负载型咪唑类离子液体催化CO<sub>2</sub>转化合成碳酸丙烯酯研究

滑淑清; 王景芸; 孙京; 周明东

doi:10.19906/j.cnki.JFCT.2023027

负载型咪唑类离子液体催化CO₂转化合成碳酸丙烯酯研究

doi: 10.19906/j.cnki.JFCT.2023027

辽宁石油化工大学石油化工学院, 辽宁抚顺 113001

详细信息

通讯作者:
E-mail: sunjing@lnpu.edu.cn

中图分类号: TQ2
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出版历程
- 收稿日期: 2023-02-23
- 修回日期: 2023-03-21
- 录用日期: 2023-03-22
- 网络出版日期: 2023-04-06
- 刊出日期: 2023-10-10

Synthesis of propylene carbonate from CO₂ catalyzed by supported imidazoles ionic liquids

School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, China

摘要

摘要: CO₂是导致全球气候变暖的主要温室气体之一，但同时又是丰富的C1资源，故其高值化利用受到了人们关注。环状碳酸酯是电池及电容器的优良介质，在工业生产中应用极为广泛。因此，从环境保护和资源利用的角度看，将CO₂转化为环状碳酸酯具有重要的意义。本工作合成了一系列聚苯乙烯树脂负载的咪唑类非均相催化剂，考察了此类催化剂在高压反应釜中催化二氧化碳环加成反应的活性。结果表明，催化剂PS-TBIM-PCIMBr₂表现出优秀且稳定的催化活性，PS-TBIM-PCIMBr₂在固定床连续反应器上可以连续运行500 h，反应依旧可以获得91%的产率。
- 二氧化碳 /
- 环氧丙烷 /
- 环状碳酸酯 /
- 咪唑离子液体 /
- 多相催化剂
Abstract: Carbon dioxide is one of the most main greenhouse gases causing the global warming, however, as a rich C1 resource, the high value utilization of CO₂ has attracted wide attention. Cyclic carbonate is an excellent medium for batteries and capacitors, which is widely used in industrial production. Therefore, it is of great significance to convert CO₂ into cyclic carbonate from the viewpoint of environmental protection and resource utilization. In this paper, we synthesized a series of imidazole heterogeneous catalysts supported on polystyrene resin, and the catalytic activity for cycloaddition reaction of CO₂ in high pressure reactor was studied. The results showed that PS-TBIM-PCIMBr₂ exhibited the excellent and stable catalytic activity. PS-TBIM-PCIMBr₂ was also used to prepare propylene carbonate in the continuous fixed-bed reactor and the yield of PC was still 91% after 500 h.
- carbon dioxide /
- propylene oxide /
- cyclic carbonate /
- imidazole ionic liquid /
- heterogeneous catalyst

HTML全文

FIG. 2710. FIG. 2710.

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图 1 二氧化碳与环氧化物制备环状碳酸酯的示意图

Figure 1 Schematic diagram of preparing cyclic carbonate from carbon dioxide and epoxides

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图 2 各固载化离子液体催化剂的结构示意图

Figure 2 Structural schematic diagram of immobilized ionic liquid catalyst

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图 3 氯球和催化剂的FT-IR谱图

Figure 3 FT-IR spectra of PS-Cl and catalysts

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图 4 催化剂的热重分析曲线

Figure 4 TGA curves of catalysts

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图 5 PS-Cl和催化剂的扫描电镜照片

Figure 5 SEM image of PS-Cl and catalysts

(Each set of (a) refers to a large SEM image of the sample; each set of (b) refers to a locally enlarged SEM image of the sample)

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图 6 催化剂用量对CO₂环加成反应的影响

Figure 6 Effect of catalyst usage on thecycloaddition reaction

（Reaction conditions: PO 0.137 mol, 120 ℃, CO₂ 2 MPa, 4 h）

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图 7 二氧化碳压力对CO₂环加成反应的影响

Figure 7 Effect of CO₂ pressure on the cycloaddition reaction

（Reaction conditions: PO 0.137 mol, PS-TBIM-PCIMBr₂ 20%, 120 ℃, 4 h）

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图 8 反应温度对CO₂环加成反应的影响

Figure 8 Effect of temperature on thecycloaddition reaction

（Reaction conditions: PO 0.137 mol, PS-TBIM-PCIMBr₂ 20%, CO₂ 2 MPa, 4 h）

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图 9 反应时间对CO₂环加成反应的影响

Figure 9 Effect of reaction time on the cycloaddition reaction

（Reaction conditions: PO 0.137 mol, PS-TBIM-PCIMBr₂ 20%, CO₂ 2 MPa, 120 ℃）

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图 10 催化剂PS-TBIM-PCIMBr₂的稳定性试验

Figure 10 Stability test of catalyst PS-TBIM-PCIMBr₂

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图 11 催化剂PS-TBIM-PCIMBr₂的固定床分析

Figure 11 The behavior of fixed bed reactor of PS-TBIM-PCIMBr₂

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表 1 催化剂的元素分析

Table 1 Elemental analysis data of catalysts

Entry	Catalyst	N /%	C /%	H /%	IL grafting amount /(mmol·g⁻¹)
1	PS-MIMCl	6.25	83.94	7.35	2.23
2	PS-CPIMBr	7.71	60.13	5.63	2.75
3	PS-TBIM-PCIMBr₂	7.95	60.19	6.71	1.42
4	PS-TBIM-IMPCOOHTMGBr₂	9.53	55.44	6.11	0.97

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表 2 CO₂制备碳酸丙烯酯反应的催化活性^a

Table 2 Catalytic activity of the preparation of propylene carbonate from CO₂^a

Entry	Catalyst	Selectivity^b /%	Yield^b /%
1	−	−	0
2	PS-Cl	−	0
3	PS-MIMCl	99	40
4	PS-CPIMBr	99	83
5	PS-TBIM-PCIMBr₂	99	90
6	PS-TBIM-IMPCOOHTMGBr₂	99	91
^a: Reaction conditions: PO 0.137 mol, catalyst 20%, 120 ℃, CO₂ 2 MPa, 4 h; ^b: Determined by GC analysis

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表 3 各种环氧化物与二氧化碳反应的催化活性^a

Table 3 Catalytic activity of various epoxides with carbon dioxide^a

Entry	Epoxide	Cyclic carbonate	Selectivity^b /%	Yield^b/%
1			99	99
2			99	99
3			99	98
4			99	96
5			99	68
6			99	95
^a: Reaction conditions: Epoxide (0.137 mol), PS-TBIM-PCIMBr₂ (20%), 120 ℃, CO₂ 2 MPa, 5 h, ^b: Determined by GC analysis

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