基于CuAl-LDH载体制备高分散Cu/ZnO/Al2O3催化剂及其催化性能

doi:10.16085/j.issn.1000-6613.2020-0572

摘要/Abstract

摘要：

通过沉积沉淀法制备了以层状CuAl-LDH为载体负载不同Cu/Zn比例的前体，经热处理得到CuZnAl-LDO复合催化剂，应用于合成气制甲醇反应。采用电感耦合等离子体发射光谱（ICP）、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）、N₂O化学吸附、N₂吸脱附、透射电镜（TEM）和X射线光电子能谱技术（XPS）等手段对前体及催化剂进行表征，考察了水滑石的限域效应和金属-载体相互作用对催化剂活性及稳定性的影响。结果发现：由于水滑石特殊的层状结构，具有较大比表面积和丰富孔道结构，促进了Cu物种的分散，有利于催化剂表面对CO和H₂的吸附，增加了Cu、Zn之间的相互作用，提高了催化剂的催化活性。在水滑石前体拓扑转变过程中，层板羟基和水脱除后形成的粗糙表面对所负载的Cu活性物种起到限域作用，抑制了Cu的迁移和团聚。其中，Cu_0.6Zn_0.3Al_0.1-LDO催化剂催化合成甲醇的时空收率达到883mg/(g?h)，且反应120h后仅下降2.8%，较共沉淀制备催化剂失活速率降低了81%，表现出较好的催化活性及稳定性。

关键词: 铜锌铝催化剂, 水滑石, 限域效应, 合成气, 甲醇

Abstract:

The CuZnAl-LDO composite catalysts with different Cu/Zn ratios were prepared by using the deposition-precipitation method and layered CuAl-LDH as the carrier. The ICP, XRD, H₂-TPR, N₂O-chemisorption, N₂ sorption isotherms, TEM and XPS analyses were performed to characterize the textural properties of the precursors and the catalysts. The results showed that the special layered structure of hydrotalcite with large specific surface area and abundant pore structure promoted the dispersion of Cu species and increased the interaction between Cu and ZnO, which were conducive to the adsorption of CO and H₂ on the catalyst surface and hence increased the catalytic activity. In the topological transformation of hydrotalcite precursor, the rough surface formed by the removal of lamellar hydroxyl and water confined the loaded Cu active species and inhibited their the migration and agglomeration. The space-time yield of methanol for Cu_0.6Zn_0.3Al_0.1-LDO reached 883mg/g/h, and decreased by just 2.8% after 120h. The deactivation rate of the present catalyst decreased by 81% as that of the catalyst prepared by the co-precipitation method, suggesting its excellent catalytic activity and stability.

Key words: CuZnAl catalysts, layered double hydroxides, confined effect, syngas, methanol

中图分类号:

TQ426.6

张华成, 孔令奇, 李忠, 郑华艳. 基于CuAl-LDH载体制备高分散Cu/ZnO/Al₂O₃催化剂及其催化性能[J]. 化工进展, 2021, 40(2): 881-889.

Huacheng ZHANG, Lingqi KONG, Zhong LI, Huayan ZHENG. Preparation of highly dispersed Cu/ZnO/Al₂O₃ catalyst based on CuAl-LDH carrier and its catalytic performance[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 881-889.

图/表 9

参考文献 30

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催化剂	比表面积/m²?g^-1		Cu分散度^③ /%	介孔体积^④ /cm³?g^-1	平均孔径^⑤ /nm	晶粒尺寸^⑥/nm
催化剂	催化剂^①	Cu^②	Cu分散度^③ /%	介孔体积^④ /cm³?g^-1	平均孔径^⑤ /nm	CuO	Cu
Cu_0.6Zn_0.3Al_0.1-CP	61.5	10.9	21.5	0.3	17.7	11.3	13.1
Cu_0.7Zn_0.2Al_0.1-LDO	34.0	21.8	6.4	0.2	28.7	6.0	18.2
Cu_0.6Zn_0.3Al_0.1-LDO	67.4	45.1	24.4	0.3	17.4	4.8	7.0
Cu_0.5Zn_0.4Al_0.1-LDO	45.7	27.5	11.8	0.3	21.9	5.7	7.5
CuAl-LDO	25.5	63.3	16.8	0.1	21.8	—	13.5

催化剂	比表面积/m²?g^-1		Cu分散度^③ /%	介孔体积^④ /cm³?g^-1	平均孔径^⑤ /nm	晶粒尺寸^⑥/nm
催化剂	催化剂^①	Cu^②	Cu分散度^③ /%	介孔体积^④ /cm³?g^-1	平均孔径^⑤ /nm	CuO	Cu
Cu_0.6Zn_0.3Al_0.1-CP	61.5	10.9	21.5	0.3	17.7	11.3	13.1
Cu_0.7Zn_0.2Al_0.1-LDO	34.0	21.8	6.4	0.2	28.7	6.0	18.2
Cu_0.6Zn_0.3Al_0.1-LDO	67.4	45.1	24.4	0.3	17.4	4.8	7.0
Cu_0.5Zn_0.4Al_0.1-LDO	45.7	27.5	11.8	0.3	21.9	5.7	7.5
CuAl-LDO	25.5	63.3	16.8	0.1	21.8	—	13.5

催化剂	结合能/eV		表面原子分数/%		X_Cu/X_Zn
催化剂	Cu_2P	Zn_2p	Cu	Zn	X_Cu/X_Zn
Cu_0.6Zn_0.3Al_0.1-CP	934.24	1021.36	15.06	18.74	0.80
Cu_0.7Zn_0.2Al_0.1-LDO	934.94	1021.36	25.66	12.30	2.08
Cu_0.6Zn_0.3Al_0.1-LDO	934.12	1021.66	21.09	18.13	1.16
Cu_0.5Zn_0.4Al_0.1-LDO	934.15	1021.30	17.57	22.40	0.78

催化剂	结合能/eV		表面原子分数/%		X_Cu/X_Zn
催化剂	Cu_2P	Zn_2p	Cu	Zn	X_Cu/X_Zn
Cu_0.6Zn_0.3Al_0.1-CP	934.24	1021.36	15.06	18.74	0.80
Cu_0.7Zn_0.2Al_0.1-LDO	934.94	1021.36	25.66	12.30	2.08
Cu_0.6Zn_0.3Al_0.1-LDO	934.12	1021.66	21.09	18.13	1.16
Cu_0.5Zn_0.4Al_0.1-LDO	934.15	1021.30	17.57	22.40	0.78

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基于CuAl-LDH载体制备高分散Cu/ZnO/Al₂O₃催化剂及其催化性能

Preparation of highly dispersed Cu/ZnO/Al₂O₃ catalyst based on CuAl-LDH carrier and its catalytic performance

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