以CoMn<sub>2</sub>O<sub>4</sub>为催化剂氧化二甲苯的研究

摘要探索催化剂的制备条件，包括搅拌温度、干燥温度、煅烧温度及煅烧时间对二甲苯氧化效果的影响，结果表明煅烧温度对氧化效果的影响最为明显。在其它制备条件（搅拌温度为60 ℃、干燥温度为60 ℃和煅烧时间为3 h）不变的前提下，通过改变煅烧温度（温度分别350、450和550 ℃），比较3种二甲苯氧化难易以及不同煅烧温度下氧化同一构型二甲苯的差异。整体而言，煅烧温度为350 ℃的催化剂性能最佳。邻、间和对3种二甲苯完全氧化的温度相差约15 ℃，其中，邻二甲苯最难氧化，完全氧化需260 ℃，间二甲苯次之，对二甲苯最易氧化。与此同时，利用XRD、XPS、N₂吸附-脱附和H₂-TPR等表征手段来分析煅烧温度造成3种不同构型二甲苯氧化程度差异性的原因。

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	宇富航
	李永红
	鲁倩文
	李肖静

关键词：二甲苯复合金属氧化物催化氧化

Abstract： In this experiment, the effect of preparation conditions, including stirring temperature, drying temperature, calcination temperature and time on the catalytic performance for xylene oxidation was investigated. The experimental results indicated that calcination temperature was the most significant influencing factor on oxidation. When stirring temperature is 60 ℃, drying temperature is 60 ℃ and calcination time is 3 h, the effect of the calcination temperature (350 ℃, 450 ℃, 550 ℃on the difficulty degree of oxidation of these three xylenes and the difference of xylene oxidation with same configuration were investigated. Overall, catalyst with calcination temperature of 350 ℃ was the best, and the three isomeric xylenes had a complete oxidation difference of about 15 ℃. Among them, o-xylenes was the most difficult to be oxidized, and the temperature required for complete oxidation was 260 ℃. m-Xylene was the second difficult to be oxidized, followed by p-xylene. Meanwhile, XRD, XPS, N₂ adsorption and desorption, H₂-TPR and other characterizations were used to analyze the reason why calcination temperature caused the difference in oxidation degree among the three different configurations of xylene.

Keywords： xylene； composite metal oxide； catalytic oxidation

Received 2020-06-12;

Corresponding Authors: 李永红,E-mail:yhli@tju.edu.cn。 Email: yhli@tju.edu.cn

About author: 宇富航(1995-),男,硕士研究生,现从事VOCs催化氧化方面的研究。

引用本文:

宇富航, 李永红, 鲁倩文, 李肖静.以CoMn₂O₄为催化剂氧化二甲苯的研究[J]. 化学工业与工程, 2021,38(4): 25-36

Yu Fuhang, Li Yonghong, Lu Qianwen, Li Xiaojing.Study on the Oxidation of Xylene with CoMn₂O₄ as Catalyst[J]. Chemcial Industry and Engineering, 2021,38(4): 25-36

[1] Zheng J, Yu Y, Mo Z, et al. Industrial sector-based volatile organic compound (VOC) source profiles measured in manufacturing facilities in the Pearl River Delta, China[J]. Science of the Total Environment, 2013, 456/457:127-136
[2] Yuan B, Shao M, Lu S, et al. Source profiles of volatile organic compounds associated with solvent use in Beijing, China[J]. Atmospheric Environment, 2010, 44(15):1919-1926
[3] Wang H, Qiao Y, Chen C, et al. Source profiles and chemical reactivity of volatile organic compounds from solvent use in Shanghai, China[J]. Aerosol and Air Quality Research, 2014, 14(1):301-310
[4] Wu F, Yu Y, Sun J, et al. Characteristics, source apportionment and reactivity of ambient volatile organic compounds at Dinghu Mountain in Guangdong Province, China[J]. Science of the Total Environment, 2016, 548/549:347-359
[5] Liu Z, Li N, Wang N. Characterization and source identification of ambient VOCs in Jinan, China[J]. Air Quality, Atmosphere & Health, 2016, 9(3):285-291
[6] He Q, Yan Y, Li H, et al. Characteristics and reactivity of volatile organic compounds from non-coal emission sources in China[J]. Atmospheric Environment, 2015, 115:153-162
[7] Huang S, Yang D, Tang Q, et al. Pt-loaded ellipsoidal nanozeolite as an active catalyst for toluene catalytic combustion[J]. Microporous and Mesoporous Materials, 2020, doi:10.1016/j.micromeso.2020.110292
[8] Huang S, Deng W, Zhang L, et al. Adsorptive properties in toluene removal over hierarchical zeolites[J]. Microporous and Mesoporous Materials, 2020, doi:10.1016/j.micromeso.2020.110204
[9] 赵倩, 葛云丽, 纪娜,等. 催化氧化技术在可挥发性有机物处理的研究[J]. 化学进展, 2016, 28(12):1847-1859 Zhao Qian,Ge Yunli,Ji Na, et al. Removal of volatile organic compounds by catalytic oxidation technology[J]. Progress in Chemistry, 2016, 28(12):1847-1859(in Chinese)
[10] 席劲瑛, 武俊良, 胡洪营, 等. 工业VOCs气体处理技术应用状况调查分析[J]. 中国环境科学, 2012, 32(11):1955-1960 Xi Jinying, Wu Junliang, Hu Hongying, et al. Application status of industrial VOCs gas treatment techniques[J]. China Environmental Science, 2012, 32(11):1955-1960(in Chinese)
[11] Wang Y, Zhang C, He H. Cover feature:Insight into the role of Pd state on Pd-based catalysts in o-xylene oxidation at low temperature[J]. ChemCatChem, 2018, 10(5):998-1004
[12] Qiao Nanli, Zhang Xin, He Chi, et al. Enhanced performances in catalytic oxidation of o-xylene over hierarchical macro-/mesoporous silica-supported palladium catalysts[J]. 中国环境科学与工程前沿:英文版, 2016(3):458-466
[13] Xie S, Liu Y, Deng J, et al. Mesoporous CoO-supported palladium nanocatalysts with high performance for o-xylene combustion[J]. Catalysis Science & Technology, 2018, 8(3):806-816
[14] 陈孟秋, 王钰, 杨登尧, 等. 载铂多级孔ZSM-5分子筛用于邻二甲苯的"吸附-催化燃烧"循环脱除[J]. 无机材料学报, 2019, 34(2):57-62 Chen Mengqiu, Wang Yu, Yang Dengyao,, et al. Pt supported hierarchical ZSM-5 zeolite as adsorbent/catalytic combustion catalyst for o-xylene elimination[J]. Journal of Inorganic Materials, 2019, 34(2):57-62(in Chinese)
[15] Luu C, Nguyen T, Hoang T, et al. The role of carriers in properties and performance of Pt-CuO nanocatalysts in low temperature oxidation of CO and p-xylene[J]. Advances in Natural Sciences:Nanoscience and Nanotechnology, 2014, doi:10.1088/2043-6262/6/1/015011
[16] Wu Y, Feng R, Song C, et al. Effect of reducing agent on the structure and activity of manganese oxide octahedral molecular sieve (OMS-2) in catalytic combustion of o-xylene[J]. Catalysis Today, 2017, 281:500-506
[17] Wu Y, Yuan S, Feng R, et al. Comparative study for low-temperature catalytic oxidation of o-xylene over doped OMS-2 catalysts:Role of Ag and Cu[J]. Molecular Catalysis, 2017, 442:164-172
[18] Genuino H C, Dharmarathna S, Njagi E C, et al. Gas-phase total oxidation of benzene, toluene, ethylbenzene, and xylenes using shape-selective manganese oxide and copper manganese oxide catalysts[J]. The Journal of Physical Chemistry C, 2012, 116(22):12066-12078
[19] Zhang X, Wu D. Ceramic monolith supported Mn-Ce-M ternary mixed-oxide (M=Cu, Ni or Co) catalyst for VOCs catalytic oxidation[J]. Ceramics International, 2016, 42(15):16563-16570
[20] Xie S, Liu Y, Deng J, et al. Insights into the active sites of ordered mesoporous cobalt oxide catalysts for the total oxidation of o-xylene[J]. Journal of Catalysis, 2017, 352:282-292
[21] Li W, Lin Y. A novel spinel-type Co/Mn catalyst for methane oxidation at low temperatures[J]. Chemistry Letters, 2002, 31(1):84-85
[22] Tang W, Wu X, Li S, et al. Porous Mn-Co mixed oxide nanorod as a novel catalyst with enhanced catalytic activity for removal of VOCs[J]. Catalysis Communications, 2014, 56:134-138
[23] Tomatis M, Xu H, Wei C, et al. A comparative study of Mn/Co binary metal catalysts supported on two commercial diatomaceous earths for oxidation of benzene[J]. Catalysts, 2018, doi:10.3390/catal8030111
[24] Yao L, Zhang L, Liu Y, et al. MnCo₂O₄ and CoMn₂O₄ octahedral nanocrystals synthesized via a one-step co-precipitation process and their catalytic properties in benzyl alcohol oxidation[J]. CrystEngComm, 2016, 18(46):8887-8897
[25] Liu L, Yang Y. Shape-controlled synthesis of MnCo complex oxide nanostructures via a polyol-based precursor route and their catalytic properties[J]. Superlattices and Microstructures, 2013, 54:26-38
[26] Qu Z, Gao K, Fu Q, et al. Low-temperature catalytic oxidation of toluene over nanocrystal-like Mn-Co oxides prepared by two-step hydrothermal method[J]. Catalysis Communications, 2014, 52:31-35
[27] Tang W, Wu X, Li S, et al. Porous Mn-Co mixed oxide nanorod as a novel catalyst with enhanced catalytic activity for removal of VOCs[J]. Catalysis Communications, 2014, 56:134-138
[28] 曲振平, 董翠. 一种用于VOCs催化氧化的纳米花尖晶石CoMn₂O₄催化剂、制备方法以及应用:CN, 108295866A[P]. 2018-07-20
[29] Liu L, Zhang H, Jia J, et al. Direct molten polymerization synthesis of highly active samarium manganese perovskites with different morphologies for VOC removal[J]. Inorganic Chemistry, 2018, 57(14):8451-8457
[30] Chen J, Chen X, Chen X, et al. Homogeneous introduction of CeO_y into MnO_x-based catalyst for oxidation of aromatic VOCs[J]. Applied Catalysis B:Environmental, 2018, 224:825-835
[31] Xia Y, Xia L, Liu Y, et al. Concurrent catalytic removal of typical volatile organic compound mixtures over Au-Pd/α-MnO₂ nanotubes[J]. Journal of Environmental Sciences, 2018, 64:276-288
[32] Clarke T J, Kondrat S A, Taylor S H. Total oxidation of naphthalene using copper manganese oxide catalysts[J]. Catalysis Today, 2015, 258:610-615
[33] Tang W, Li W, Li D, et al. Synergistic effects in porous Mn-Co mixed oxide nanorods enhance catalytic deep oxidation of benzene[J]. Catalysis Letters, 2014, 144(11):1900-1910
[34] Tang W, Ren Z, Lu X, et al. Scalable integration of highly uniform Mn_xCo_3-xO₄ nanosheet array onto ceramic monolithic substrates for low-temperature propane oxidation[J]. Chem Cat Chem, 2017, 9(21):4112-4119