双功能催化剂<strong>(Cu-Co/<i>X</i>-MMT)</strong>的制备和性能

doi:10.11901/1005.3093.2023.493

材料研究学报

2024, Vol. 38

Issue (11): 872-880 DOI: 10.11901/1005.3093.2023.493

研究论文

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双功能催化剂(Cu-Co/X-MMT)的制备和性能

罗洪旭, 赵永华(

), 张家慷, 冯效迁, 张启俭, 王欢

辽宁工业大学化学与环境工程学院锦州 121001

Preparation and Properties of Bi-functional Catalysts (Cu-Co/X-MMT)

LUO Hongxu, ZHAO Yonghua(

), ZHANG Jiakang, FENG Xiaoqian, ZHANG Qijian, WANG Huan

School of Chemistry & Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China

引用本文:

罗洪旭, 赵永华, 张家慷, 冯效迁, 张启俭, 王欢. 双功能催化剂(Cu-Co/X-MMT)的制备和性能[J]. 材料研究学报, 2024, 38(11): 872-880.
Hongxu LUO, Yonghua ZHAO, Jiakang ZHANG, Xiaoqian FENG, Qijian ZHANG, Huan WANG. Preparation and Properties of Bi-functional Catalysts (Cu-Co/X-MMT)[J]. Chinese Journal of Materials Research, 2024, 38(11): 872-880.

全文: PDF(7139 KB) HTML

摘要:

先使用钠基蒙脱土制备不同氧化物柱撑蒙脱土(X-MMT，X = SiO₂、Al₂O₃、ZrO₂、TiO₂)，然后以其为固体酸、以铜为活性组分、钴为助剂用浸渍法制备出一系列双功能催化剂(Cu-Co/X-MMT)。使用X射线衍射(XRD)分析、N₂吸附-脱附、NH₃-TPD、H₂-TPR和X射线光电子能谱(XPS)分析等手段对其表征，研究了不同氧化物柱撑对双功能催化剂(Cu-Co/X-MMT)性能的影响。结果表明，与钠基蒙脱土相比，氧化物柱撑蒙脱土的结构和酸性均发生了明显的变化，变化的程度与氧化物的种类密切相关。不同氧化物柱撑影响铜颗粒的大小和还原程度，进而影响双功能催化剂的二甲醚水蒸气重整反应(SRD)性能。Cu-Co/SiO₂-MMT催化剂具有较好的SRD性能，在0.1 MPa、350℃和反应空速(GHSV)为3000 mL/(g·h)条件下二甲醚转化率和氢气收率分别达到80.3%和57.3%。

关键词 ：复合材料, 柱撑蒙脱土, 二甲醚, 水蒸气重整, 制氢

Abstract：

A series of bi-functional catalysts (Cu-Co/X-MMT) were prepared via the impregnation method with oxide-pillared montmorillonite (X-MMT, X = SiO₂, Al₂O₃, ZrO₂, TiO₂) obtained from Na-montmorillonite (Na-MMT) as the solid acid, Cu as active component and Co as promoter. The acquired catalysts were characterized by XRD, N₂ adsorption-desorption at low temperature, NH₃-TPD, H₂-TPR, and XPS. The effect of different kinds of X-MMT on the steam reforming of dimethyl ether (SRD) reaction performance of the acquired bi-functional catalysts was investigated. The results show that the structure and acidity of X-MMT are significantly changed compared with Na-MMT, which is dependent on the type of oxide X, meanwhile, different X-MMT affects the particle size and reduction degree of copper, and thus influencing the SRD reaction performance of bi-functional catalysts. Among others, the Cu-Co/SiO₂-MMT bifunctional catalyst exhibits the best SRD performance, with the dimethyl ether conversion and H₂ yield reaching 80.3% and 57.3% under the conditions of 0.1 MPa, 350^oC and gas hour space velocity (GHSV) of 3000 mL/(g·h), respectively.

Key words： composite pillared montmorillonite dimethyl ether steam reforming hydrogen production

收稿日期: 2023-10-08

ZTFLH:

O643.3

基金资助:国家自然科学基金(22075120);辽宁省应用基础研究计划(2023JH2/101300216)

通讯作者: 赵永华，教授，lgdzyh@163.com，研究方向为多相催化与能源化学

Corresponding author: ZHAO Yonghua, Tel: (0416)4199013, E-mail: lgdzyh@163.com

作者简介: 罗洪旭，男，1998年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2023.493 或 https://www.cjmr.org/CN/Y2024/V38/I11/872

图1 Cu-Co/X-MMT的XRD谱

图2 Cu-Co/X-MMT的TEM照片

图3 还原后Cu-Co/X-MMT的XRD谱

表1 还原后催化剂Cu的粒径

图4 样品的氮气吸附-脱附等温线

表2 样品的孔结构特征

图5 样品的NH3-TPD图

图6 Cu-Co/X-MMT的H2-TPR图

图7 还原催化剂Cu 2p的XPS谱

图8 还原催化剂的Cu LMM俄歇能谱

表3 还原后催化剂的Cu LMM XAES分峰数据

图9 Cu-Co/X-MMT的DME转化率和氢气收率

图10 双功能催化剂含碳产物的选择性

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