Table 1 The actual of Pd loads in monolithic catalysts

样品	Pd的实际负载量/%(mass)
Pd/SiO₂₍₀₎/NF	0.4920
Pd/SiO₂₍₂₀₀₎/NF	0.4951
Pd/SiO₂₍₅₀₀₎/NF	0.4879
Pd/SiO₂₍₈₀₀₎/NF	0.5009
Pd/SiO_2(1200)/NF	0.4910
Pd/SiO_2(1500)/NF	0.4881

图4 NF、NF（酸蚀后）、Pd/SiO2(0)/NF、Pd/SiO2(1200)/NF的XRD谱图

Fig.4 XRD patterns of NF, NF after acid etching, Pd/SiO2(0)/NF and Pd/SiO2(1200)/NF

图5 Pd/SiO2(0)/NF和Pd/SiO2(1200)/NF的N2吸脱附曲线和孔径分布

Fig.5 Nitrogen adsorption-desorption curve and pore size distribution of Pd/SiO2(0)/NF and Pd/SiO2(1200)/NF

图6 Pd/SiO2(1200)/NF的XPS图

Fig.6 XPS spectra of Pd/SiO2(1200)/NF

图7 Pd/SiO2(1200)/NF的SEM图和能谱仪面扫图

Fig.7 SEM image and relevant EDS mappings of Pd/SiO2(1200)/NF

图8 转速对涂层负载脱落质量的影响

Fig.8 Effect of rotational speed on the mass of coating loading and spalling

图9 转速对涂层负载脱落率的影响

Fig.9 Effect of rotational speed on the mass loss rate

图10 Pd/SiO2(x)/NF黏附性测试前后SEM图

Fig.10 SEM images of Pd/SiO2(x)/NF before and after adhesion test

图11 催化剂催化活性评价结果

Fig.11 Catalytic activity of Pd/SiO2(x)/NF(temperature:80℃; pressure:2 MPa)

图12 Pd/SiO2(1200)/NF催化剂稳定性测试结果

Fig.12 Catalytic stability of Pd/SiO2(1200)/NF

图13 Pd/SiO2(1200)/NF催化稳定性测试前后的SEM图

Fig.13 SEM images of Pd/SiO2(1200)/NF before and after catalytic stability test

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高黏附性Pd/SiO₂/NF整体式催化剂的制备及加氢性能研究

Preparation of high adhesion Pd/SiO₂/NF monolithic catalyst and its hydrogenation performance

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