湿法再生CO2空气捕集材料的能耗与性能优化

doi:10.11949/0438-1157.20200756

化工学报 ›› 2021, Vol. 72 ›› Issue (3): 1409-1418.DOI: 10.11949/0438-1157.20200756

湿法再生CO₂空气捕集材料的能耗与性能优化

倪佳¹(),孙雪艳¹,税子怡¹,贺飞鸿²,惠小敏³,朱亮亮¹(),陈曦⁴()

^1.西北大学化工学院，陕西西安 710069
^2.中国石化达州天然气净化有限公司，四川达州 635000
^3.中国石油化工股份有限公司中原油田分公司石油工程技术研究院，河南濮阳 457001
^4.哥伦比亚大学地球工程中心地球与环境工程系，美国纽约 NY100 27

收稿日期:2020-06-16 修回日期:2020-10-23 出版日期:2021-03-05 发布日期:2021-03-05
通讯作者: 朱亮亮,陈曦
作者简介:倪佳(1996—)，女，硕士研究生，jiani@stumail.nwu.edu.cn
基金资助:
西安市科技计划项目(2019112713CXSF005SF015)

Energy consumption and performance optimization of moisture swing sorbents for direct air capture of CO₂

NI Jia¹(),SUN Xueyan¹,SHUI Ziyi¹,HE Feihong²,HUI Xiaomin³,ZHU Liangliang¹(),CHEN Xi⁴()

^1.School of Chemical Engineering, Northwest University, Xi’an 710069, Shaanxi, China
^2.Dazhou Natural Gas Purification Co. , Ltd. , SINOPEC, Dazhou 635000, Sichuan, China
^3.Petroleum Engineering Technology Research Institute, Zhongyuan Oilfield Company, SINOPEC, Puyang 457001, Henan, China
^4.Department of Earth and Environmental Engineering, Earth Engineering Center, Columbia University, NY 10027, United States

Received:2020-06-16 Revised:2020-10-23 Online:2021-03-05 Published:2021-03-05
Contact: ZHU Liangliang,CHEN Xi

摘要/Abstract

摘要：

湿法再生阴离子交换树脂膜材料，可通过调控湿度驱动CO₂的吸附与脱附，材料再生成本极低。该材料需经过高温水热预处理张开孔结构，增强气体扩散速率，能耗较高；此外，利用液态水润湿材料以驱动脱附时，材料的解吸比（脱附量/吸附量）只有~30%。通过系统研究不同预处理水温及时间下膜材料的CO₂吸附/脱附性能，发现采用常温水浸泡预处理亦可获得良好的材料微观孔结构以及碳捕集性能，显著降低预处理能耗；更重要的是，基于微观尺度的气体吸附和液体浸润相关理论，实验发现超声雾化所获得的微米级水颗粒，由于更易扩散进入孔隙，可将解吸比从~30%提升到~60%，极大提升了树脂膜材料的再生性能。这些预处理能耗与脱附性能的优化，为大规模空气捕集的工程化实施提供了有利条件。

关键词: 二氧化碳, 吸附, 脱附, 空气捕集, 离子交换树脂, 湿法再生

Abstract:

The reduction of the number of water molecules in a nano-system actively promotes the hydrolysis of CO₃^2- to HCO₃^- and OH^-, leading to a moisture-swing nano-structured CO₂ sorbent that spontaneously binds CO₂ in ambient air when dry, while releasing it when wet. As it trades the input of heat in a thermal swing or the mechanical energy in a pressure swing of the traditional sorbents, against the consumption of water, the energy input for CO₂ capture is very low. This brings about an inexpensive and efficient direct air capture technology for mitigating the greenhouse problem. The sorbents are usually heterogeneous sheets composed of amine-based anion exchange resins and a matrix polymer. In order to obtain a hierarchical microporous structure to allow sufficient access of the air to the ion-exchange resins buried inside the matrix, previously, hydrothermal pretreatment of the resin sheets was employed before put into operation. In addition, the desorption ratio (desorption quantity/adsorption quantity) of the material is only ~30% when desorption is activated by exposing to bulk water. The present work aims to reduce the energy consumption for pretreatment and improve the desorption performance. The hydrothermal pretreatment time and temperature are studied systematically. It was found that the room-temperature soaking pretreatment instead of hydrothermal pretreatment of the resin sheets, can also lead to excellent microporous structures and carbon capture performances, concerning both the capture capacity and kinetics. More importantly, based on the infiltration mechanism of gas and liquid into nanopores, we found that the micron-sized water particles produced by ultrasonic atomization could greatly promote the desorption ratio, from ~30% to ~60%, compared to that by exposing the sorbent to bulk water. The mechanism is analyzed from the perspectives of the water quantity, water particle size and its diffusion/infiltration ability. The optimization of these pretreatment energy consumption and desorption performance provides favorable conditions for the engineering implementation of large-scale air capture.

Key words: carbon dioxide, adsorption, desorption, direct air capture, ion exchange resin, moisture-swing

中图分类号:

倪佳, 孙雪艳, 税子怡, 贺飞鸿, 惠小敏, 朱亮亮, 陈曦. 湿法再生CO₂空气捕集材料的能耗与性能优化[J]. 化工学报, 2021, 72(3): 1409-1418.

NI Jia, SUN Xueyan, SHUI Ziyi, HE Feihong, HUI Xiaomin, ZHU Liangliang, CHEN Xi. Energy consumption and performance optimization of moisture swing sorbents for direct air capture of CO₂[J]. CIESC Journal, 2021, 72(3): 1409-1418.

图/表 10

图1 湿法再生阴离子交换树脂的CO2捕集原理

Fig.1 Schematic illustration of reversible CO2 capture by moisture swing

表1 聚乙烯异相阴离子交换树脂膜的详细参数

Table 1 Manufacturer data on the commercial heterogeneous polyethylene anion exchange membrane

厚度/mm

含水率/%

离子交换容量/

(mol/kg)

尺寸变化率/%

爆破强度/

MPa

图2 CO2吸附-脱附性能测试装置

Fig.2 The experimental system for CO2 absorption/desorption

图3 不同预处理时间、不同预处理方法所获得的QAR500树脂膜的SEM图

Fig.3 SEM images of the microporous structure of QAR500 sheets with different pretreatment time and methods

图4 不同预处理时间、预处理方法所得QAR500膜的CO2吸附容量

Fig.4 CO2 adsorption capacity of QAR500 with different pretreatment methods and time

图5 不同预处理方式所得QAR500膜的CO2吸附动力学过程

Fig. 5 Adsorption kinetics of QAR500 sheets with different pretreatment methods

表2 QAR500膜材料MPFO理论模型拟合吸附参数

Table 2 Fitting adsorption parameters of the MPFO model for QAR500 sheets

预处理方法	Q_e/(mmol/g)	k₁/min^-1	k₂/min^-1	R²	吸附平衡时间/min
水热处理48 h	0.77	0.035	0.159	0.9992	160
常温水浸泡5 d	0.78	0.026	0.037	0.9991	180

图6 QAR500膜材料在不同加湿方案下的脱附过程以及MPFO模型理论曲线

Fig.6 Desorption kinetics of QAR500 sheets with different humidification methods

表3 不同脱附方法下MPFO模型拟合脱附参数

Table 3 Fitting desorption parameters of the MPFO model for QAR500 sheets with different humidification methods

脱附方法	预处理方法	Q_e/(mmol/g)	解吸比R_des/%	k₁/min^-1	k₂/min^-1	R²	脱附平衡时间/min
超声加湿	水热处理 (48 h)	0.530	68.83	0.223	0.092	0.9960	40
超声加湿	常温水浸泡 (5 d)	0.510	65.38	0.205	0.099	0.9980	40
浸润加湿	水热处理 (48 h)	0.240	31.17	0.869	0.078	0.9920	40
浸润加湿	常温水浸泡 (5 d)	0.210	26.92	0.826	0.077	0.9960	40
自然蒸发加湿	水热处理 (48 h)	0.170	22.08	0.156	0.076	0.9912	40
自然蒸发加湿	常温水浸泡 (5 d)	0.160	20.51	0.142	0.073	0.9933	40

图7 不同预处理方法和预处理时间所得QAR500膜的脱附性能

Fig.7 Desorption performance of QAR500 sheets with different pretreatment methods and time

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湿法再生CO₂空气捕集材料的能耗与性能优化

Energy consumption and performance optimization of moisture swing sorbents for direct air capture of CO₂

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