微反应器共沉淀反应制备铜锰催化剂

doi:10.11949/0438-1157.20221575

摘要/Abstract

摘要：

在Caterpillar微反应器中采用共沉淀法制备了不同铜锰比的共沉淀物，直接焙烧得到铜锰复合氧化物催化剂。采用X射线衍射(XRD)、热重分析(TG)、拉曼光谱(Raman)和X射线光电子能谱(XPS)对沉淀物和催化剂进行了物相和结构分析。结果显示，随着Cu含量的增加，催化剂中Mn³⁺所占比例逐渐下降，表面晶格氧含量呈现先上升后下降的趋势，催化甲苯降解的活性呈现先上升后下降的规律。微反应器中的流动反应特性使得催化剂中的Cu、Mn保持良好分散性，有利于提高催化剂中Mn³⁺含量，此时表面晶格氧成为催化活性的制约因素。

关键词: 微反应器, 沉淀, 铜锰配比, 铜锰复合氧化物, 催化剂

Abstract:

Cu-Mn coprecipitates with different copper manganese molar ratios were synthesised by co-precipitation method in the Caterpillar microreactor, and Cu-Mn composite oxide catalysts were prepared after calcining. The phase and structure of the precipitates and catalysts were analyzed by X-ray diffraction (XRD), thermogravimetric analysis (TG), Raman spectroscopy (Raman spectrum) and X-ray photoelectron spectroscopy (XPS). The results show that with the content of Cu increasing, the proportion of Mn³⁺ in the catalyst decreased gradually, the content of the surface lattice oxygen increased first and then decreased, and the catalytic performance of oxidation of toluene increased first and then decreased. The flow reaction characteristics of microreactor make Cu and Mn element in the catalyst maintain good dispersion, which contributes to increasing the content of Mn³⁺ in the catalyst. On the basis of high Mn³⁺ catalyst, the surface lattice oxygen becomes the dominating factor of catalytic performance.

Key words: microreactor, precipitation, copper manganese molar ratio, copper manganese compound oxide, catalyst

中图分类号:

TQ 426.6

付家崴, 陈帅帅, 方凯伦, 蒋新. 微反应器共沉淀反应制备铜锰催化剂[J]. 化工学报, 2023, 74(2): 776-783.

Jiawei FU, Shuaishuai CHEN, Kailun FANG, Xin JIANG. Advantage of microreactor on the synthesis of high-activity Cu-Mn catalyst by co-precipitation[J]. CIESC Journal, 2023, 74(2): 776-783.

图/表 12

图1 微反应器制备流程及结构

Fig.1 Flow diagram of preparation process and structure of microreactor

图2 铜锰催化剂考评装置

Fig.2 Schematic diagram of catalytic process for Cu-Mn catalyst

图3 催化剂中Cu含量对甲苯催化降解的影响

Fig.3 Effect of Cu content in catalyst on catalytic degradation of toluene

图4 不同铜锰配比的沉淀物的XRD谱图

Fig.4 XRD patterns of precipitates with different ratios of Cu to Mn

图5 沉淀物的TG-MS曲线

Fig.5 TG-MS curves of the precipitates

图6 Cu-Mn沉淀物的DTG曲线

Fig.6 DTG curves of Cu-Mn precipitates

图7 Cu-Mn催化剂的XRD谱图

Fig.7 XRD patterns of Cu-Mn catalysts

图8 Cu-Mn催化剂的拉曼谱图

Fig.8 Raman spectra of Cu-Mn catalysts

图9 Cu-Mn催化剂的XPS谱图

Fig.9 XPS spectra of Cu-Mn catalysts

表1 基于XPS谱图的催化剂表面物种含量

Table 1 Surface species content of catalyst based on XPS spectra

催化剂	O_latt/O_ads	Mn³⁺/Mn⁴⁺	Cu⁺/Cu²⁺
Cu_0.1Mn_0.9	1.36	2.25	0.20
Cu_0.2Mn_0.8	1.76	2.16	0.81
Cu_0.3Mn_0.7	1.96	1.94	0.08
Cu_0.4Mn_0.6	0.72	1.47	0
Cu_0.5Mn_0.5	0.65	1.14	0

图10 Cu-Mn催化剂的表面物种变化趋势

Fig.10 Surface species variation trend of Cu-Mn catalyst

图11 不同Mn3+和Olatt下的Cu-Mn催化剂的T90活性

Fig.11 T90 activity of Cu-Mn catalysts with different Mn3+ and Olatt

参考文献 30

1	Lyu Y, Li C T, Du X Y, et al. Catalytic removal of toluene over manganese oxide-based catalysts: a review[J]. Environmental Science and Pollution Research, 2020, 27(3): 2482-2501.
2	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(3/4): 275-286.
3	Wang Y, Yang D Y, Li S Z, et al. Layered copper manganese oxide for the efficient catalytic CO and VOCs oxidation[J]. Chemical Engineering Journal, 2019, 357: 258-268.
4	Ye Z P, Wang G J, Giraudon J M, et al. Investigation of Cu-Mn catalytic ozonation of toluene: crystal phase, intermediates and mechanism[J]. Journal of Hazardous Materials, 2022, 424: 127321.
5	Li W B, Liu Z X, Liu R F, et al. Rod-like CuMnO _x transformed from mixed oxide particles by alkaline hydrothermal treatment as a novel catalyst for catalytic combustion of toluene[J]. Physical Chemistry Chemical Physics: PCCP, 2016, 18(33): 22794-22798.
6	Wei G C, Zhang Q L, Zhang D H, et al. The influence of annealing temperature on copper-manganese catalyst towards the catalytic combustion of toluene: the mechanism study[J]. Applied Surface Science, 2019, 497: 143777.
7	Ye Z, Giraudon J M, Nuns N, et al. Influence of the preparation method on the activity of copper-manganese oxides for toluene total oxidation[J]. Applied Catalysis B: Environmental, 2018, 223: 154-166.
8	Einaga H, Kiya A, Yoshioka S, et al. Catalytic properties of copper-manganese mixed oxides prepared by coprecipitation using tetramethylammonium hydroxide[J]. Catalysis Science & Technology, 2014, 4(10): 3713-3722.
9	Xiao Z, Yang J S, Ren R, et al. Facile synthesis of homogeneous hollow microsphere Cu-Mn based catalysts for catalytic oxidation of toluene[J]. Chemosphere, 2020, 247: 125812.
10	Liu Y, Jia L, Lin Y, et al. Catalytic combustion of toluene over Cu-Mn mixed oxide catalyst[J]. Journal of Chemical Engineering of Japan, 2018, 51(9): 769-777.
11	方凯伦, 陈帅帅, 付家崴, 等. 微反应器研究陈化过程对铜锰催化剂的影响[J]. 化工学报, 2022, 73(10): 4438-4447.
	Fang K L, Chen S S, Fu J W, et al. Effect of aging process on copper manganese composite catalyst[J]. CIESC Journal, 2022, 73(10): 4438-4447.
12	Jiang X, Chen S S, Chen X C, et al. Effect of turbulence in micro-reactors on ultrafast competitive reactions in Cu-Zn co-precipitation[J]. AIChE Journal, 2021, 67(7): 17240.
13	Jiang X, Qin X F, Ling C, et al. The effect of mixing on co-precipitation and evolution of microstructure of Cu-ZnO catalyst[J]. AIChE Journal, 2018, 64(7): 2647-2654.
14	Xiong S C, Huang N, Peng Y, et al. Balance of activation and ring-breaking for toluene oxidation over CuO-MnO _x bimetallic oxides[J]. Journal of Hazardous Materials, 2021, 415: 125637.
15	顾欧昀, 廖永涛, 陈锐杰, 等. 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.
	Gu O Y, Liao Y T, Chen R J, et al. Catalytic combustion of toluene over Cu-Mn mixed oxide catalyst[J]. CIESC Journal, 2016, 67(7): 2832-2840.
16	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.
17	Hutchings G J, Mirzaei A A, Joyner R W, et al. Ambient temperature CO oxidation using copper manganese oxide catalysts prepared by coprecipitation: effect of ageing on catalyst performance[J]. Catalysis Letters, 1996, 42(1): 21-24.
18	Wang H P, Lu Y Y, Han Y X, et al. Enhanced catalytic toluene oxidation by interaction between copper oxide and manganese oxide in Cu-O-Mn/γ-Al₂O₃ catalysts[J]. Applied Surface Science, 2017, 420: 260-266.
19	Li D, Yu Q, Li S S, et al. The remarkable enhancement of CO-pretreated CuO-Mn₂O₃/γ-Al₂O₃ supported catalyst for the reduction of NO with CO: the formation of surface synergetic oxygen vacancy[J]. Chemistry, 2011, 17(20): 5668-5679.
20	Li J R, Zhang W P, Li C, et al. Efficient catalytic degradation of toluene at a readily prepared Mn-Cu catalyst: catalytic performance and reaction pathway[J]. Journal of Colloid and Interface Science, 2021, 591: 396-408.
21	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.
22	Lee H J, Yang J H, You J H, et al. Sea-urchin-like mesoporous copper-manganese oxide catalysts: influence of copper on benzene oxidation[J]. Journal of Industrial and Engineering Chemistry, 2020, 89: 156-165.
23	Ponce S, Peña M A, Fierro J L G. Surface properties and catalytic performance in methane combustion of Sr-substituted lanthanum manganites[J]. Applied Catalysis B: Environmental, 2000, 24(3/4): 193-205.
24	Chen S H, Li H, Hao Y, et al. Porous Mn-based oxides for complete ethanol and toluene catalytic oxidation: the relationship between structure and performance[J]. Catalysis Science & Technology, 2020, 10(6): 1941-1951.
25	Xu H M, Yan N Q, Qu Z, et al. Gaseous heterogeneous catalytic reactions over Mn-based oxides for environmental applications: a critical review[J]. Environmental Science & Technology, 2017, 51(16): 8879-8892.
26	Sun H, Liu Z G, Chen S, et al. The role of lattice oxygen on the activity and selectivity of the OMS-2 catalyst for the total oxidation of toluene[J]. Chemical Engineering Journal, 2015, 270: 58-65.
27	Li J R, Zhang W P, Li C, et al. Insight into the catalytic performance and reaction routes for toluene total oxidation over facilely prepared Mn-Cu bimetallic oxide catalysts[J]. Applied Surface Science, 2021, 550: 149179.
28	Xu Y, Qu Z P, Ren Y W, et al. Enhancement of toluene oxidation performance over Cu-Mn composite oxides by regulating oxygen vacancy[J]. Applied Surface Science, 2021, 560: 149983.
29	Luo M M, Cheng Y, Peng X Z, et al. Copper modified manganese oxide with tunnel structure as efficient catalyst for low-temperature catalytic combustion of toluene[J]. Chemical Engineering Journal, 2019, 369: 758-765.
30	Niu J R, Qian H L, Liu J, et al. Process and mechanism of toluene oxidation using Cu_1- _y Mn₂Ce _y O _x /sepiolite prepared by the co-precipitation method[J]. Journal of Hazardous Materials, 2018, 357: 332-340.

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