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

doi:10.15541/jim20140672

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 8

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

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

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

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

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

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

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

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

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

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