焙烧温度对Cu-Mn/γ-Al2O3催化剂催化氧化甲苯性能的影响

doi:10.15541/jim20140672

无机材料学报 ›› 2015, Vol. 30 ›› Issue (7): 694-698.DOI: 10.15541/jim20140672

焙烧温度对Cu-Mn/γ-Al₂O₃催化剂催化氧化甲苯性能的影响

郑遗凡^1,2, 仲淑彬¹, 吕德义¹, 周环², 郇昌永³

(1. 浙江工业大学化学工程学院, 杭州 310014; 2. 浙江工业大学分析测试中心, 杭州310014; 3. 宁波化学工业区博士后科研工作站, 宁波315204)

收稿日期:2014-12-25 修回日期:2015-03-13 出版日期:2015-07-20 网络出版日期:2015-06-25
作者简介:郑遗凡(1964–), 男, 博士. E-mail: zhengyifan@zjut.edu.cn
基金资助:
国土资源部粘土矿物重点实验室开放课题(2014-K4);中国地质大调查项目(12120113015100);浙江省公益性技术应用研究(分析测试)项目(2012C37013)

Effect of Calcination Temperature of Cu-Mn/γ-Al₂O₃ Catalysts on Performance for Catalytic Oxidation of Toluene

ZHENG Yi-Fan^1,2, ZHONG Shu-Bin¹, LV De-Yi¹, ZHOU Huan², HUAN Chang-Yong³

(1. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China; 2. Research Center of Analysis and Measurment, Zhejiang University of Technology, Hangzhou 310014, China; 3. National Post-Doctoral Scientific Research Center of Ningbo Petrochemical Economic & Technological Development Zone, Ningbo 315204, China)

Received:2014-12-25 Revised:2015-03-13 Published:2015-07-20 Online:2015-06-25
About author:ZHENG Yi-Fan. E-mail: zhengyifan@zjut.edu.cn
Supported by:
Open Fund from Key Laboratory of Clay Minerals of the Ministry of Land and Resources, China(2014-K4);Project of China Geological Survey (12120113015100);Zhejiang Province Public Technology Applied Research Project (2012C37013)

摘要/Abstract

摘要：

采用浸渍法合成了Cu-Mn/γ-Al₂O₃催化剂, 通过XRD、BET、H₂-TPR和XPS等方法对经不同温度(300~600℃)焙烧的催化剂进行表征, 采用固定床管式反应装置考察了焙烧温度对催化剂催化氧化甲苯的影响, 并讨论活性组分、表面Cu⁺/(Cu⁺+Cu²⁺)和Mn⁴⁺/(Mn⁴⁺+Mn³⁺)摩尔比值与催化剂活性的关系。结果发现, 550℃焙烧温度的催化剂活性最好, 氧化能力最强, 其转化率为95%时对应的反应温度T₉₅(286 ℃)最低, CO₂的选择性达100%。在550℃焙烧时生成的Cu_1.4Mn_1.6O₄新相以及催化剂表面中相对含量更高的Cu⁺和Mn⁴⁺是催化剂具有高活性的主要原因。

关键词: 铜锰氧化物, 催化氧化, 甲苯, 焙烧温度

Abstract:

Cu-Mn/γ-Al₂O₃ catalysts were prepared by impregnation method and calcined at different temperatures (300-600℃), which were characterized by XRD, BET, H₂-TPR and XPS. Their performances for catalytic oxidation of toluene were evaluated in a fixed-bed tubular reactor, and the correlation of catalytic activity with active phases or mole ratios of both Cu⁺/(Cu⁺+Cu²⁺) and Mn⁴⁺/(Mn⁴⁺+Mn³⁺) was discussed. Among all catalysts, the Cu-Mn/ γ-Al₂O₃ catalyst calcined at 550℃ shows the best catalytic activity, with a lowest reaction temperature (T₉₅is 286℃) and 100% selectivity of CO₂. The generation of new phase (Cu_1.4Mn_1.6O₄) and more amount of Cu⁺ and Mn⁴⁺ ions present on the surface of the catalyst calcined at 550℃ are responsible for its high activity.

Key words: copper-manganese oxide, catalytic oxidation, toluene, calcination temperature

中图分类号:

TQ174

郑遗凡, 仲淑彬, 吕德义, 周环, 郇昌永. 焙烧温度对Cu-Mn/γ-Al₂O₃催化剂催化氧化甲苯性能的影响[J]. 无机材料学报, 2015, 30(7): 694-698.

ZHENG Yi-Fan, ZHONG Shu-Bin, LV De-Yi, ZHOU Huan, HUAN Chang-Yong. Effect of Calcination Temperature of Cu-Mn/γ-Al₂O₃ Catalysts on Performance for Catalytic Oxidation of Toluene[J]. Journal of Inorganic Materials, 2015, 30(7): 694-698.

图/表 8

图1 经不同温度焙烧的铜锰氧化物催化剂催化氧化甲苯的转化率随反应温度的变化

Fig. 1 Toluene conversion as a function of the reaction temperature for Cu-Mn/γ-Al2O3 catalysts calcined at various temperatures

表1 经不同温度焙烧的铜锰氧化物催化剂的T50, T95和比表面积

Table 1 T50, T95 and speciﬁc surface areas (SSA) for Cu-Mn/γ-Al2O3 catalysts calcined at various temperatures

Catalysts	T₅₀/℃	T₉₅/℃	SSA/(m²•g^-1)
Cu-Mn/γ-Al₂O₃-300	263	287	78
Cu-Mn/γ-Al₂O₃-400	265	301	73
Cu-Mn/γ-Al₂O₃-500	277	324	75
Cu-Mn/γ-Al₂O₃-550	276	286	70
Cu-Mn/γ-Al₂O₃-600	282	369	57

表2 不同焙烧温度的铜锰氧化物催化剂的活性组成和晶粒度

Table 2 Crystalline phases and crystalline size of Cu-Mn/γ-Al2O3 catalysts calcined at various temperatures

Calcination temperature/℃	Crystalline phases	Crystalline phases
Calcination temperature/℃	Crystalline phases	CuO	Cu_1.4Mn_1.6O₄
300	CuO, Cu_0.451Mn_0.549O₂, γ-Al₂O₃	18.5	-
400	CuO, Cu_0.451Mn_0.549O₂, γ-Al₂O₃	20.0	-
500	CuO, Cu_0.451Mn_0.549O₂, γ-Al₂O₃	21.0	-
550	CuO, Cu_1.4Mn_1.6O₄, γ-Al₂O₃	23.0	20
600	CuO, Cu_1.4Mn_1.6O₄, γ-Al₂O₃	26.0	25

图2 焙烧温度为300℃和550℃的铜锰氧化物催化剂对CO2选择性随反应温度的变化

Fig. 2 CO2 selectivity as a function of the reaction temperature for Cu-Mn/γ-Al2O3 catalysts calcined at 300℃and 550℃

图 3 经不同温度焙烧的铜锰氧化物催化剂的XRD图谱

Fig. 3 XRD patterns of Cu-Mn/γ-Al2O3 catalysts calcined at various temperatures (a) Cu-Mn/γ-Al2O3-300; (b) Cu-Mn/γ-Al2O3-400; (c) Cu-Mn/γ-Al2O3-500; (d) Cu-Mn/γ-Al2O3-550; (e) Cu-Mn/γ-Al2O3-600

图4 经不同温度焙烧的铜锰氧化物催化剂的Mn2p(A)和Cu2p (B)的XPS谱图

Fig. 4 Mn2p (A) and Cu2p (B) XPS spectra of Cu-Mn/γ- Al2O3 catalysts calcined at various temperatures (a) Cu-Mn/γ-Al2O3-400; (b) Cu-Mn/γ-Al2O3-550

表3 不同焙烧温度的Cu2p与Mn2p的结合能和表面Cu+占总铜与Mn4+占总锰的比值

Table 3 Binding energy of Cu2p and Mn2p and proportion of Cu +and Mn4+ in all Cu and Mn of Cu-Mn/γ-Al2O3 catalysts calcined at various temperatures

Catalysts	Binding energy/eV				Cu⁺/(Cu⁺+Cu²⁺)	Mn^{4 +}/(Mn³⁺+Mn^{4 +})
Catalysts	Cu⁺	Cu²⁺	Mn^{3 +}	Mn⁴⁺	Cu⁺/(Cu⁺+Cu²⁺)	Mn^{4 +}/(Mn³⁺+Mn^{4 +})
Cu-Mn/γ-Al₂O₃-300	-	933.8	641.2	642.5	-	0.85
Cu-Mn/γ-Al₂O₃-400	931.2	933.4	641.1	642.4	0.06	0.82
Cu-Mn/γ-Al₂O₃-500	931.1	933.4	641.0	642.3	0.07	0.80
Cu-Mn/γ-Al₂O₃-550	931.4	934.1	641.0	642.5	0.12	0.86
Cu-Mn/γ-Al₂O₃-600	931.4	934.1	641.1	642.5	0.11	0.81

图5 经不同温度焙烧的铜锰氧化物催化剂的H2-TPR图

Fig. 5 H2-TPR profiles of Cu-Mn/γ-Al2O3 catalysts calcined at various temperatures

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焙烧温度对Cu-Mn/γ-Al₂O₃催化剂催化氧化甲苯性能的影响

Effect of Calcination Temperature of Cu-Mn/γ-Al₂O₃ Catalysts on Performance for Catalytic Oxidation of Toluene

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