沉淀过程对锰孔雀石结构及其演化过程的影响

doi:10.16085/j.issn.1000-6613.2019-1439

摘要/Abstract

摘要：

锰孔雀石中的Mn含量对其后续演变和Cu-Mn催化剂的活性有重要的影响。本文利用搅拌釜反应器和微反应器制备了铜锰的碱式碳酸盐共沉淀物，研究了混合过程对Cu²⁺、Mn²⁺的共沉淀反应过程及共沉淀产物的后续演变过程的影响。采用X射线衍射（XRD）、热重质谱联用（TG-MS）、氢气程序升温还原（H₂-TPR）分析了前体、催化剂的结构及演变过程。研究发现，在混合较好的微反应器制备的样品中，锰孔雀石中的极限Mn质量分数为25%左右，明显高于文献研究从搅拌釜中得到的数值。通过对扩散-反应过程的分析发现，反应过程中的混合效果越好，制备得到的前体中锰孔雀石的含量越多且其中的锰含量越高。高锰含量的锰孔雀石在焙烧时会形成更多的Cu-Mn界面，进而产生更多的高温碳酸盐，最终的铜锰催化剂中Cu、Mn相互作用更强，催化活性更高。

关键词: 锰孔雀石, 微反应器, 沉淀, 锰含量, 混合

Abstract:

The Mn content in manganese malachite has an important influence on its subsequent evolution and the activity of Cu-Mn catalyst. A series of copper manganese co-precipitate were prepared by using a batch reactor and several different microreactors, and the effect of the mixing on the co-precipitation of Cu²⁺ and Mn²⁺ and the evolution of precipitate was investigated. X-ray diffraction (XRD), thermogravimetry-mass spectrometry (TG-MS) and hydrogen temperature programmed reduction (H₂-TPR) were used for analyzing the structure of the precursors and catalysts. The results indicated that the limit Mn content in manganese malachite prepared by the microreactors with better mixing was about 25%, which was significantly higher than the value reported in the literature. The analysis of diffusion-reaction process revealed that as the mixing increased during the precipitation process, more manganese malachite with higher Mn content was formed in precursors. During the subsequent calcination, these precursors decomposed into mixed oxides with more Cu-Mn interfaces, leading to the preservation of more high-temperature carbonate. The catalysts prepared in flow pattern with excellent mixing had stronger Cu-Mn interaction and better catalytic performance.

Key words: manganese malachite, microreactor, precipitation, manganese content, mixing

中图分类号:

TQ426.6

陈帅帅, 陈鑫超, 凌晨, 蒋新. 沉淀过程对锰孔雀石结构及其演化过程的影响[J]. 化工进展, 2020, 39(5): 1707-1713.

Shuaishuai CHEN, Xinchao CHEN, Chen LING, Xin JIANG. Influence of the precipitation process on the structure and evolution of manganese malachite[J]. Chemical Industry and Engineering Progress, 2020, 39(5): 1707-1713.

参考文献

1	GONCALVES R V, WOJCIESZAK R, WENDER H, et al. Easy access to metallic copper nanoparticles with high activity and stability for CO oxidation[J]. ACS Appl. Mater. Interfaces, 2015, 7(15): 7987-7994.
2	STONE F S, WALLER D. Cu-ZnO and Cu-ZnO/Al₂O₃ catalysts for the reverse water-gas shift reaction. The effect of the Cu/Zn ratio on precursor characteristics and on the activity of the derived catalysts[J]. Top. Catal., 2003, 22(3/4): 305-318.
3	BEHRENS M. Meso- and nano-structuring of industrial Cu/ZnO/(Al₂O₃) catalysts[J]. J. Catal., 2009, 267(1): 24-29.
4	ZANDER S, KUNKES E L, SCHUSTER M E, et al. The role of the oxide component in the development of copper composite catalysts for methanol synthesis[J]. Angew. Chem. Int. Ed., 2013, 52(25): 6536-6540.
5	SMITH P J, KONDRAT S A, CHATER P A, et al. A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by coprecipitation[J]. Chem. Sci., 2017, 8(3): 2436-2447.
6	LIU Q, WANG L, CHEN M, et al. Waste-free soft reactive grinding synthesis of high-surface-area copper-manganese spinel oxide catalysts highly effective for methanol steam reforming[J]. Catal. Lett., 2008, 121(1/2): 144-150.
7	KASATKIN I, KURR P, KNIEP B, et al. Role of lattice strain and defects in copper particles on the activity of Cu/ZnO/Al₂O₃ catalysts for methanol synthesis[J]. Angew. Chem. Int. Ed., 2007, 46(38): 7324-7327.
8	BEHRENS M, GIRGSDIES F, TRUNSCHKE A, et al. Minerals as model compounds for Cu/ZnO catalyst precursors: structural and thermal properties and IR spectra of mineral and synthetic (zincian) malachite, rosasite and aurichalcite and a catalyst precursor mixture[J]. Eur. J. Inorg. Chem, 2009(10): 1347-1357.
9	BEHRENS M, GIRGSDIES F. Structural effects of Cu/Zn substitution in the malachite-rosasite system[J]. Z. Anorg. Allg. Chem., 2010, 636(6): 919-927.
10	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 J., 2018, 64(7): 2647-2654.
11	凌晨, 蒋新, 汪志勇, 等. 微反应器中的混合对Cu-ZnO催化剂微结构形成过程的影响[J]. 化工学报, 2018, 69(2): 718-726.
11	LING Chen, JIANG Xin, WANG Zhiyong, et al. Influence of mixing inside microreactor on microstructural evolution of CU-ZnO catalyst[J]. CIESC J., 2018, 69(2): 718-726.
12	陈玉萍, 蒋新, 卢建刚. 微通道反应过程对铜锌催化剂微结构的影响[J]. 化工学报, 2015, 66(10): 3895-3902.
12	CHEN Yuping, JIANG Xin, LU Jiangang. Effects of reaction progress in microchannel on microstructure of Cu-Zn catalyst[J]. CIESC J., 2015, 66(10): 3895-3902.
13	PORTA P, MORETTI G, JACONO M L, et al. Characterization of copper-manganese hydroxysalts and oxysalts[J]. J. Mater. Chem., 1991, 1(1): 129-135.
14	WANG Z X, ZHU J L, SUN P, et al. Nanostructured Mn-Cu binary oxides for supercapacitor[J]. J. Alloys Compd., 2014, 598: 166-170.
15	QIAN K, QIAN Z X, QING H, et al. Structure-activity relationship of CuO/MnO₂ catalysts in CO oxidation[J]. Appl. Surf. Sci., 2013, 273: 357-363.
16	LIU Y, JIA L, LIN Y, et al. Catalytic combustion of toluene over Cu-Mn mixed oxide catalyst[J]. J. Chem. Eng. Jpn., 2018, 51(9): 769-777.
17	PIERO P, GIULIANO M, MONICA M, et al. Copper-manganese mixed oxides: formation, characterization and reactivity under different conditions[J]. Solid State Ionics, 1993, 63/64/65: 257-267.
18	BEMS B, SCHUR M, DASSENOY A, et al. Relations between synthesis and microstructural properties of copper/zinc hydroxycarbonates[J]. Chem. Eur. J., 2003, 9(9): 2039-2052.
19	MILLAR G J, HOLM I H, UWINS P R, et al. Characterization of precursors to methanol synthesis catalysts Cu/ZnO system[J]. J. Chem. Soc., Faraday Trans, 1998, 94(4): 593-600.
20	刘兆信, 黎维彬. 在类棒状铜锰复合氧化物上甲苯的催化燃烧活性及其失活[J]. 物理化学学报, 2016, 32(7): 1795-1800.
20	LIU Zhaoxin, LI Weibin. Catalytic activity and deactivation of toluene combustion on rod-like copper-manganese mixed oxides[J]. Acta Phys. Chim. Sin., 2016, 32(7): 1795-1800.
21	BUCIUMAN F C, PATCAS F, HAHN T. A spillover approach to oxidation catalysis over copper and manganese mixed oxides[J]. Chem. Eng. Process, 1999, 38(4/6): 563-569.
22	EINAGA H, KIYA A, YOSHIOKA S, et al. Catalytic properties of copper-manganese mixed oxides prepared by coprecipitation using tetramethylammonium hydroxide[J]. Catal. Sci. Technol., 2014, 4(10): 3713-3722.
23	CLARKE T J, KONDRAT S A, TAYLOR S H. Total oxidation of naphthalene using copper manganese oxide catalysts[J]. Catal. Today, 2015, 258: 610-615.
24	STOBBE E R, DE BOER B A, GEUS J W. The reduction and oxidation behaviour of manganese oxides[J]. Catal. Today, 1999, 47(1/4): 161-167.
25	HOSSEINI S A, NIAEI A, SALARI D, et al. Study of correlation between activity and structural properties of Cu-(Cr, Mn and Co)₂ nano mixed oxides in VOC combustion[J]. Ceram. Int., 2014, 40(4): 6157-6163.
26	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]. J. Rare Earths, 2012, 30(9): 871-877.
27	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.
27	GU Ouyun, LIAO Yongtao, CHEN Ruijie, et al. Catalytic combustion of toluene over Cu-Mn mixed oxide catalyst[J]. CIESC J., 2016, 67(7): 2832-2840.
28	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.
28	LI Weibin, GONG Hao. Recent progress in the removal of volatile organic compounds by catalytic combustion[J]. Acta Phys. Chim. Sin., 2010, 26(4): 885-894.
29	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]. Appl. Catal. B, 2018, 223: 154-166.

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