络合-溶剂热法制备钯基催化剂及其催化氧化间二甲苯性能

doi:10.11949/j.issn.0438-1157.20181083

化工学报 ›› 2019, Vol. 70 ›› Issue (3): 937-943.DOI: 10.11949/j.issn.0438-1157.20181083

• 催化、动力学与反应器 • 上一篇下一篇

络合-溶剂热法制备钯基催化剂及其催化氧化间二甲苯性能

赫帅^1,²(),郭凤²(),康国俊¹(),余剑²,任雪峰¹,许光文³

1. 中国矿业大学化学化工学院，江苏省煤基CO2捕集与地质储存重点实验室，江苏徐州 221116
2. 中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
3. 沈阳化工大学，辽宁沈阳 110142

收稿日期:2018-09-26 修回日期:2018-12-07 出版日期:2019-03-05 发布日期:2019-03-05
通讯作者: 郭凤,康国俊
作者简介:<named-content content-type="corresp-name">赫帅</named-content>（1994—），女，硕士研究生，<email>shuaih@cumt.edu.cn</email>|郭凤（1983—），女，博士，助理研究员，<email>guofeng@ipe.ac.cn</email>;通信作者:|康国俊（1979—），男，博士，助理研究员，<email>gjkang@cumt.edu.cn</email>
基金资助:
国家重点研发计划项目(2016YFB0600303);中央高校基本科研业务费专项资金(2017XKQY065);多项复杂系统国家重点实验室自主研究课题(MPCS-2017-D-11)

Preparation of palladium-based catalysts by complexing-solvothermal method and catalytic oxidation of m-xylene

Shuai HE^1,²(),Feng GUO²(),Guojun KANG¹(),Jian YU²,Xuefeng REN¹,Guangwen XU³

1. Key Laboratory of Coal-based CO2 Capture and Geological Storage, School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
2. State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
3. Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China

Received:2018-09-26 Revised:2018-12-07 Online:2019-03-05 Published:2019-03-05
Contact: Feng GUO,Guojun KANG

摘要/Abstract

摘要：

通过采用络合-溶剂热法、水热法和浸渍法三种方法制备了负载量为0.6%（质量分数）的Pd/Al₂O₃催化剂，重点考察不同制备方法催化氧化间二甲苯作为典型的挥发性有机化合物的能力。结果表明：络合-溶剂热法制备的Pd/Al₂O₃-com催化剂催化氧化间二甲苯的能力最强，间二甲苯体积分数为0.002%时完全转化温度（T₁₀₀）为130℃，低于浸渍法制备催化剂的完全转化温度30℃。对Pd/Al₂O₃催化剂进行了比表面积（BET）、X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电镜（SEM）等表征分析，发现Pd/Al₂O₃-com中Pd主要以还原态Pd⁰高度分散于载体表面，而另两种方法制备的催化剂均有明显的Pd²⁺存在。结合性能测试及表征分析，表明络合-溶剂热法制备的Pd/Al₂O₃-com催化剂活性组分Pd的高度分散，增强了催化活性，可满足高浓度间二甲苯、宽气体体积空速条件下催化氧化脱除间二甲苯的工业应用要求。

关键词: 钯基催化剂, 催化氧化, 挥发性有机化合物, 络合-溶剂热法, 还原

Abstract:

The Pd/Al₂O₃ catalysts with a loading of 0.6% (mass fraction) were prepared by complexation-solvent thermal method, hydrothermal method and impregnation method. The effect of different preparation methods on the performance of the catalyst was evaluated by using m-xylene as the representative of volatile organic compounds (VOCs). The results showed that the most effective catalyst Pd/Al₂O₃-com was prepared by complexing-solvothermal. The m-xylene with volume fraction of 0.002% can completely converted to CO₂ and H₂O (T₁₀₀) at 130℃ over Pd/Al₂O₃-com catalyst from the complexing-solvothermal method, which was lower about 30℃ than the catalyst (Pd/Al₂O₃-imp) from the impregnation method. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) and scanning electron microscopy (SEM) techniques were performed to characterize the physico-chemical properties of synthesized Pd/Al₂O₃ catalysts. The results indicated that the Pd element of Pd/Al₂O₃-com was mainly dispersed on the surface of the support at the reduction state Pd⁰, while the Pd element of Pd/Al₂O₃-imp and Pd/Al₂O₃-hyd catalyst was at the form of Pd²⁺ with poor dispersion. Combined with the catalytic activity performance and evaluation results, a highly dispersed and reduction state form of Pd active component on the surface of the carrier resulted in a remarkable catalytic activity on m-xylene conversion. The Pd/Al₂O₃-com catalyst with these features exhibit good activity for removing VOCs under high concentration (0.02%－0.07%, vol) and wide space velocity (5 $×$ 10⁴－10 $×$ 10⁴ h^-1) conditions, and thus meet well the requirements of industrial application.

Key words: palladium-based catalyst, catalytic oxidation, volatile organic compounds, complexing-solvothermal method, reduction

中图分类号:

O 643.36

赫帅, 郭凤, 康国俊, 余剑, 任雪峰, 许光文. 络合-溶剂热法制备钯基催化剂及其催化氧化间二甲苯性能[J]. 化工学报, 2019, 70(3): 937-943.

Shuai HE, Feng GUO, Guojun KANG, Jian YU, Xuefeng REN, Guangwen XU. Preparation of palladium-based catalysts by complexing-solvothermal method and catalytic oxidation of m-xylene[J]. CIESC Journal, 2019, 70(3): 937-943.

图/表 11

图1 催化剂评价装置

Fig.1 Experimental set-up for catalytic tests

表1 Pd/Al2O3催化剂的XRF结果

Table1 XRF analysis results for Pd/Al2O3 catalyst/%(mass)

样品	Pd	Al	O	Others
Pd/Al₂O₃-com	0.45	51.98	46.68	0.89
Pd/Al₂O₃-hyd	0.48	51.82	46.79	0.91
Pd/Al₂O₃-imp	0.39	51.68	47.13	0.8

图2 不同方法制备的催化剂的XRD谱图

Fig.2 XRD patterns of Pd/Al2O3 catalyst from different preparation methods

图3 载体及不同方法制备的催化剂的吸附、脱附等温线

Fig.3 Adsorption isotherms and desorption isotherms of carrier and Pd/Al2O3 catalyst from different preparation methods

图4 载体及不同方法制备的催化剂的孔径分布

Fig.4 Pore size distribution of carrier and Pd/Al2O3 catalyst from different preparation methods

表2 载体及催化剂的孔结构参数和Pd粒径

Table2 BET surface area, pore volume and pore diameter of carrier and catalysts

样品	比表面积/(m²/g)	孔容/(cm³/g)	孔径/nm
Al₂O₃	187	0.42	9.09
Pd/Al₂O₃-com	149	0.31	8.27
Pd/Al₂O₃-hyd	174	0.29	6.71
Pd/Al₂O₃-imp	162	0.35	8.73

图5 不同方法制备的催化剂的XPS谱图

Fig.5 XPS spectra of Pd/Al2O3 catalysts from different preparation methods

图6 不同方法制备催化剂的SEM图及EDS图

Fig.6 SEM and EDS images of Pd/Al2O3catalysts from different preparation methods

图7 不同方法制备的催化剂的催化氧化间二甲苯活性

Fig.7 Catalytic performance of synthesized Pd/Al2O3 from different preparation methods

图8 不同间二甲苯浓度及空速对络合-溶剂热法制备催化剂的影响

Fig.8 Catalytic performance of Pd/Al2O3-com catalyst varied with concentrations and space velocities of m-xylene

图9 Pd/Al2O3-com催化剂活性稳定性测试结果

Fig.9 Stability performance of Pd/Al2O3-com(260℃,0.07%(vol.), GHSV:5×104 h-1)

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络合-溶剂热法制备钯基催化剂及其催化氧化间二甲苯性能

Preparation of palladium-based catalysts by complexing-solvothermal method and catalytic oxidation of m-xylene

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