铜锰氧化物催化低浓度甲醛动力学模型研究

doi:10.19964/j.issn.1006-4990.2022-0515

摘要/Abstract

摘要：

选取典型空气净化材料铜锰氧化物（CuO/MnO₂），参照ASHRAE标准搭建了测试实验系统，探究其去除低浓度甲醛的性能。并利用红外光谱（FT-IR）、扫描电镜（SEM）、X射线衍射（XRD）和X射线光电子能谱（XPS）等方法对反应前后催化剂的理化性质及结构进行了表征。实验结果表明：CuO/MnO₂催化剂在室内典型环境［25 ℃，相对湿度（RH）为50%］下，对室内甲醛典型浓度水平［（0.3~1.0）×10^-6］的去除效率达到80%。CuO/MnO₂去除室内甲醛的效率受浓度、温度的影响显著，其中，反应温度对甲醛分解率的影响最大，温度越高，甲醛分解率越高。室温下在较长的一段时间内（20 h），铜锰催化剂对室内甲醛典型浓度水平的去除效率能达60%，稳定性较好。挥发性有机化合物完全催化氧化机理Mars-van Krevelen（MVK）模型可以较好地描述铜锰催化剂催化氧化甲醛的反应过程。以上表明，CuO/MnO₂催化剂稳定性较好，再加上可再生的性质，该催化剂在室内等常温低浓度环境下的甲醛催化氧化有着广泛的应用前景。

关键词: CuO/MnO₂, 室内空气品质, 低浓度甲醛, 机理模型

Abstract:

CuO/MnO₂as a typical air purification material was selected and a test experimental system was built with reference to ASHRAE standards to investigate its performance in removing low concentrations of formaldehyde.The physical and chemical properties and structures of the catalysts before and after the reaction were also characterized by FT-IR，SEM，XRD and XPS.The experimental results showed that the efficiency of the CuO/MnO₂ catalyst for the removal of indoor formaldehyde at typical concentration levels［（0.3~1.0）×10^-6］ in a typical indoor environment（25 ℃，50% RH） reached 80%.The efficiency of CuO/MnO₂ in removing indoor formaldehyde was significantly affected by concentration and temperature.Among them，the reaction temperature had the greatest impact on the decomposition rate of formaldehyde，and the higher the temperature，the higher the decomposition rate of formaldehyde.The copper-manganese catalyst was able to achieve 60% removal efficiency for typical indoor formaldehyde concentration levels with good stability over a longer period of time（20 h） at room temperature.The MVK model could better describe the catalytic oxidation of formaldehyde by CuO/MnO₂ catalysts.The above results showed that the stability of CuO/MnO₂ catalyst was good，and coupled with its regenerative nature，the catalyst had a wide application in the catalytic oxidation of formaldehyde at low concentrations and room temperature，such as indoors.

Key words: CuO/MnO₂, indoor air quality, low concentration formaldehyde, mechanistic model

中图分类号:

TQ132.21

王志强, 刘相成, 张俊杰, 金梧凤. 铜锰氧化物催化低浓度甲醛动力学模型研究[J]. 无机盐工业, 2023, 55(6): 142-150.

WANG Zhiqiang, LIU Xiangcheng, ZHANG Junjie, JIN Wufeng. Study on kinetic model of low concentration formaldehyde catalyzed by copper-manganese oxide[J]. Inorganic Chemicals Industry, 2023, 55(6): 142-150.

图/表 14

图1

表1

表2

图2

表3

单变量（表面浓度Cs）动力学模型拟合

模型	反应速率公式	温度/℃	k/（10^-42m·s^-1）	K/10⁶	k′/（10^-6m·s^-1）	A/（10⁹m^-1·s）	R²
一阶模型	$r = k' C s$	25	—	—	0.303	—	0.179
一阶模型	$r = k' C s$	60	—	—	0.320	—	0.179
L-H	$r = k K C s / 1 + K C s 2$	25	250.083	0.001	—	—	0.178
L-H	$r = k K C s / 1 + K C s 2$	60	294.005	0.001	—	—	0.178
MVK	$r = k' C s / 1 + k' A C s$	25	—	—	0.017	-25.367	0.941
MVK	$r = k' C s / 1 + k' A C s$	60	—	—	0.018	-24.022	0.941

表3

图3

图4

图5

图6

图7

图8

图9

图10

图11

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催化剂	填充厚度/mm	进气浓度/10^-6	催化温度/℃	初始去除效率/%	穿透时间/h
CuO/MnO₂-1	13	0.196	25	70.7	19.9
CuO/MnO₂-2	13	0.304	25	77.9	18.4
CuO/MnO₂-3	13	0.406	25	83.7	19.4
CuO/MnO₂-4	13	0.502	25	88.5	19.4
CuO/MnO₂-5	13	0.304	25	77.9	18.3
CuO/MnO₂-6	13	0.304	30	82.8	19.0
CuO/MnO₂-7	13	0.304	40	84.0	18.4
CuO/MnO₂-8	13	0.304	50	86.8	19.4
CuO/MnO₂-9	13	0.304	60	89.7	16.9
CuO/MnO₂-10	3	0.199	40	72.3	19.9
CuO/MnO₂-11	3	0.334	40	72.5	18.4
CuO/MnO₂-12	3	0.607	40	70.9	19.4
CuO/MnO₂-13	3	1.130	40	70.7	16.9
CuO/MnO₂-14	3	1.153	40	71.4	17.6

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