Catalytic combustion of toluene over Cu-Mn mixed oxide catalyst

doi:10.11949/j.issn.0438-1157.20151864

Abstract

Abstract:

A series of copper manganese mixed oxide catalysts Cu₁_-xMn_x (x 0—1.0) with high surface area were synthesized by using carbonate co-precipitation method and their performance in catalytic combustion reaction of toluene was investigated by varying the mole ratio of Cu and Mn. XRD, H₂-TPR, XPS and N₂ adsorption/ desorption were used to characterize the structure and textural properties of catalysts. The resulting Cu₁_-xMn_x catalyst showed higher catalytic activity than mono-metal oxide catalyst, especially when a small amount of copper was doped into manganese oxide. With increasing the manganese content from 0 to 1.0, a volcanic tendency for catalytic activity was observed. Results of catalyst characterization revealed that the promoted catalytic activity can be associated with some interrelated factors, such as depressed crystallinity, highly dispersed oxide species onto the other, easier catalyst reducibility, more surface oxygen and enhanced surface area. It was difficult to attribute the promoted catalytic activity only to a single and specific factor. A synergistic effect between manganese and copper species was considered to be the most intrinsic reason.

Key words: toluene, catalytic combustion, copper, manganese, mixed metal oxides, catalyst, reactivity, numerical analysis

摘要：

采用碳酸盐共沉淀法在全范围内制备了一系列具有高比表面积的铜锰互相掺杂的复合氧化物，通过调变铜锰摩尔比考察了其在甲苯催化燃烧反应中的表现。铜锰复合氧化物催化剂，尤其是掺杂低浓度铜的氧化锰，在甲苯催化燃烧中表现出了超越单组分氧化物的性能。随掺杂量的变化，反应活性呈现火山状的趋势。XRD、H₂-TPR、XPS及BET等表征结果显示氧化物粒子的结晶度及分散度、催化剂的可还原性、表面氧浓度、催化剂的比表面积等诸多因素均对催化活性产生了一定的影响，然而复合氧化物催化性能上升的根本原因在于铜物种和锰物种之间存在的较强的相互协同作用。

关键词: 甲苯, 催化燃烧, 铜, 锰, 复合金属氧化物, 催化剂, 活性, 数值分析

CLC Number:

TQ032
O643

GU Ouyun, LIAO Yongtao, CHEN Ruijie, JIA Lu, KAMEYAMA Hideo, LIN Yi, ZHOU Lü, MA Hua, GUO Yu. Catalytic combustion of toluene over Cu-Mn mixed oxide catalyst[J]. CIESC Journal, 2016, 67(7): 2832-2840.

顾欧昀, 廖永涛, 陈锐杰, 贾璐, 龟山秀雄, 林益, 周吕, 马华, 郭燏. 铜锰复合氧化物催化剂上甲苯的催化燃烧[J]. 化工学报, 2016, 67(7): 2832-2840.

References 26

[1]	LAMB A B, BRAY W C, FRAZER J C W. The removal of carbon monoxide from air [J]. Ind. Eng. Chem., 1920, 12 (3): 213-221.
[2]	CHEN H, WANG J H, LI H, et al. Low temperature combustion of ethylene in a carbon dioxide stream over a cordierite monolith- supported Cu-Mn Hopcalite catalyst [J]. Applied Catalysis A: General, 2012, 427/428: 73-78.
[3]	HOSSEINI S A, NIAEI A, SALARI D, et al. Study of correlation between activity and structural properties of Cu-(Cr, Mn and Co) nano mixed oxides in VOC combustion [J]. Ceramics International, 2014, 40 (4): 6157-6163.
[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. LI W B, GONG H. Recent progress in the removal of volatile organic compounds by catalytic combustion [J]. Acta Phys.-Chim. Sin., 2010, 26 (4): 885-894.
[5]	CAO H Y, LI X S, CHEN Y Q, et al. Effect of loading content of copper oxides on performance of Mn-Cu mixed oxide catalysts for catalytic combustion of benzene [J]. Journal of Rare Earths, 2012, 30 (9): 871-877.
[6]	HE C, YU Y K, SHI J W, et al. Mesostructured Cu-Mn-Ce-O composites with homogeneous bulk composition for chlorobenzene removal: catalytic performance and micro activation course [J]. Materials Chemistry and Physics, 2015, 157: 87-100.
[7]	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.
[8]	LU H F, KONG X X, HUANG H F, et al. Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene [J]. Journal of Environmental Sciences, 2015, 32: 102-107.
[9]	邓丽杰, 陈平, 楼辉, 等. 铜掺杂Mn-Ce-O固溶体催化剂用于甲醛催化燃烧的性能研究 [J]. 浙江大学学报, 2011, 38 (4): 424-427. DENG L J, CHEN P, LOU H, et al. Catalytic combustion of formaldehyde over Cu-doped Mn-Ce-O solid solution catalysts [J]. Journal of Zhejiang University, 2011, 38 (4): 424-427.
[10]	SAQER S M, KONDARIDES D I, VERYKIOS X E. Catalytic oxidation of toluene over binary mixtures of copper, manganese and cerium oxides supported on γ-Al2O3 [J]. Applied Catalysis B: Environmental, 2011, 103: 275-286.
[11]	DELIMARIS D, IOANNIDES T. VOC oxidation over MnOx-CeO2 catalysts prepared by a combustion method [J]. Applied Catalysis B: Environmental, 2008, 84: 303-312.
[12]	DELIMARIS D, IOANNIDES T. VOC oxidation over CuO-CeO2 catalysts prepared by a combustion method [J]. Applied Catalysis B: Environmental, 2009, 89: 295-302.
[13]	TANASOI S, MITRANA G, TANCHOUX N, et al. Transition metal-containing mixed oxides catalysts derived from LDH precursors for short-chain hydrocarbons oxidation [J]. Applied Catalysis A: General, 2011, 395: 78-86.
[14]	蔡丽娜. 铜锰氧化物制备改性及其CO催化氧化性能研究 [D]. 大连:大连理工大学, 2014. CAI L N. Modification of copper manganese oxide and its catalytic performance in carbon monoxide oxidation [D]. Dalian: Dalian University of Technology, 2014.
[15]	QIAN K, QIAN Z, HUA Q, et al. Structure-activity relationship of CuO/MnO2 catalysts in CO oxidation [J]. Applied Surface Science, 2013, 273: 357-363.
[16]	HABIBI M H, KARIMI B. Preparation of nanostructure CuO/ZnO mixed oxide by sol-gel thermal decomposition of a CuCO3 and ZnCO3: TG, DTG, XRD, FESEM and DRS investigations [J]. Journal of Industrial and Engineering Chemistry, 2014, 20: 925-929.
[17]	刘意, 刘勇, 陈建峰, 等. 不同氧化锰载体对费托钴基催化剂合成低碳烯烃的影响 [J]. 化工学报, 2015, 66 (9): 3413-3420. LIU Y, LIU Y, CHEN J F, et al. Effects of MnOx supports on light olefin synthesis using cobalt catalyst in Fischer-Tropsch reaction [J]. CIESC Journal, 2015, 66 (9): 3413-3420.
[18]	ZHAO F Z, ZHANG G H, ZENG P H. Preparation of CuxCo1-x/Al2O3/Cordierite monolithic catalysts and the catalytic combustion of toluene [J]. Chinese Journal of Catalysis, 2011, 32 (5): 821-826.
[19]	卢晗锋, 黄金星, 周瑛, 等. 沉淀剂对Cu-Mn-Ce复合氧化物催化剂结构和性能的影响 [J]. 化工学报, 2015, 66 (6): 2105-2111. LU H F, HUANG J X, ZHOU Y, et al. Effect of precipitants on structure and performance of Cu-Mn-Ce mixed oxide catalysts [J]. CIESC Journal, 2015, 66 (6): 2105-2111.
[20]	ZIMIWSKA M, MICHALIK Z A, JANIK R, et al. Catalytic combustion of toluene over mixed Cu-Mn oxides [J]. Catalysis Today, 2007, 119 (1/2/3/4): 321-326.
[21]	JOAN P, GEORGE A, THEOPHILOS I. Combined steam reforming of methanol over Cu-Mn spinel oxide catalysts [J]. Journal of Catalysis, 2007, 251: 7-20.
[22]	孟凡会, 常慧蓉, 李忠. Ni-Mn/Al2O3催化剂在浆态床中CO甲烷化催化性能 [J]. 化工学报, 2014, 65 (8): 2997-3003. MENG F H, CHANG H R, LI Z. Catalytic performance of Ni-Mn/Al2O3 catalyst for CO methanation in slurry-bed reactor [J]. CIESC Journal, 2014, 65 (8): 2997-3003.
[23]	胡菊, 潘亚林, 黎汉生, 等. 铈改性甲醇合成铜基催化剂的制备及其性能 [J]. 化工学报, 2014, 65 (7): 2770-2775. HU J, PAN Y L, LI H S, et al. Preparation and properties of cerium modified Cu-based catalysts for methanol synthesis [J]. CIESC Journal, 2014, 65 (7): 2770-2775.
[24]	BIELANSKI A, HABER J. Oxygen in catalysis on transition metal oxides [J]. Catal. Rev. Sci. Eng., 1979, 19 (1): 1-41.
[25]	FEYEN M, WEIDENTHALE C, SCHUTH F, et al. Synthesis of structurally stable colloidal composites as magnetically recyclable acid catalysts [J]. Chem. Mater., 2010, 22 (9): 2955-2961.
[26]	GARCIA T, SELICK D, VARELA F, et al. Total oxidation of naphthalene using bulk manganese oxide catalysts [J]. Applied Catalysis A: General, 2013, 450: 169-177.