介孔材料为硅源合成多级孔Mo/H-IM-5催化剂及其在甲烷无氧芳构化反应中的应用

刘恒; 阚秋斌

介孔材料为硅源合成多级孔Mo/H-IM-5催化剂及其在甲烷无氧芳构化反应中的应用

刘恒^1, ,,
阚秋斌²

1.
长春理工大学纳米技术研究中心, 吉林长春 130022
2.
吉林大学化学学院, 吉林长春 130023

基金项目:

长春理工大学青年基金 XJJLG-2015-12

详细信息

通讯作者:
刘恒, Tel:0431-85583121, E-mail:liuhengjlu@163.com

中图分类号: O643
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- 文章访问数: 144
- HTML全文浏览量: 46
- PDF下载量: 5
- 被引次数: 0
出版历程
- 收稿日期: 2016-06-24
- 修回日期: 2016-08-08
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-11-10

Synthesis of hierarchical Mo/H-IM-5 catalysts by using mesoporous material as the silica source and its application in methane non-oxidative aromatization

LIU Heng^{1
, ,},
KAN Qiu-bin²

1.
Research Center for Nanotechnology, Changchun University of Science and Technology, Changchun 130022, China
2.
College of Chemistry, Jilin University, Changchun 130023, China

Funds:

Youth Fund of Changchun University of Science and Technology XJJLG-2015-12

摘要

摘要: 在IM-5分子筛的合成体系中以介孔材料KIT-6作为硅源，制备出了多级孔IM-5复合分子筛（IM-5-K）。利用X射线衍射、扫描电镜、透射电镜、比表面积分析、NH₃-TPD等手段对样品的物理性质和酸性进行表征。将经过钼修饰的Mo-IM-5-K催化剂应用于甲烷无氧芳构化反应中，考察其活性。催化测试结果显示，多级孔Mo-IM-5-K催化剂的最高甲烷转化率和芳烃产率为12.4%和6.9%，高于常规Mo-IM-5-C催化剂。同时，Mo-IM-5-K催化剂有更好的稳定性。催化剂反应活性和稳定性的差异是由于其具有不同的孔道结构和酸性所致。介孔的存在会影响活性Mo物种的落位及分布状态，有利于反应物与活性位的接触和芳烃产物的扩散，进而提高催化剂的活性和稳定性。
- IM-5 /
- 介孔 /
- 钼 /
- 甲烷芳构化
Abstract: A novel hierarchical porous IM-5 (IM-5-K) was synthesized by using mesoporous silica KIT-6 as the silica sources. The physical properties and acidities of the samples were characterized by XRD, SEM, TEM, BET and NH₃-TPD. Moreover, Mo-modified catalyst, Mo-IM-5-K was prepared for non-oxidative aromatization of methane. Compared with Mo-IM-5-C, the Mo-IM-5-K catalyst showed higher conversion of methane and yields of aromatics. In addition, Mo-IM-5-K exhibited better stability than Mo-IM-5-C. Different activities and stabilities of the catalysts may be due to their different structure properties and acidities. The existence of secondary mesoporous systems may influence the location and state of the active Mo species, simultaneously lead to easier access to the active sites for reactants and better diffusion of aromatic products, thus improvs the activities of the catalysts.
- IM-5 /
- mesoporous /
- molybdenum /
- methane dehydroaromatiztion

HTML全文

图 1 KIT-6催化剂的小角XRD谱图和扫描电镜照片

Figure 1 XRD pattern and SEM image of KIT-6 catalyst

下载: 全尺寸图片幻灯片

图 2 IM-5-C和IM-5-K催化剂的广角XRD谱图

Figure 2 XRD patterns of IM-5-C and IM-5-K catalysts

下载: 全尺寸图片幻灯片

图 3 IM-5-C和IM-5-K催化剂的扫描电镜和透射电镜照片

Figure 3 SEM (a), (c) and TEM (b), (d) images of IM-5-C and IM-5-K catalysts

下载: 全尺寸图片幻灯片

图 4 催化剂的N₂吸附-脱附曲线和孔径分布

Figure 4 N₂ adsorption-desorption isotherms and pore size distributions of the catalysts

(a): IM-5-C; (b): IM-5-K

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图 5 催化剂的NH₃-TPD谱图

Figure 5 NH₃-TPD profiles of the catalysts

a: H-IM-5-K; b: Mo-IM-5-K; c: H-IM-5-C; d: Mo-IM-5-C

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图 6 Mo-IM-5-K和Mo-IM-5-C催化剂在甲烷无氧芳构化反应中的性能

Figure 6 Catalytic performance of Mo-IM-5-K (▲) and Mo-IM-5-C (■) catalysts in methane non-oxidative aromatization reaction conditions: t=700 ℃, 1.01×10⁵ Pa, GHSV=1 500 h^-1

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图 7 Mo-IM-5-C和Mo-IM-5-K催化剂的热重分析曲线

Figure 7 TG curves of Mo-IM-5-C and Mo-IM-5-K catalysts

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图 8 Mo-IM-5-K催化剂在甲烷芳构化反应中的回收实验

Figure 8 Recycling experiment of Mo-IM-5-K catalyst in methane aromatization

: methane conversion; : aromatics yield; : benzene yield; : naphthalene yield

下载: 全尺寸图片幻灯片

表 1 IM-5-C、IM-5-K、Mo-IM-5-C和Mo-IM-5-K催化剂的结构性质

Table 1 Textural properties of IM-5-C, IM-5-K, Mo-IM-5-C and Mo-IM-5-K

Sample	A_BET/(m²·g^-1)	v_total/(cm³·g^-1)	A_micro/(m²·g^-1)	v_micro/(cm³·g^-1)
IM-5-C	366	0.21	329	0.16
IM-5-K	382	0.27	291	0.14
Mo-IM-5-C	311	0.18	283	0.14
Mo-IM-5-K	332	0.23	262	0.12

下载: 导出CSV

表 2 H-IM-5-C、Mo-IM-5-C、H-IM-5-K和Mo-IM-5-K催化剂的酸量

Table 2 Acidity capacities of H-IM-5-C, Mo-IM-5-C, H-IM-5-K and Mo-IM-5-K

Sample	Contents of MoO₃ w/%	Area (a.u.)
Sample	Contents of MoO₃ w/%	peak (L)	peak (M)	peak (H)
H-IM-5-C	-	452	-	545
Mo-IM-5-C	5.4	391	238	290
H-IM-5-K	-	386	-	377
Mo-IM-5-K	5.5	349	195	169

下载: 导出CSV

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