Cu-Zn-Zr/SBA-15介孔催化剂的制备及CO2加氢合成甲醇的催化性能

doi:10.7503/cjcu20140684

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (12): 2616.doi: 10.7503/cjcu20140684

Cu-Zn-Zr/SBA-15介孔催化剂的制备及CO₂加氢合成甲醇的催化性能

李志雄^1,², 纳薇^1,²(), 王华^1,², 高文桂^1,²

1. 昆明理工大学, 云南省部共建复杂有色金属资源清洁利用国家重点实验室, 昆明 650093
2. 昆明理工大学,教育部冶金节能减排工程研究中心, 昆明 650093

收稿日期:2014-07-24 出版日期:2014-12-10 发布日期:2014-11-29
作者简介:联系人简介: 纳薇, 女, 博士, 副教授, 主要从事CO₂加氢合成甲醇铜基催化剂的研究. E-mail:weina@kmust.edu.cn
基金资助:
国家科技支撑计划项目(批准号: 2011BAC01B03)、国家自然科学基金(批准号: 51404122)和云南省自然科学基金(批准号: 2011FZ030)资助

Direct Syntheses of Cu-Zn-Zr/SBA-15 Mesoporous Catalysts for CO₂ Hydrogenation to Methanol^†

LI Zhixiong^1,², NA Wei^1,^2,^*(), WANG Hua^1,², GAO Wengui^1,²

1. State Key Laboratory Breeding Base of Complex Nonferrous Metal Resources Cleaning in Yunnan Province, Kunming University of Science and Technology, Kunming 650093, China
2. Engineering Research Center of Metallurgical Energy Conservation and Emission Reduction,Ministry of Education, Kunming University of Science and Technology, Kunming 650093, China

Received:2014-07-24 Online:2014-12-10 Published:2014-11-29
Contact: NA Wei E-mail:weina@kmust.edu.cn
Supported by:
† Supported by the National Key Technologies R&D Program of China(No.2011BAC01B03), the National Natural Science Foundation of China(No.51404122) and the Natural Science Foundation of Yunnan Province, China(No.2011FZ030)

摘要/Abstract

摘要：

以具有骨架结构的SBA-15介孔分子筛为载体, 采用浸渍法合成了具有高比表面积、不同金属氧化物含量的Cu-Zn-Zr介孔催化剂CZZ_x/SBA-15(x=0.3, 0.4, 0.5, 0.6). 采用N₂吸附-脱附(BET)、 X射线衍射(XRD)、 H₂程序升温还原(H₂-TPR)、 CO₂吸附(CO₂-TPD)和透射电子显微镜(TEM)等手段对样品进行了表征. 在固定床反应器上评价了其CO₂加氢合成甲醇的催化性能. 实验结果表明, CZZ_x/SBA-15催化剂具有介孔结构, 负载的CuO, ZnO和ZrO₂能够很好地分散在表面, 并且负载氧化物晶粒尺寸不同. 催化剂的铜比表面积S_Cu与甲醇催化活性呈近似线性关系, 其中CZZ_0.4/SBA-15催化剂表现出最大甲醇选择性(54.32%), 与CZZ相比, 甲醇选择性增加24.85%. 随着金属氧化物负载量的增大, 催化剂比表面积和S_Cu明显减小, 甲醇选择性与收率也相应减小, 负载型CZZ_x/SBA-15催化剂表面结构对CO₂加氢合成甲醇反应活性起关键作用.

关键词: 浸渍法, Cu-Zn-Zr催化剂, SBA-15分子筛, CO₂加氢, 甲醇选择性

Abstract:

A series of high surface areas and different mental oxide contents of Cu-Zn-Zr/SBA-15 mesoporous catalysts CZZ_x/SBA-15(x=0.3, 0.4, 0.5, 0.6) was directly synthesized by impregnation method. The catalysts were characterized by N₂ adsorption-desorption(BET), X-ray diffraction(XRD), transmission electron microscopy(TEM), H₂ temperature-programmed reduction(H₂-TPR), CO₂ temperature-programmed desorption(CO₂-TPD) and N₂O titration technique(N₂O-RFC). The catalytic activities of these catalysts were determined on the hydrogenation of CO₂ to methanol in a fixed-bed reactor. The results showed that CZZ_x/SBA-15 catalysts possessed a highly ordered mesoporous structure, in which different grain size CuO, ZnO, ZrO₂ species dispersed on the surface of SBA-15. A approximate linear relationship between the methanol synthesis activity and the total Cu⁰ surface area S_Cu was observed. CZZ_0.4/SBA-15 catalyst showed the largest methanol selectivity $S C H 3 OH$ =54.32%, which increased by 24.85% as compared with CZZ catalyst. However, the methanol synthesis selectivity and yield decreased with the increasing of metal oxide content, which strongly suggested that the surface structure of the CZZ_x/SBA-15 catalysts played an important role in CO₂ hydrogenation to methanol.

Key words: Impregnation method, Cu-Zn-Zr catalyst, SBA-15 molecular seive, CO₂ hydrogenation, Methanol selectivity

中图分类号:

O643

TrendMD:

李志雄, 纳薇, 王华, 高文桂. Cu-Zn-Zr/SBA-15介孔催化剂的制备及CO₂加氢合成甲醇的催化性能. 高等学校化学学报, 2014, 35(12): 2616.

LI Zhixiong, NA Wei, WANG Hua, GAO Wengui. Direct Syntheses of Cu-Zn-Zr/SBA-15 Mesoporous Catalysts for CO₂ Hydrogenation to Methanol^†. Chem. J. Chinese Universities, 2014, 35(12): 2616.

图/表 10

Fig.1 N2 adsorption-desorption isotherms of catalysts a. CZZ; b. CZZ0.6/SBA-15; c. CZZ0.5/SBA-15;d. CZZ0.4/SBA-15; e. CZZ0.3/SBA-15; f. SBA-15.

Table 1 Textural properties of catalysts

Catalyst	S_BET/(m²·g^-1)	V_BJH/(cm³·g^-1)	D_BJH/nm
SBA-15	872.28	1.23	7.57
CZZ	70.51	0.09	3.04
CZZ_0.3/SBA-15	419.40	0.65	5.69
CZZ_0.4/SBA-15	417.90	0.46	4.94
CZZ_0.5/SBA-15	336.73	0.39	4.35
CZZ_0.6/SBA-15	273.15	0.41	4.95

Fig.2 Small-angle XRD patterns of catalysts a. SBA-15; b. CZZ0.3/SBA-15; c. CZZ0.4/SBA-15;d. CZZ0.5/SBA-15; e. CZZ0.6/SBA-15; f. CZZ.

Fig.3 XRD patterns of catalysts a. CZZ0.3/SBA-15; b. CZZ0.4/SBA-15; c. CZZ0.5/SBA-15;d. CZZ0.6/SBA-15; e. CZZ.

Table 2 Chemical composition and textural properties of catalysts*

Catalyst	Content(%, mass fraction)			d(CuO)/nm	d(ZnO)/nm	$S Cu a$ /(m²·g^-1)	$D Cu b$ (%)
Catalyst	CuO	ZnO	ZrO₂	d(CuO)/nm	d(ZnO)/nm	$S Cu a$ /(m²·g^-1)	$D Cu b$ (%)
CZZ	42.2	43.2	14.5	17.6	24.3	15.6	7.1
CZZ_0.3/SBA-15	16.0	16.4	5.6	16.3	18.6	21.4	16.5
CZZ_0.4/SBA-15	20.0	20.5	7.0	17.5	24.9	25.9	19.2
CZZ_0.5/SBA-15	22.8	23.3	7.8	19.9	25.8	16.3	11.5
CZZ_0.6/SBA-15	25.0	25.5	8.6	22.4	27.8	13.6	9.8

Table 2 Chemical composition and textural properties of catalysts*

Catalyst	Content(%, mass fraction)			d(CuO)/nm	d(ZnO)/nm	$S Cu a$ /(m²·g^-1)	$D Cu b$ (%)
Catalyst	CuO	ZnO	ZrO₂	d(CuO)/nm	d(ZnO)/nm	$S Cu a$ /(m²·g^-1)	$D Cu b$ (%)
CZZ	42.2	43.2	14.5	17.6	24.3	15.6	7.1
CZZ_0.3/SBA-15	16.0	16.4	5.6	16.3	18.6	21.4	16.5
CZZ_0.4/SBA-15	20.0	20.5	7.0	17.5	24.9	25.9	19.2
CZZ_0.5/SBA-15	22.8	23.3	7.8	19.9	25.8	16.3	11.5
CZZ_0.6/SBA-15	25.0	25.5	8.6	22.4	27.8	13.6	9.8

Fig.4 TEM image(A) and EDX pattern(B) of the representative CZZ0.4/SBA-15 catalyst

Fig.5 H2-TPR profiles of catalysts a. CZZ; b. CZZ0.3/SBA-15; c. CZZ0.4/SBA-15;d. CZZ0.5/SBA-15; e. CZZ0.6/SBA-15.

Fig.6 CO2-TPD profiles of catalysts a. CZZ; b. CZZ0.3/SBA-15; c. CZZ0.4/SBA-15;d. CZZ0.5/SBA-15; e. CZZ0.6/SBA-15.

Table 3 Catalytic performance for methanol synthesis

Catalyst	CO₂ conversion(%)	Selectivity(%)			Yield(CH₃OH)/ (g·mL^-1·h^-1)
Catalyst	CO₂ conversion(%)	$S C H 4$	S_CO	$S C H 3 OH$	Yield(CH₃OH)/ (g·mL^-1·h^-1)
CZZ	15.01	5.10	65.43	29.47	0.04
CZZ_0.3/SBA-15	14.81	4.16	53.01	42.83	0.07
CZZ_0.4/SBA-15	16.45	1.92	43.76	54.32	0.08
CZZ_0.5/SBA-15	13.19	2.25	58.88	38.86	0.05
CZZ_0.6/SBA-15	10.36	2.84	65.96	31.19	0.03

Table 3 Catalytic performance for methanol synthesis

Catalyst	CO₂ conversion(%)	Selectivity(%)			Yield(CH₃OH)/ (g·mL^-1·h^-1)
Catalyst	CO₂ conversion(%)	$S C H 4$	S_CO	$S C H 3 OH$	Yield(CH₃OH)/ (g·mL^-1·h^-1)
CZZ	15.01	5.10	65.43	29.47	0.04
CZZ_0.3/SBA-15	14.81	4.16	53.01	42.83	0.07
CZZ_0.4/SBA-15	16.45	1.92	43.76	54.32	0.08
CZZ_0.5/SBA-15	13.19	2.25	58.88	38.86	0.05
CZZ_0.6/SBA-15	10.36	2.84	65.96	31.19	0.03

Fig.7 Turnover frequency(TOF) and CH3OH selectivity as a function of the metallic copper surface areas

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Cu-Zn-Zr/SBA-15介孔催化剂的制备及CO₂加氢合成甲醇的催化性能

Direct Syntheses of Cu-Zn-Zr/SBA-15 Mesoporous Catalysts for CO₂ Hydrogenation to Methanol^†

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