低温等离子体协同CeO2/13X催化降解甲苯

doi:10.11949/0438-1157.20201914

摘要/Abstract

摘要：

低温等离子体协同催化剂技术（NTP-CAT）由于操作方便、能耗低等特点，特别适合用于工业非连续或连续消除低浓度VOCs过程。本研究发现NTP-CAT体系中CeO₂基催化剂更适合负载于13X载体以降解甲苯，并进一步考察CeO₂负载量对VOCs消除效果的影响。结果发现，NTP-CAT 体系中30% CeO₂/13X表现出最优性能，其可降解约85%的甲苯，CO₂产物选择性可达55%。表征结果也表明，Ce组分在30% CeO₂/13X表面仍可较好分散，而且表面的Ce³⁺物种含量最高。O₂-TPD实验结果证实表面Ce³⁺物种来源于Ce⁴⁺物种的等离子体处理。而且，表面Ce³⁺含量越高，有利于产生更多的氧物种，随后将与其周边13X吸附活化的甲苯反应。因此，甲苯降解在NTP-CAT体系中应存在分工协同机制。

关键词: 低温等离子体, 甲苯, CeO₂/13X, 催化氧化, 反应机理

Abstract:

The low-temperature plasma combined with catalyst technology (NTP-CAT) has feature of convenience in operation and relatively low energy consumption. It can be applied to industrial elimination of low concentration VOCs both continuous or batch. It was found the 13X supported CeO₂ catalyst has higher efficiency to decompose toluene in NTP-CAT system, and then it is further explored the effect of CeO₂ content on toluene degradation. The results showed that 30% CeO₂/13X was the best for toluene degradation using NTP-CAT, and around 85% of toluene can be decomposed with about 55% CO₂ selectivity. The characterization results demonstrated that Ce component was dispersed relatively evenly on the surface of 13X for 30% CeO₂/13X. Specially, the maximum amount of Ce³⁺ was found on its surface, and the Ce³⁺ was originated from the Ce⁴⁺ species as deduced from the results of O₂-TPD. Moreover, the increased amount of Ce³⁺ was beneficial for producing more active oxygen species, which can react with the NTP-treated toluene adsorbed on the 13X. Therefore, it can be concluded that the NTP-CAT system has synergic effect for toluene degradation.

Key words: low temperature plasma, toluene, CeO₂/13X, catalytic oxidation, reaction mechanism

中图分类号:

TQ 032.4

叶凯, 刘香华, 姜月, 于颖, 赵亚飞, 庄烨, 郑进保, 陈秉辉. 低温等离子体协同CeO₂/13X催化降解甲苯[J]. 化工学报, 2021, 72(7): 3706-3715.

YE Kai, LIU Xianghua, JIANG Yue, YU Ying, ZHAO Yafei, ZHUANG Ye, ZHENG Jinbao, CHEN Binghui. Combing low-temperature plasma with CeO₂/13X for toluene degradation[J]. CIESC Journal, 2021, 72(7): 3706-3715.

图/表 13

图1 实验装置及流程

Fig.1 Experiment device and flow chart

图2 等离子体放电时的Lissajous图形

Fig.2 Discharge properties (Lissajous plot)

图3 等离子体协同铈基催化剂处理甲苯

Fig.3 Supported CeO2-based catalysts with NTP to decompose toluene

图4 等离子体协同不同负载量的铈基催化剂处理甲苯

Fig.4 The effect of CeO2 loading on toluene degradation in NTP-CAT system

图5 13X和40%Ce/13X吸附甲苯的性能

Fig.5 The performance of adsorbing toluene for 13X and 40%Ce/13X

图6 不同催化剂反应前后的N2-等温吸脱附曲线和孔径分布

Fig.6 Nitrogen adsorption-desorption isotherms and corresponding pore size distribution curves (inset) of different CeO2-based catalysts

表1 CeO2基催化剂的比表面积、孔容和孔径

Table 1 Textural properties of CeO2-based catalysts

Catalyst	S_BET/(m2/g)	V_pore/(cm3/g)	Pore size/nm
fresh 10%Ce/13X	379.4	0.052	5.0
used 10%Ce/13X	313.0	0.063	4.5
fresh 20%Ce/13X	346.7	0.042	5.1
used 20%Ce/13X	342.6	0.046	5.0
fresh 30%Ce/13X	286.1	0.035	5.0
used 30%Ce/13X	173.9	0.032	6.5
fresh 40%Ce/13X	200.7	0.027	4.7
used 40%Ce/13X	179.2	0.030	5.2

图7 不同催化剂XRD谱图

Fig.7 XRD patterns of different CeO2-based catalysts

图8 不同催化剂的Ce 3d XPS谱图

Fig.8 Ce 3d XPS spectra of different CeO2-based catalysts

图9 不同催化剂反应前后的O 1s 谱图

Fig.9 O 1s XPS spectra of different CeO2-based catalysts

表2 不同催化剂元素的表面组成

Table 2 The surface composition of different CeO2-based catalysts

Catalysts	CeO₂ loading/%	Ce³⁺/Ce⁴⁺	Ce/ (Si+Al)	Ce³⁺/ (Si+Al)	O_sur/O	O_sur/ (Si+Al)
10%Ce/13X
fresh	13.5	0.39	2.38	0.93	0.44	1.67
used	—	0.41	2.25	0.92	0.42	1.42
20%Ce/13X
fresh	20.7	0.28	2.87	0.80	0.4	2.63
used	—	0.37	2.90	1.07	0.44	2.86
30%Ce/13X
fresh	27.7	0.23	6.74	1.55	0.57	4.11
used	—	0.31	8.13	2.52	0.61	4.57
40%Ce/13X
fresh	35.1	0.12	10.8	1.30	0.55	3.11
used	—	0.19	9.3	1.77	0.58	3.42

图10 不同催化剂的H2-TPR谱图

Fig.10 The H2-TPR profiles of different CeO2-based catalysts

图11 不同反应条件下30%Ce/13X催化剂的O2-TPD

Fig.11 The O2-TPD of 30%Ce/13X catalyst under different reaction conditions

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低温等离子体协同CeO₂/13X催化降解甲苯

Combing low-temperature plasma with CeO₂/13X for toluene degradation

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