工业烟道气碳捕集膜技术放大研究进展

doi:10.11949/0438-1157.20240992

化工学报 ›› 2025, Vol. 76 ›› Issue (2): 504-518.DOI: 10.11949/0438-1157.20240992

• 综述与专论 • 上一篇

工业烟道气碳捕集膜技术放大研究进展

杨晋宁¹(), 王卫凡²(), 徐冬¹(), 刘毅¹, 翁小涵¹, 原野², 王志²()

^1.国家能源集团新能源技术研究院有限公司，北京 102209
^2.天津大学化工学院化学工程研究所，天津市膜科学与海水淡化技术重点实验室，化学工程联合国家重点实验室（天津大学），天津化学化工协同创新中心，天津 300350

收稿日期:2024-09-02 修回日期:2024-10-02 出版日期:2025-03-25 发布日期:2025-03-10
通讯作者: 徐冬,王志
作者简介:杨晋宁（1984—），女，硕士，工程师，jinning.yang@ceic.com
王卫凡（1999—），男，博士研究生，1024207035@tju.edu.cn
基金资助:
国家能源集团科技项目(GJNY-23-88)

Progress in the scale-up research of membrane technologies for industrial flue gas carbon capture

Jinning YANG¹(), Weifan WANG²(), Dong XU¹(), Yi LIU¹, Xiaohan WENG¹, Ye YUAN², Zhi WANG²()

^1.National Energy Group New Energy Technology Research Institute Co. , Ltd. , Beijing 102209, China
^2.Chemical Engineering Research Center, School of Chemical Engineering and Technology (Tianjin University), Tianjin Key Laboratory of Membrane Science and Desalination Technology, State Key Laboratory of Chemical Engineering (Tianjin University), Tianjin Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300350, China

Received:2024-09-02 Revised:2024-10-02 Online:2025-03-25 Published:2025-03-10
Contact: Dong XU, Zhi WANG

摘要/Abstract

摘要：

工业烟道气是全球碳排放的主要来源之一，也是碳捕集技术的重点应用领域。综述了工业烟道气碳捕集领域中的膜技术放大研究进展。首先，介绍了CO₂/N₂分离膜的工作原理。其次，总结了化石能源发电厂、水泥厂、钢铁厂烟道气的来源与成分，并分析了在这些烟道气碳捕集过程中膜分离技术所面临的挑战。然后，对烟道气碳捕集膜的放大生产、烟道气碳捕集膜组件研究、工业烟道气碳捕集膜放大测试进行现状介绍和问题分析。最后，展望了膜技术在工业烟道气碳捕集中的发展方向，包括实现CO₂分离混合基质膜放大、针对钢铁厂烟道气的CO分离膜的开发以及膜组件的优化。旨在为学者们提供工业烟气碳捕捉膜放大的最新研究进展和未来方向。

关键词: 烟道气, 二氧化碳捕集, 膜, 化石燃料发电厂, 水泥厂, 钢铁厂

Abstract:

CO₂ emissions from industrial flue gases are among the primary sources of global carbon emissions and are key areas for the application of carbon capture technologies. The research progress on scale-up of membrane technology in the field of carbon capture from industrial flue gas is reviewed. First, the working principles of CO₂/N₂ separation membranes are introduced. The sources and compositions of flue gases from fossil fuel power plants, cement plants, and steel plants are summarized, and the challenges faced by membrane separation technology in the carbon capture process of these flue gases are discussed. Next, the current status and issues related to the scale-up preparation of flue gas carbon capture membranes, research on flue gas carbon capture membrane modules, and scale-up testing of industrial flue gas carbon capture membranes are introduced and analyzed. Finally, the development trends in membrane technology for industrial flue gas carbon capture are discussed, including the scale-up of CO₂ separation mixed-matrix membranes, the development of CO separation membranes for steel mill flue gases, and the optimization of membrane modules. This review aims to provide scholars with the latest research developments and future directions in the scale-up of industrial flue gas carbon capture membranes.

Key words: flue gas, CO₂ capture, membranes, fossil fuel power plant, cement plant, steel plant

中图分类号:

TQ 028.8

杨晋宁, 王卫凡, 徐冬, 刘毅, 翁小涵, 原野, 王志. 工业烟道气碳捕集膜技术放大研究进展[J]. 化工学报, 2025, 76(2): 504-518.

Jinning YANG, Weifan WANG, Dong XU, Yi LIU, Xiaohan WENG, Ye YUAN, Zhi WANG. Progress in the scale-up research of membrane technologies for industrial flue gas carbon capture[J]. CIESC Journal, 2025, 76(2): 504-518.

图/表 18

图1 2022年全球碳排放贡献图（总排放：34.75 Gt CO2）[2]

Fig.1 Global carbon emissions contribution map 2022 (total emission: 34.75 Gt CO2)[2]

图2 以溶解扩散(a)和促进传递(b)为机理的CO2/N2分离膜的分离过程示意图

Fig.2 Schematic diagram of the separation process for CO2/N2 separation membranes based on the mechanisms of solution-diffusion (a) and facilitated transport (b)

表1 不同的化石燃料发电厂烟道气组成［22］

Table 1 Composition of flue gas from different fossil fuel power plants［22］

烟道气参数	天然气联合循环电厂	硬煤发电厂	褐煤发电厂
压力/atm	1	1	1
CO₂/%	3.89	13.3	14
N₂/%	75.34	71.62	69.61
H₂O/%	8.21	11.25	13.04
O₂/%	12.56	3.81	3.35
NO _x /10^-6	24	97	80
SO _x /10^-6	0	50	40

图3 经典的水泥生产流程

Fig.3 Classic cement production process

表2 水泥厂烟道气组成［26-27］

Table 2 Composition of flue gas from cement plants［26-27］

组成	Norcem水泥厂	San Antonio水泥厂
CO₂	17%~20%	29.58%
N₂	50%~63%	48.95%
H₂O	11%~18%	11.20%
O₂	9%~12%	10.22%
SO₂	0~130 mg/m³(标准状况)	0.04%
NO _x	180~250 mg/m³(标准状况)	0.01%

图4 典型的高炉-转炉生产工艺简图

Fig.4 Schematic diagram of the typical blast furnace-basic oxygen furnace production process

表3 典型的高炉-转炉工艺钢铁厂烟道气主要成分［33］

Table 3 Main components of flue gas from a typical blast furnace-basic oxygen furnace steelmaking process［33］

成分	含量/%
CO₂	17~25
CO	20~28
N₂	50~55
H₂	1~5

图5 Pebax典型结构(a)和PolyActive结构(b)示意

Fig.5 Typical structure of Pebax (a) and the structure of PolyActive (b)

图6 常见的用于制备CO2分离促进传递膜的多胺基聚合物化学结构

Fig.6 Chemical structures of common polyamine-based polymers used for preparing CO2 separation membrane with facilitated transport

图7 文献报道的放大制备的CO2/N2分离膜（灰色区域内）与实验室规模的高性能CO2/N2分离膜性能对比

Fig.7 The performance comparison chart of CO2/N2 separation membranes fabricated on a large scale reported in the literature (inside the gray area) and high-performance CO2/N2 separation membranes at laboratory scale

表4 CO2/N2分离膜组件汇总

Table 4 Summary of CO2/N2 separation membrane modules

膜分离层材料	组件膜面积	组件类型	文献
PVAm	1.5 m²	板框式	[52]
PolyActive^TM	12.5 m²	板框式	[53]
PVAm	300 cm²	卷式	[54]
PVAm	1.4 m²	卷式	[55]
PVAm	2.94 m²	卷式	[56]
PVAm	35 m²	卷式	[43]
Polaris^TM	—	卷式	[57]
PVAm	0.4 m²	卷式	[58]
PVAm	5 m²	卷式	[58]
PVAm	25 m², 31 m²	卷式	[59]
PVA/ProK	200 cm²	中空纤维	[60]
PVAm	4.2 m²	中空纤维	[18]
SHPAA/PVA/pGO	200 cm²	中空纤维	[61]

表5 中试及以上规模的水泥厂和化石能源发电厂烟道气碳捕集膜技术项目情况

Table 5 Carbon capture membrane technology projects for flue gas at pilot scale and above in cement plants and fossil fuel power plants

气源	规模^①	膜分离层材料	能耗或成本	CO₂捕集率/%	CO₂纯度/%	文献
天然气电厂	1000 m³/d(标准状况)	PES	—	70~95	95~99	[62]
燃煤电厂	1.5 m²	PVAm	—	—	75	[52]
水泥厂	1.5 m²	PVAm	333.6 kWh	60~70	72	[26]
燃煤电厂	—	PRISM	—	—	—	[35]
燃煤电厂	12.5 m²	PolyActivetm^TM	—	42.7	68.2	[41]
燃煤电厂	1 t/d	Polaris^®	—	90	70	[63]
水泥厂	18 m²	PVAm	333.6 kWh	80	95	[64]
燃煤电厂	8.4 m²	PVAm	—	—	60	[18]
燃煤电厂	1.4 m²	PVAm/PZEA-Sar	—	40	94.5	[55]
燃煤电厂	75 m²	PVAm	809 kWh	60.7	87.2	[65]
燃煤电厂	50000 m³/d(标准状况)	PVAm	844.6 kWh	81.1	96.6	[51]
水泥厂	200 cm²	SHPAA/ PVA/pGO	89.11 EUR/t CO₂	—	55	[61]

图8 四级膜分离工艺示意图[62]

Fig.8 Schematic diagram of a four-stage membrane separation process[62]

图9 基于Polaris膜的碳捕集系统流程[63]

Fig.9 Process flow of a carbon capture system based on Polaris membrane[63]

图10 三级耦合三段的膜法燃煤电厂烟气碳捕集工业示范装置工艺流程图[65]

Fig.10 Process flow diagram of a three-stage coupled, three-section membrane-based industrial demonstration system for flue gas carbon capture in coal-fired power plants[65]

图11 50000 m3/d（标准状况）烟气膜法碳捕集工业示范装置[51]

Fig.11 Photographs of the industrial membrane demonstration plant for CO2 capture at a flue gas treating capacity of 50000 m3/d[51]

表6 钢铁厂废气碳捕集膜技术的模拟和实验研究

Table 6 Simulation and experimental studies of carbon capture membrane technology for steel plant flue gas

膜材料	膜过程	CO₂捕集率/%	CO₂纯度/%	文献
PVAm	两级膜过程	79~97	—	[67]
Polaris^®	两级膜过程	99	95	[33]
PVAm	两级膜过程	95.5	94	[68]
Polaris^TM	两级膜过程	80	81	[69]
PVAm	两级膜过程	81.5	80.7	[51]

图12 Luca等[68]设计的结合回流吹扫的两级膜分离工艺

Fig.12 A two-stage membrane separation process with refluxed permeate gas as sweep gas designed by Luca et al.[68]

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工业烟道气碳捕集膜技术放大研究进展

Progress in the scale-up research of membrane technologies for industrial flue gas carbon capture

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