微反应器研究陈化过程对铜锰催化剂的影响

doi:10.11949/0438-1157.20220798

摘要/Abstract

摘要：

陈化过程是共沉淀法制备Cu-Mn复合催化剂的关键步骤，沉淀物在形成初期快速的结构变化过程是研究的难点和盲点。采用微反应器制备Cu-Mn催化剂，并利用延长管进行陈化以研究极短陈化时间对Cu-Mn沉淀物及催化剂结构的影响，采用高倍电镜（HRTEM）、X射线衍射（XRD）、热重分析（TG）、拉曼光谱（Raman spectra）、X射线光电子能谱（XPS）对不同陈化时间的沉淀物和催化剂的理化性质进行分析。结果显示，在陈化过程中沉淀物中的MnCO₃在数分钟内快速完成了从无定形到结晶态的转变，而Cu²⁺进入结晶态MnCO₃结构的过程需要数十分钟才能完成。结晶态MnCO₃的形成使Cu和Mn相互分离，而Cu-Mn复合碳酸盐的形成使得Cu-Mn分散性又逐渐变好。这导致了催化剂的结构参数呈现规律变化，使催化剂性能随陈化时间呈现先迅速变差后缓慢变好的规律。

关键词: 微反应器, 沉淀, 陈化过程, 铜锰复合氧化物, 催化剂

Abstract:

Aging process is a significant process in the preparation of Cu-Mn composite oxide catalyst by co-precipitation method, during which the rapid structural change process of precipitates at the very initial stage of formation remain to be explored. In this paper, Cu-Mn catalyst was prepared in a microreactor and aged in an extended section to study the effect of very short aging time on the structure of Cu-Mn precipitate and catalyst. High resolution transmission electron microscope (HRTEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to analyze the species and structural properties of precursors and catalysts obtained at different aging time. The results show that MnCO₃ in the precipitate has rapidly completed the transformation from amorphous to crystalline within a few minutes of aging, while the process of Cu²⁺ entering the crystalline MnCO₃ structure takes tens of minutes. The formation of crystalline MnCO₃ separates Cu and Mn, while the formation of Cu-Mn composite carbonate gradually improves the dispersion of Cu and Mn. This leads to a regular change in the structural parameters of the catalyst, which makes the catalyst performance first rapidly deteriorate and then slowly improve with aging time.

Key words: microreactor, precipitation, aging process, copper manganese compound oxide, catalyst

中图分类号:

TQ 426.6

方凯伦, 陈帅帅, 付家崴, 蒋新. 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.

Kailun FANG, Shuaishuai CHEN, Jiawei FU, Xin JIANG. Effect of aging process on copper manganese composite catalyst[J]. CIESC Journal, 2022, 73(10): 4438-4447.

图/表 11

图1 样品制备流程图

Fig.1 Flow diagram of preparation process

图2 不同陈化时间的Cu-Mn催化剂甲苯催化性能

Fig.2 Toluene catalytic performance of Cu-Mn catalyst with different aging time

图3 不同陈化时间沉淀物的XRD谱图

Fig.3 XRD patterns of precipitates at different aging time

图4 不同陈化时间沉淀物的拉曼谱图

Fig.4 Raman spectra of precipitates at different aging time

图5 沉淀物的TG-MS曲线

Fig.5 TG-MS curves of the precipitates

图6 沉淀物的TGA分析

Fig.6 TGA analysis of the precipitates

图7 陈化过程沉淀物结构变化示意图

Fig.7 Schematic diagram of structural changes of precipitates during aging

图8 不同陈化时间催化剂的XRD谱图

Fig.8 XRD patterns of catalysts with different aging time

图9 不同陈化时间催化剂的拉曼谱图

Fig.9 Raman spectra of catalysts with different aging time

图10 不同陈化时间催化剂的XPS谱图

Fig.10 XPS spectra of catalysts with different aging time

图11 不同陈化时间催化剂表面物种变化趋势

Fig.11 Surface species change trend of catalysts at different aging time

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