Catalytic combustion of toluene over cerium modified CuMn/Al2O3/cordierite monolithic catalyst
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摘要: 本研究以堇青石为载体，采用超声浸渍法制备了一系列CuMnCex/Al2O3/堇青石整体式催化剂，同时，通过N2吸附-脱附、XRD、SEM、EDX、H2-TPR、O2-TPD、XPS和EPR等方法对样品的物理、化学性质进行了系统的表征分析。实验结果表明，CuMnCex/Al2O3/堇青石整体式催化剂中的Ce含量明显影响甲苯催化燃烧性能。其中，CuMnCe2/Al2O3/堇青石整体式催化剂对甲苯氧化具有最高活性，当甲苯浓度为1 g/L、空速为78000 mL/(g·h)、温度为263 °C时甲苯转化率达到90%，究其原因为CeO2在CuMnOx上分散均匀，不仅提高了氧空位的浓度和氧物种的迁移率，还增强了催化剂的低温还原性。同时，CuMnCe2/Al2O3/堇青石整体式催化剂在长期评价和循环测试中呈现良好的稳定性。
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关键词:
- 甲苯 /
- 催化燃烧 /
- 整体式催化剂 /
- CuMnCex复合氧化物
Abstract: Catalytic combustion is an effective approach to remove volatile organic compounds, in which the development of highly active and durable catalyst is extremely crucial. Herein, a series of CuMnCex/Al2O3/cordierite monolithic catalysts were synthesized by using the ultrasonic-assisted impregnation method. The physicochemical properties were comprehensively characterized via the BET, XRD, SEM, EDX, H2-TPR, O2-TPD, XPS and EPR techniques. The results showed that the catalytic activity of CuMnCex/Al2O3/Cor for toluene combustion was strongly affected by the Ce content. The CuMnCe2/Al2O3/Cor monolithic catalyst showed the best catalytic activity with toluene conversion of 90% at 263 °C under toluene concentration of 1 g/L and space velocity of 78000 mL/(g·h). Meanwhile, the well-dispersed CeO2 in the CuMn matrix not only improved the content of oxygen vacancies and the mobility of oxygen species, but also enhanced the low-temperature reducibility of the catalyst. Moreover, the CuMnCe2/Al2O3/Cor monolithic catalyst exhibited an excellent stability in the long-term test and cycle ability test.-
Key words:
- toluene /
- catalytic combustion /
- monolithic catalyst /
- CuMnCex composite oxide
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Figure 1 N2 adsorption-desorption isotherms (a) and pore size distributions (b) of CuMnCex/Al2O3/Cor monolithic catalysts
Figure 3 SEM images of CuMnCex/Al2O3/Cor monolithic catalysts
(a): CuMn/Al2O3/Cor; (b): CuMnCe0.5/Al2O3/Cor; (c): CuMnCe0.8/Al2O3/Cor; (d): CuMnCe2/Al2O3/Cor; (e): CuMnCe3/Al2O3/Cor.
Figure 4 EDX images of CuMnCex/Al2O3/Cor monolithic catalysts
(a): CuMnCe0.5/Al2O3/Cor; (b): CuMnCe0.8/Al2O3/Cor; (c): CuMnCe2/Al2O3/Cor; (d): CuMnCe3/Al2O3/Cor.
Figure 9 Catalytic performance of CuMnCex/Al2O3/Cor (x=0, 0.5, 0.8, 2, 3) catalysts for toluene combustion
Reaction conditions: toluene concentration=1 g/L, total flow rate=130 mL/min, GHSV=78000 mL/(g·h).
Figure 10 Long-term evaluation (a) and recycling performance (b) of CuMnCe2/Al2O3/Cor catalyst for toluene oxidation
Reaction conditions: toluene concentration=1 g/L, temperature=270 °C, total flow rate=130 mL/min, GHSV=78000 mL/(g·h).
Table 1 Structural properties, loading percentages and weight loss of monolithic catalyst
Sample ${S_{ {\rm{BET} } }}^{\rm{a}}$
/(m2·g−1)${v_{{\rm{total}}}}^{\rm{b}} $
/(cm3·g−1)dpc
/nmLoadingd
w/%Weight losse w/% Cordierite 0.2 − − − − CuMn 11.5 0.0304 7.0 18.5 0.45 CuMnCe0.5 9.4 0.0233 6.2 19.6 0.42 CuMnCe0.8 12.4 0.0291 6.1 20.3 0.48 CuMnCe2 17.8 0.0413 6.6 26.0 0.51 CuMnCe3 10.8 0.0404 9.0 27.0 0.52 Note: a: Obtained by BET method; b: Estimated from the amount adsorbed at p/p0=0.99; c: Calculated using the BJH method; d: Active component load rate; e: Weight loss rate of active component. 
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Table 2 Surface elemental analysis of CuMn and CuMnCex monolithic catalysts
Sample Mn4+/Mn Ce3+/Ce Cu+/Cu2+ Osur/Ototal CuMn 0.25 − 0.11 0.36 CuMnCe0.5 0.27 0.17 0.09 0.38 CuMnCe0.8 0.31 0.18 0.09 0.44 CuMnCe2 0.37 0.20 0.09 0.46 CuMnCe3 0.32 0.14 0.10 0.43
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Table 3 Catalytic activity of several related catalysts for toluene combustion
Catalyst Toluene concentration
/(g·L−1)Catalyst amount
/gGHSV
/(mL·g–1·h–1)t50
/°Ct90
/°CRef. CuMn/Al2O3/Cor 1 0.1 78000 286 300 this work CuMnCe0.5/Al2O3/Cor 1 0.1 78000 274 287 this work CuMnCe0.8/Al2O3/Cor 1 0.1 78000 267 282 this work CuMnCe2/Al2O3/Cor 1 0.1 78000 244 263 this work CuMnCe3/Al2O3/Cor 1 0.1 78000 262 284 this work Cu-Co/Halloysite 0.6 0.2 60000 272 301 [58] CeO2/δ-MnO2 1 0.2 15000 237 277 [59] MnCe/ZrO2 1 0.1 36000 257 290 [60] MOx/HZSM-5 1 0.4 15000 276 285 [61] Cu-Mn-Ce/Al2O3 0.5 0.5 20000 315 340 [62]
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