UiO-66-NH2接枝吡啶亚胺钴系催化剂的合成及催化乙烯齐聚性能

doi:10.19894/j.issn.1000-0518.210084

摘要/Abstract

摘要：

以金属有机骨架（MOFs）UiO-66-NH₂和吡啶-2-甲醛为原料，采用后合成修饰法制备一种UiO-66-NH₂接枝吡啶亚胺配体，然后以UiO-66-NH₂接枝吡啶亚胺配体和CoCl₂·6H₂O为原料，经配合反应，合成出一种UiO-66-NH₂接枝吡啶亚胺钴系催化剂。采用傅里叶红外变换光谱（FT-IR）、X射线衍射（XRD）、扫描电子显微镜（SEM）、电感耦合等离子体质谱（ICP-MS）和氮气吸附-脱附等方法对合成产物的结构进行了表征，并考察了该催化剂在乙烯齐聚反应中的催化性能。研究结果表明，反应温度、n（Al）／n（Co）和乙烯压力对催化乙烯齐聚活性和产物选择性均有较大的影响，当以环己烷为溶剂，甲基铝氧烷（MAO）为助催化剂，在反应温度为25℃、n（Al）／n（Co）为1000、乙烯压力为1.0 MPa时，UiO-66-NH₂接枝吡啶亚胺钴系催化剂催化乙烯齐聚的活性可达1.23×10⁵g／（mol_Co·h），对丁烯的选择性为88.96%。

关键词: 金属有机骨架, 乙烯齐聚, 催化剂, 反应, 活性, 选择性

Abstract:

UiO-66-NH₂grafted pyridineimine ligand was prepared by post synthetic modification with metal organic frameworks (MOFs) UiO-66-NH₂and 2-pyridinecarboxaldehyde as raw materials, and then a novel UiO-66-NH₂grafted pyridineimine cobalt catalyst was synthesized by complexation reaction with UiO-66-NH₂ grafted pyridineimine ligand and CoCl₂·6H₂O as raw materials. The structure of the products was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, inductively coupled plasma mass spectrometry and nitrogen adsorption-desorption, and the catalytic performance of the UiO-66-NH₂grafted pyridineimine cobalt catalyst in ethylene oligomerization was investigated. The results show that the reaction temperature, Al/Co molar ratio and ethylene pressure have a significant effect on the catalytic activity and products selectivity. The catalytic activity of 1.23×10⁵g/ (mol_Co·h) and 88.96% selectivity of butene are obtained under the condition of the reaction temperature 25℃, Al/Co molar ratio of 1000 and ethylene pressure of 1.0 MPa.

Key words: Metal organic frameworks, Ethylene oligomerization, Catalyst, Activity, Selectivity

中图分类号:

O631

唐静, 张娜, 史冬旭, 张芳慧, 唐健杰. UiO-66-NH₂接枝吡啶亚胺钴系催化剂的合成及催化乙烯齐聚性能[J]. 应用化学, 2022, 39(02): 258-265.

Jing TANG, Na ZHANG, Dong-Xu SHI, Fang-Hui ZHANG, Jian-Jie TANG. Synthesis of UiO-66-NH₂Grafted Pyridineimine Cobalt Catalyst and Its Catalytic Performance in Ethylene Oligomerization[J]. Chinese Journal of Applied Chemistry, 2022, 39(02): 258-265.

图/表 11

图1 UiO-66-NH2（a）、UiO-66-Pyr（b）及UiO-66-Pyr-Co（c）的FT-IR谱图

Fig.1 FT-IR spectra of UiO-66-NH2（a），UiO-66-Pyr（b）and UiO-66-Pyr-Co（c）

图2 UiO-66-NH2、UiO-66-Pyr及UiO-66-Pyr-Co的XRD谱图

Fig.2 XRD spectra of UiO-66-NH2，UiO-66-Pyr and UiO-66-Pyr-Co

图3 UiO-66-NH2（A）、UiO-66-Pyr（B）和UiO-66-Pyr-Co（C）的SEM图

Fig.3 SEM images of UiO-66-NH2（A），UiO-66-Pyr（B）and UiO-66-Pyr-Co（C）

图4 UiO-66-NH2和UiO-66-Pyr-Co氮气吸附-脱附曲线

Fig.4 N2adsorption-desorption isotherms of UiO-66-NH2，UiO-66-Pyr and UiO-66-Pyr-Co

表1 UiO-66-NH2和UiO-66-Pyr-Co的孔结构参数

Table 1 Pore structural parameters of UiO-66-NH2and UiO-66-Pyr-Co

样品名称	比表面积	孔容	孔径
Sample	BET／（m²·g^－1）	Pore volume／（cm³·g^－1）	Pore size／nm
UiO-66-NH₂	1020.41	0.77	3.63
UiO-66-Pyr-Co	910.21	0.62	2.74

表2 反应温度对催化乙烯齐聚性能的影响

Table 2 Effect of reaction temperature on the property of ethylene oligomerization

温度	活性	产物选择性
Temperature／℃	10^－5Activity／（g·mol^－1　_Co·h^－1）	Product selectivity／%
Temperature／℃	10^－5Activity／（g·mol^－1　_Co·h^－1）	C₄	C₆	C₈
15	0.36	87.42	11.59	0.99
25	0.52	90.17	8.76	1.07
35	0.47	90.89	7.95	1.16
45	0.40	92.39	7.25	0.36
55	0.29	92.52	7.00	0.48

表3 　n（Al）／n（Co）对催化乙烯齐聚性能的影响

Table 3 Effect of n（Al）／n（Co）on the property of ethylene oligomerization

n（Al）／n（Co）	活性	产物选择性
	10^－5Activity／（g·mol^－1　_Co·h^－1）	Product selectivity／%
	10^－5Activity／（g·mol^－1　_Co·h^－1）	C₄	C₆	C₈
300	0.29	86.16	12.38	1.46
500	0.52	90.17	8.76	1.07
700	0.57	91.20	8.03	0.77
1000	0.81	91.62	7.99	0.39
1500	0.74	93.35	6.16	0.49

表4 乙烯压力对催化乙烯齐聚性能的影响

Table 4 Effect of ethylene pressure on the property of ethylene oligomerization

压力	活性	产物选择性
Pressure／MPa	10^－5Activity／（g·mol^－1　_Co·h^－1）	Product selectivity／%
Pressure／MPa	10^－5Activity／（g·mol^－1　_Co·h^－1）	C₄	C₆	C₈
0.1	0.50	93.78	6.11	0.11
0.3	0.79	91.85	8.02	0.13
0.5	0.81	91.62	7.99	0.39
0.7	0.94	89.03	9.14	1.83
1.0	1.23	88.96	9.59	1.44

表5 UiO-66-NH2接枝吡啶亚胺钴系催化剂循环利用性

Table 5 The recyclability of UiO-66-NH2grafted pyridineimine cobalt catalyst

循环次数	活性	产物选择性
Cycles	10^-5Activity／（g·mol^－1　_Co·h^－1）	Product selectivity／%
Cycles	10^-5Activity／（g·mol^－1　_Co·h^－1）	C₄	C₆	C₈
1	1.23	88.96	9.59	1.44
2	1.06	90.31	8.86	0.83
3	0.92	89.25	9.97	0.78
4	0.68	91.04	8.35	0.61

图5 吡啶亚胺钴系催化剂结构

Fig.5 Structures of pyridineimine cobalt catalysts

表6 催化剂结构对催化乙烯齐聚性能的影响

Table 6 Effect of catalyst structure on the property of ethylene oligomerization

催化剂	活性	产物选择性
Catalyst	10^－5Activity／（g··h^－1）	Product selectivity／%
Catalyst	10^－5Activity／（g··h^－1）	C₄	C₆	C₈₊
Uio-66-Pyr-Co ^a	1.23	88.96	9.59	1.44
Pyr-Co ^b	0.20	81.67	13.11	5.22

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UiO-66-NH₂接枝吡啶亚胺钴系催化剂的合成及催化乙烯齐聚性能

Synthesis of UiO-66-NH₂Grafted Pyridineimine Cobalt Catalyst and Its Catalytic Performance in Ethylene Oligomerization

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