直接空气捕集二氧化碳技术研究进展

doi:10.16085/j.issn.1000-6613.2023-0606

摘要/Abstract

摘要：

直接空气捕集（DAC）二氧化碳技术作为负碳排放技术的一种，可助力实现“双碳”目标，是一项极具发展前景的碳捕集技术。本文简述了DAC的发展历史与现有DAC项目的运行及发展情况，介绍了碱性氢氧化物溶液、胺溶液、氨基酸盐溶液/BIGs与碱度浓度变化四种液体DAC技术，以及固体碱（土）金属、固态胺、金属有机框架MOFs材料及变湿吸附等固体DAC技术。对各种DAC技术的工艺流程及相关设备进行了综述，详述了各种DAC技术的原理、二氧化碳捕集方法及吸附/吸收剂再生方式，重点分析了每种DAC技术在吸附/吸收剂性能、再生温度、再生能耗及循环稳定性等方面的优缺点。指出需进一步研发低成本、高吸附/吸收性能且循环稳定性好的DAC吸附/吸收剂，优化或开发吸附/吸收剂再生工艺，同时开发适用于DAC技术的过程强化技术，为DAC的后续规模化与商业化应用奠定基础。

关键词: 二氧化碳, 直接空气捕集, 吸附, 吸收法, 解吸

Abstract:

Direct air capture (DAC) of carbon dioxide technology is a kind of negative carbon technology. As one of the important technologies to help achieving the carbon peaking and carbon neutrality goals, DAC technology has great development prospects. The development history of DAC and the operation and development of existing DAC projects were briefly described, and some liquid DAC technologies and solid DAC technologies were introduced. The liquid DAC technologies included aqueous hydroxide sorbents, aqueous basic solutions, aqueous amino acids/BIGs and alkalinity concentration swing technologies. The solid DAC technologies included solid alkali carbonates, solid-supported amine materials, MOFs materials,moisture swing technology and so on. The technological process and related equipment of various DAC technology were summarized. The principle of various DAC technologies, carbon dioxide capture methods and adsorbent/absorbent regeneration methods were described in detail. The advantages and disadvantages of each DAC technology in terms of adsorbent/absorbent performance, regeneration temperature, regeneration energy consumption and cycle stability were analyzed. It was pointed out that it was necessary to further develop DAC adsorbents/absorbents with low cost, high adsorption/absorption performance and good cycle stability, optimize and develop adsorbent/absorbent regeneration process, and develop process strengthening technology suitable for DAC technology, so as to lay a foundation for the subsequent large-scale and commercial application of DAC.

Key words: carbon dioxide, direct air capture, adsorption, absorption, desorption

中图分类号:

TQ028

廖昌建, 张可伟, 王晶, 曾翔宇, 金平, 刘志禹. 直接空气捕集二氧化碳技术研究进展[J]. 化工进展, 2024, 43(4): 2031-2048.

LIAO Changjian, ZHANG Kewei, WANG Jing, ZENG Xiangyu, JIN Ping, LIU Zhiyu. Progress on direct air capture of carbon dioxide[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 2031-2048.

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载体	胺基	实验环境	最大吸附容量 /mmol∙g^-1	吸附-脱附循环条件	循环吸附量 /mmol∙g^-1	参考文献
SBA-15	TEPA（质量分数50%）	400μg/g CO₂	2.30（600min）	吸附25℃， 60min；脱附110℃， 15min	1.72~1.66（10次循环）	[74]
大孔硅	PA（10.98mmol /g）	400μg/g CO₂	2.65	10%CO₂：吸附50℃，40min；脱附110℃，10min	3.86~3.78（120次循环）	[75]
介孔炭	PEI（质量分数55%）	400μg/g CO₂	2.25（720min）	吸附25℃；脱附110℃，45min	2.25~2.18（10次循环）	[76]
多壁碳纳米管（NWCN）	PEI（质量分数20%乙醇）	350μg/g CO₂	2.12（720min）	吸附30℃，10min；脱附90℃，20min	1.07~0.96（10次循环）	[77]
纳米纤维（NFC）	AEAPDMS （4.9mmol/g）	506μg/g CO₂, RH40%	1.39（720min）	吸附25℃，120min；脱附90℃，60min	平均0.695（20次循环）	[78]
Mg_0.55Al-CO₃LDHs	TEPA（质量分数67%）	400μg/g CO₂	3.0（180min）	吸附25℃，100min；脱附100℃，10min	1.31~1.19（80次循环）	[79]
Mg_0.55Al-CO₃LDHs	TEPA（质量分数67%）	400μg/g CO₂	3.0（180min）	吸附25℃， 180min；脱附100℃，15min	2.55~2.31（20次循环）	[79]
Mg_0.55Al-CO₃LDHs	TRI（6.399mmol∙g^-1）	400μg/g CO₂	1.05（120min）	吸附25℃， 60min；脱附120℃，15min	0.912（50次循环）	[80]
层状SiO₂	TEPA（质量分数70%）	400μg/g CO₂	5.2（700min）	吸附30℃，25min；脱附110℃，30min	4.5~3.5（10次循环）	[81]
Mg₂（dobdc）	N₂H₄（6.01mmol∙g^-1）	400μg/g CO₂	3.89	15%CO₂：吸附40℃，40min；脱附130℃	3.86（5次循环）	[82]
聚丙烯腈（PAN）中空纤维	TEPA（质量分数30.1%）	470μg/g CO₂, RH25%	2.15（440min）	吸附25℃；脱附100℃	2.03（20次循环）	[83]

载体	胺基	实验环境	最大吸附容量 /mmol∙g^-1	吸附-脱附循环条件	循环吸附量 /mmol∙g^-1	参考文献
SBA-15	TEPA（质量分数50%）	400μg/g CO₂	2.30（600min）	吸附25℃， 60min；脱附110℃， 15min	1.72~1.66（10次循环）	[74]
大孔硅	PA（10.98mmol /g）	400μg/g CO₂	2.65	10%CO₂：吸附50℃，40min；脱附110℃，10min	3.86~3.78（120次循环）	[75]
介孔炭	PEI（质量分数55%）	400μg/g CO₂	2.25（720min）	吸附25℃；脱附110℃，45min	2.25~2.18（10次循环）	[76]
多壁碳纳米管（NWCN）	PEI（质量分数20%乙醇）	350μg/g CO₂	2.12（720min）	吸附30℃，10min；脱附90℃，20min	1.07~0.96（10次循环）	[77]
纳米纤维（NFC）	AEAPDMS （4.9mmol/g）	506μg/g CO₂, RH40%	1.39（720min）	吸附25℃，120min；脱附90℃，60min	平均0.695（20次循环）	[78]
Mg_0.55Al-CO₃LDHs	TEPA（质量分数67%）	400μg/g CO₂	3.0（180min）	吸附25℃，100min；脱附100℃，10min	1.31~1.19（80次循环）	[79]
Mg_0.55Al-CO₃LDHs	TEPA（质量分数67%）	400μg/g CO₂	3.0（180min）	吸附25℃， 180min；脱附100℃，15min	2.55~2.31（20次循环）	[79]
Mg_0.55Al-CO₃LDHs	TRI（6.399mmol∙g^-1）	400μg/g CO₂	1.05（120min）	吸附25℃， 60min；脱附120℃，15min	0.912（50次循环）	[80]
层状SiO₂	TEPA（质量分数70%）	400μg/g CO₂	5.2（700min）	吸附30℃，25min；脱附110℃，30min	4.5~3.5（10次循环）	[81]
Mg₂（dobdc）	N₂H₄（6.01mmol∙g^-1）	400μg/g CO₂	3.89	15%CO₂：吸附40℃，40min；脱附130℃	3.86（5次循环）	[82]
聚丙烯腈（PAN）中空纤维	TEPA（质量分数30.1%）	470μg/g CO₂, RH25%	2.15（440min）	吸附25℃；脱附100℃	2.03（20次循环）	[83]

技术名称	优点	缺点
碱性氢氧化物溶液DAC技术	技术成熟，吸收速率高	再生温度高、再生能耗高，损失大量水分
胺溶液DAC技术	吸收速率较高	伴随胺液挥发且再生效率较低
氨基酸盐溶液/BIGs DAC技术	吸收速率高，再生温度较低，溶剂损失少	能耗较高，捕集效果因BIGs 而异
碱度浓度变化DAC技术	吸收速率较高，再生温度与能耗较低，可与海水淡化研究合作	捕集效果与溶液浓缩技术相关联，用水量大
固体碱（土）金属DAC技术	吸附效率较高，再生稳定性较好	再生能耗较高，成本较高
固态胺吸附剂DAC技术	技术成熟，吸附速率快，再生温度低	吸附剂的热稳定性有待进一步提高
MOFs材料DAC技术	在较低温度下有应用优势	捕集效果受环境中水含量影响较大，原材料成本较高
变湿吸附DAC技术	吸附与解吸速率高，再生温度及再生能耗较低	用水量大，对水质要求高，得到的CO₂分压较低
DACM技术	可同时实现CO₂捕集与转化，受湿度影响较小	再生温度较高，催化剂起决定性作用
光诱导摆动吸附DAC技术	再生能耗较低	需在材料内嵌入光反应因子
MI-DAC技术	再生能耗较低，可应用于海水	捕集效果主要取决于微生物

技术名称	优点	缺点
碱性氢氧化物溶液DAC技术	技术成熟，吸收速率高	再生温度高、再生能耗高，损失大量水分
胺溶液DAC技术	吸收速率较高	伴随胺液挥发且再生效率较低
氨基酸盐溶液/BIGs DAC技术	吸收速率高，再生温度较低，溶剂损失少	能耗较高，捕集效果因BIGs 而异
碱度浓度变化DAC技术	吸收速率较高，再生温度与能耗较低，可与海水淡化研究合作	捕集效果与溶液浓缩技术相关联，用水量大
固体碱（土）金属DAC技术	吸附效率较高，再生稳定性较好	再生能耗较高，成本较高
固态胺吸附剂DAC技术	技术成熟，吸附速率快，再生温度低	吸附剂的热稳定性有待进一步提高
MOFs材料DAC技术	在较低温度下有应用优势	捕集效果受环境中水含量影响较大，原材料成本较高
变湿吸附DAC技术	吸附与解吸速率高，再生温度及再生能耗较低	用水量大，对水质要求高，得到的CO₂分压较低
DACM技术	可同时实现CO₂捕集与转化，受湿度影响较小	再生温度较高，催化剂起决定性作用
光诱导摆动吸附DAC技术	再生能耗较低	需在材料内嵌入光反应因子
MI-DAC技术	再生能耗较低，可应用于海水	捕集效果主要取决于微生物

捕集能力	吸附剂/吸收剂	解吸温度/℃	能源	能耗	CO₂压力/bar	CO₂纯度	成本/USD·t^-1	参考文献
1Mt/a	KOH	900	天然气	8.81GJ/t	150	97.1%	94~232	[35]
1Mt/a	KOH	900	天然气+电力	5.25GJ/t+366kWh/t	150	97.1%	94~232	[35]
1Mt/a	KOH	900	电力	1535kWh/t	1	>97%	186	[131]
0.291t/h	MEA	123.1	电力	1452kWh/t	2	—	676	[41]
0.36Mt/a	K₂CO₃	80~100	余热	7.5GJ/t+694kWh/t	—	>99%	135~177	[131]
3600t/a	K₂CO₃	80~100	余热	7.5GJ/t+694kWh/t	—	>99%	203~244	[131]
—	CaO	875	太阳能	240.9 GJ/t	—	—	—	[50]
—	K₂CO₃/γ-Al₂O₃	150	热能+机械能	7.3GJ/t+0.27GJ/t	—	—	—	[58]
300t/a	胺基	100	余热	5.4~7.2GJ/t+200~300Wh/t	—	99.9%	预计大规模75	[131]
—	氨基聚合物	85~95	蒸汽	4.2~5.1GJ/t+150~260Wh/t	—	>98.5%	<113	[131]
—	氨基聚合物	75	低温蒸汽	—	—	>98.5%	≤50	[95]
140g/d	MOFs	80，真空	余热	—	—	70%~80%	34~350	[101]
166.08t/h	变湿吸附剂+胺液	—	太阳能	306GJ/t	—	97%	93.1	[130]
365t/a	变湿吸附剂	变湿	电力	316kWh/t	—	—	99 （预期<30）	[131]
—	变湿吸附剂	45	余热	0.81GJ/t	—	3%	34.68	[117]
—	氨基酸盐溶液/m-BBIG	60~120	余热	8.2GJ/t	—	—	—	[43]
—	氨基酸盐溶液/PyBIG	80~120	余热	6.5GJ/t	—	—	—	[43]
—	ACS	RO	电力	1011~1200kWh/t	1	99.8%	—	[46]
—	ACS	MCDI	电力	1072~2400kWh/t	1	99.8%	—	[46]
1Mt/a	MI-DAC	pH改变	生物能	—	—	—	30.54	[129]