蜜勒胺催化剂的制备及在环碳酸酯合成中的应用研究

张源萍; 李晓云; 邸亚丽; 赵雨花; 亢茂青; 李其峰; 王军威

doi:10.19906/j.cnki.JFCT.2021020

蜜勒胺催化剂的制备及在环碳酸酯合成中的应用研究

doi: 10.19906/j.cnki.JFCT.2021020

1.
中国科学院山西煤炭化学研究所，山西太原 030001
2.
中国科学院大学，北京 100049
3.
北京机电工程总体设计部，北京 100000

基金项目: 山西省重点研发计划项目(20181101012)，山西省重点研发计划项目(201903D121104)和山西省青年基金（201901D211586）资助

详细信息

通讯作者:
Tel：13934558196，E-mail：liqf@sxicc.ac.cn

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2020-10-14
- 修回日期: 2020-11-25
- 网络出版日期: 2021-03-19
- 刊出日期: 2021-03-19

Study on the synthesis of melem catalyst and its application in synthesis of cyclic carbonate

1.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
General Design Department of Mechanical and Electrical Engineering, Beijing 100000, China

Funds: The project was supported by Key Research and Development Program of Shanxi Province (20181101012), Key Research and Development Program of Shanxi Province (201903D121104) and Shanxi Province Science Foundation for Youths (201901D211586)

摘要

摘要: 以纳米二氧化硅 (SiO₂) 为模板，以三聚氰胺为前驱体，采用固相反应法制备一系列介孔蜜勒胺 (melem) 材料。通过调控硬模板剂和前驱体的用量，最终得到一系列高比表面积 (40−92 m²/g) 和孔体积 (0.179−0.407 cm³/g)的介孔 melem材料。将其作为催化剂用于1, 4 -丁二醇二缩水甘油醚 (BDODGE) 与CO₂的环加成反应中，结果表明，随着比表面积增大，催化剂活性相比未加入模板剂的melem样品有了显著提高。三聚氰胺与纳米SiO₂的质量比为2时制备的催化剂，在130 ℃、20 h、2.0 MPa条件下，BDODGE转化率为99.3%，环碳酸酯选择性为99.5%。
- 三聚氰胺 /
- 介孔melem材料 /
- 环氧化合物 /
- 环状碳酸酯 /
- CO₂
Abstract: In this paper, a series of mesoporous melem materials were prepared from melamine by solid-phase reaction using nano-silica (SiO₂) as the template. The mesoporous melem materials with high specific surface area (40−92 m²/g) and pore volume (0.179−0.407 cm³/g) were obtained by adjusting the ratio of SiO₂ template and melamine. The obtained melem was used as catalyst for the cycloaddition reaction between BDODGE and CO₂. The results showed that the catalytic activity was greatly improved with the increase of specific surface area of the catalysts. The catalyst mp-CN-450-2 showed the best performance. After 20 h reaction at 130 ºC, 2.0 MPa, 99.3% of BDODGE conversion and 99.5% of cyclic carbonate selectivity were acquired, respectively.
- melamine /
- mesoporous melem materials /
- epoxide /
- cyclic carbonate /
- CO₂

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图 1 类石墨相氮化碳 (g-C₃N₄) 的合成过程

Figure 1 Synthesis reaction process of g-C₃N₄

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图 2 蜜勒胺 (melem) 催化剂的合成路线示意图

Figure 2 Synthesis process of melem catalyst

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图 3 BDODGE与CO₂的环加成反应

Figure 3 Cycloaddition reaction of BDODGE with CO₂

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图 4 样品CN-450-r (a) 和mp-CN-450-r (b) 的XRD谱图

Figure 4 XRD patterns of CN-450-r (a) and mp-CN-450-r (b) catalysts

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图 5 样品CN-450-r (a) 和mp-CN-450-r (b) 的FT-IR谱图

Figure 5 FT-IR spectra of CN-450-r (a) and mp-CN-450-r (b) catalysts

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图 6 CN-450 (a) 和mp-CN-450-r (b) 样品的SEM照片

Figure 6 SEM images of CN-450 (a) and mp-CN-450-r (b) samples

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图 7 mp-CN-450-r催化剂N₂吸附-脱附等温线 (a) 和孔径分布 (b)

Figure 7 Nitrogen adsorption-desorption isotherms (a) and Barret-Joyner-Halenda (BJH) pore size distribution plots (b) of mp-CN-450-r

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图 8 BDODGE及相应的环状碳酸酯的FT-IR和¹H NMR谱图

Figure 8 FT-IR spectra and ¹H NMR spectra of BDODGE and cyclic carbonate

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表 1 CN-450-r及mp-CN-450-r材料的织构分析

Table 1 Textual parameters of CN-450-r and mp-CN-450-r materials

Entry	Catalyst	S_BET/ (m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Average pore diameter / nm
1	CN-450	4	0.0157	16.3
2	CN-450-8	7	0.0332	19.1
3	CN-450-4	16	0.0589	14.8
4	CN-450-2	36	0.1394	15.6
5	mp-CN-450-8	40	0.1794	17.7
6	mp-CN-450-4	69	0.3275	18.9
7	mp-CN-450-2	92	0.4072	17.6
8	SiO₂	189	0.7826	16.6

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表 2 CN-450-r及mp-CN-450-r催化剂对BDODGE与CO₂环加成反应的影响

Table 2 Catalytic performance of different CN-450-r and mp-CN-450-r catalysts in the reaction of BDODGE and CO₂

Entry	Catalyst	BDODGE conversion/%	Selectivity/ %
1 ^a	CN-450	32.5	91.7
2 ^a	CN-450-8	25.8	99.0
3 ^a	CN-450-4	38.2	99.7
4 ^a	CN-450-2	33.5	94.2
5 ^b^[19]	CN-450-W	93.1	99.3
6 ^c	mp-CN-450-8	97.6	98.3
7 ^c	mp-CN-450-4	98.7	98.9
8 ^c	mp-CN-450-2	99.3	99.5
^a reaction conditions：W(BDODGE) = 30 g, W(catalyst) = 1.5 g, p(CO₂) = 2.0 MPa, t = 140 ℃, t = 20 h; ^b W(catalyst) = 2.1 g; ^c t = 130 ℃

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表 3 各种催化剂催化CO₂环加成反应对比

Table 3 Comparison of various catalysts for the cycloaddition of CO₂

Entry	Catalyst	Conversion / %	Selectivity / %	Ref.
1 ^a	m-C₃N₄	36.1	98.0	[19]
2 ^a	u-C₃N₄	51.3	98.2	[19]
3 ^b	ZnBr₂/u-CN/r-Al₂O₃	98.9	99.1	[25]
4 ^c	D296	95.8	97.1	[26]
5 ^d	LiBr	94.0	99.1	[27]
6	mp-CN-450-2	99.3	99.5	this work
^a reaction conditions：W(BDODGE) = 30 g, W(catalyst) = 5.0%, p(CO₂) = 1.0 MPa, t = 140 ℃, t = 20 h；^b W(catalyst) = 15.1%, t = 30 h；^c W(PPGDGE) = 100 g, W(catalyst) = 10%, t = 30 h；^d W(E51) = 30 g, W(catalyst) = 1.0%, W(DMF) = 25 g, t = 90 ℃

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