|
|
Preparation of Cu-Mn-Zr composite catalyst and performance for catalytic oxidation of ethyl acetate |
ZHANG Ju-ru, LI Ji-wu |
School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310012, China |
|
|
Abstract The new Cu-Mn-Zr composite catalyst with four molar ratios of different metals was prepared by sol-gel method. The catalysts were characterized by BET, XRD and XPS. The catalytic activity of Cu-Mn-Zr composite catalyst on the simulated gas of ethyl acetate was evaluated by a fixed bed tube reactor. The degradation products of the catalytic reaction were detected qualitatively. Addition of Mn significantly increases the specific surface area and total pore volume of the catalyst. The N2 adsorption-desorption isotherm of the catalyst is type IV. Copper oxide crystals and tetragonal zirconia crystals in the Cu-Zr (1:1) catalyst were observed. The copper oxide crystals decreased with the decrease of Cu ratio, and the addition of Mn resulted in the disappearance of tetragonal zirconia crystals. The catalyst was amorphous and had good dispersibility. Increasing the Mn/Zr molar ratio reduces the binding energy and improves the catalytic activity. Cu-Mn-Zr composite catalyst had good low temperature catalytic activity for ethyl acetate, and the proportion of appropriate components will increase the catalytic activity of the catalyst. The catalyzed oxidation effect of Cu-Mn-Zr (1:1:1) catalyst for ethyl acetate was the best, and its selectivity of CO2 reached 96.7% at 200℃. The analysis results of degradation products showed that the intermediate products of ethyl acetate degradation were acetic acid and ethanol, and the final degradation products were mainly CO2 and H2O.
|
Received: 26 December 2017
|
|
|
|
|
[1] |
王宇楠,叶代启,林俊敏,等.漆包线行业挥发性有机物(VOCs)排放特征研究[J]. 中国环境科学, 2012,32(6):980-987.
|
[2] |
王海林,聂磊,李靖,等.重点行业挥发性有机物排放特征与评估分析[J]. 科学通报, 2012,57(19):1739-1746.
|
[3] |
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.
|
[4] |
黎维彬,龚浩.催化燃烧去除VOCs污染物的最新进展[J]. 物理化学学报, 2010,26(4):885-894.
|
[5] |
Kamiuchi N, Mitsui T, Yamaguchi N, et al. Activation of Pt/SnO2, catalyst for catalytic oxidation of volatile organic compounds[J]. Catalysis Today, 2010,157(1-4):415-419.
|
[6] |
Chen C, Wang X, Zhang J, et al. Superior performance in catalytic combustion of toluene over mesoporous ZSM-5zeolite supported platinum catalyst[J]. Catalysis Today, 2014,144(11):1851-1859.
|
[7] |
Cordi E M, O'Neill P J, Falconer J L. Transient oxidation of volatile organic compounds on a CuO/Al2O3catalyst[J]. Applied Catalysis B Environmental, 1997,14(1/2):23-36.
|
[8] |
Aguero F N, Barbero B P, Almeida L C, et al. MnOx, supported on metallic monoliths for the combustion of volatile organic compounds[J]. Chemical Engineering Journal, 2011,166(1):218-223.
|
[9] |
Tang W, Wu X, Li S, et al. Co-nanocasting synthesis of mesoporous Cu-Mn composite oxides and their promoted catalytic activities for gaseous benzene removal[J]. Applied Catalysis B-Environmental, 2015,162:110-121.
|
[10] |
Chen H, Zhang H, Yan Y. Catalytic Combustion of Volatile Organic Compounds over a Structured Zeolite Membrane Reactor[J]. Industrial & Engineering Chemistry Research, 2013,52:12819-12826.
|
[11] |
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, 2016,42:16563-16570.
|
[12] |
Hu F, Chen J, Zhao S, et al. Toluene catalytic combustion over copper modified Mn0.5Ce0.5Ox solid solution sponge-like structures[J]. Applied Catalysis A:General, 2017,540:57-67.
|
[13] |
Lu H, Kong X, Huang H, et al. Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene[J]. Journal of Environmental Sciences-China, 2015,32:102-107.
|
[14] |
Lu H F, Zhou Y, Huang H F, Zhang B, et al. In-situ synthesis of monolithic Cu-Mn-Ce/cordierite catalysts towards VOCs combustion[J]. Journal of Rare Earths, 2011,29(9):855-859.
|
[15] |
Zimowska M, Michalik-Zym A, Janik R. et al. Catalytic combustion of toluene over mixed Cu-Mn oxides[J]. Catalysis Today, 2007,119:321-326.
|
[16] |
王淑媛,李济吾,洪亚军. Ti-Cu-Mn复合物负载石墨烯催化剂制备及其降解二甲苯性能.环境科学学报, 2016,37(7):2375-2381.
|
[17] |
Njagi E C, Chen C H, Genuino H, et al. Total oxidation of CO at ambient temperature using copper manganese oxide catalysts prepared by a redox method[J]. Applied Catalysis B Environmental, 2010, 99(1/2):103-110.
|
[18] |
Li J, Zhu P, Zhou R. Effect of the preparation method on the performance of CuO-MnOx-CeO2, catalysts for selective oxidation of CO in H2 -rich streams[J]. Journal of Power Sources, 2011,196(22):9590-9598.
|
[19] |
Gong Y, Chen H, Chen Y, et al. A Cu/Mn co-loaded mesoporous ZrO2 -TiO2, composite and its CO catalytic oxidation property[J]. Journal of Inorganic Materials, 2013,173(9):112-120.
|
[20] |
Liu L, Song Y, Fu Z, et al. Enhanced catalytic performance of Cu-and/or Mn-loaded Fe-Sep catalysts for the oxidation of CO and ethyl acetate[J]. Chinese Journal of Chemical Engineering, 2017,(10):1427-1434.
|
[21] |
Li S, Hao Q, Zhao R, et al. Highly efficient catalytic removal of ethyl acetate over Ce/Zr promoted copper/ZSM-5catalysts[J]. Chemical Engineering Journal, 2016,285:536-543.
|
[22] |
Azalim S, Franco M, Brahmi R, et al. Removal of oxygenated volatile organic compounds by catalytic oxidation over Zr-Ce-Mn catalysts.[J]. Journal of Hazardous Materials, 2011,188(1-3):422-427.
|
[23] |
Sing K S W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984)[J]. Pure & Applied Chemistry, 1985,57(4):603-619.
|
[24] |
Schittkowski J, Tölle K, Anke S, et al. 2017 On the bifunctional nature of Cu/ZrO2 catalysts applied in the hydrogenation of ethyl acetate[J]. Journal of Catalysis, 352:120-129.
|
[25] |
Lahousse C, Bernier A, Grange P, et al. Evaluation of γ-MnO2 as a VOC Removal Catalyst:Comparison with a Noble Metal Catalyst[J]. Journal of Catalysis, 1998,178(1):214-225.
|
[26] |
Sadia Akram, Zhen Wang, Lan Chen, et al. Low-temperature efficient degradation of ethyl acetate catalyzed by lattice-doped CeO2-CoOx, nanocomposites[J]. Catalysis Communications, 2016,73(1):123-127.
|
[27] |
Huang Y, Luo C, Yang S, et al. Improved Removal of Indoor Volatile Organic Compounds by Activated Carbon Fiber Filters Calcined with Copper Oxide Catalyst[J]. CLEAN-Soil, Air, Water, 2015,38(11):993-997.
|
[28] |
Ramesh K, Chen L, Chen F, et al. Re-investigating the CO oxidation mechanism over unsupported MnO, Mn2O3, and MnO2, catalysts[J]. Catalysis Today, 2008,131(1-4):477-482.
|
[29] |
Tsoncheva T, Ivanova R, Henych J, et al. Iron modified titanium-hafnium binary oxides as catalysts in total oxidation of ethyl acetate[J]. Catalysis Communications, 2016,81:14-19.
|
[30] |
Lu Z, Yin H, Wang A, et al. Hydrogenation of ethyl acetate to ethanol over Cu/ZnO/MOx, (MOx=SiO2, Al2O3, and ZrO2) catalysts[J]. Journal of Industrial & Engineering Chemistry, 2016,37:208-215.
|
[31] |
Sadia Akram, Zhen Wang, Lan Chen, et al. Low-temperature efficient degradation of ethyl acetate catalyzed by lattice-doped CeO2-CoOx, nanocomposites[J]. Catalysis Communications, 2016,73(6):123-127.
|
[32] |
Zhu X, Zhang S, Yang Y, et al. Enhanced performance for plasma-catalytic oxidation of ethyl acetate over La1-xCexCoO3+δ, catalysts[J]. Applied Catalysis B Environmental, 2017,213:97-105.
|
|
|
|