钙铜复合吸收剂CO<sub>2</sub>捕集性能优化研究进展

陈健; 孙世超; 李铭迪; 焦洪宇; 张益锋; 王业泰

doi:10.6054/j.jscnun.2022043

钙铜复合吸收剂CO₂捕集性能优化研究进展

doi: 10.6054/j.jscnun.2022043

1.
常熟理工学院汽车工程学院，常熟 215500
2.
中国能源建设集团江苏省电力设计院有限公司，南京 211102
3.
浙江新柴股份有限公司，新昌 312500

基金项目:

国家自然科学基金项目 51506011

详细信息

通讯作者:
王业泰, Email: wangyetai@cslg.edu.cn

中图分类号: TK16
计量
- 文章访问数: 32
- HTML全文浏览量: 3
- PDF下载量: 15
- 被引次数: 0
出版历程
- 收稿日期: 2022-03-12
- 网络出版日期: 2022-07-29
- 刊出日期: 2022-06-25

The Progress in the Research on Optimizing CO₂ Capture Performance of CaO/CuO Composites

1.
School of Automotive Engineering, Changshu Institute of Technology, Suzhou 215500, China
2.
China Energy Engineering Group Jiangsu Power Design Institute Co. Ltd., Nanjing 211102, China
3.
Zhejiang Xinchai Co. Ltd., Xinchang 312500, China

摘要

摘要: 开发高效、低成本的CO₂捕集技术是我国实现“碳达峰、碳中和”目标的重要途径。基于钙铜复合吸收剂的钙循环耦合化学链燃烧工艺是一种改进的钙循环技术，通过耦合化学链燃烧来替代钙循环技术中高能耗的空气分离器，可显著降低系统能耗、提高其经济性，受到了国内外学者的广泛关注。介绍了钙循环耦合化学链燃烧工艺的基本原理，阐述了目前钙循环耦合化学链燃烧工艺面临的重大挑战——钙铜复合吸收剂CO₂捕集性能在循环过程中的急剧衰减；综述了提高钙铜复合吸收剂CO₂捕集性能的改性措施，主要包括载体负载法、水蒸气活化、高温热预处理等；综合分析了各种改性方法的优缺点并指明了今后的研究方向。
- CO₂捕集 /
- 钙循环 /
- 化学链燃烧 /
- 吸附剂 /
- 烧结 /
- 改性
Abstract: The development of efficient and low-cost CO₂ capture technology is an important approach for China to achieve the goal of "carbon peak and carbon neutrality". The process of calcium looping integrated with chemical looping combustion based on CaO/CuO composites is a modified calcium looping process. In such a process, chemical looping combustion is coupled to substitute the energy-intensive air separation unit commonly used in the calcium looping, thus significantly reducing the system's energy consumption and improving the economy. The calcium looping integrated with chemical looping combustion process has attracted great attention worldwide. The basic principle of the calcium looping integrated with chemical looping combustion process is introduced, and the major challenge that the process faces is described, i.e., a rapid decline in CO₂ capture performance of CaO/CuO composites during cycling operations. Moreover, the modification methods to enhance the CO₂ capture performance of CaO/CuO composites are reviewed, mainly including the incorporation of stabilizer, steam activation and high-temperature thermal pretreatment. Finally, the advantages and disadvantages of various modification methods are analyzed comprehensively, and the direction to future research is discussed.
- CO₂ capture /
- calcium looping /
- chemical looping combustion /
- sorbent /
- sintering /
- modification

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图 1 钙循环技术示意图

Figure 1. The schema of the calcium looping process

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图 2 钙循环耦合化学链燃烧工艺示意图

Figure 2. The schema of calcium looping integrated with chemical looping combustion

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图 3 基于钙循环耦合化学链燃烧工艺的吸附强化甲烷水蒸气联合重整制氢工艺示意图

Figure 3. The schema of H₂ production through sorption-enhanced methane steam reforming process based on calcium looping integrated with chemical looping combustion

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图 4 钙铜复合吸收剂在不同次数循环后表面的元素分布图^[15]

Figure 4. The surface element distribution of CaO/CuO composites after different cycles^[15]

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图 5 采用湿法混合法时有无高温热预处理制备的钙铜复合吸收剂在循环反应中的示意图

Figure 5. The schema of CaO/CuO composites synthesized with the wet mixing method with or without high-temperature thermal pretreatment during cycling reactions

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图 6 中空微球钙铜复合吸收剂在钙循环耦合化学链燃烧工艺中的示意图

Figure 6. The schema of CaO/CuO composites with a hollow microsphere structure in calcium looping integrated with chemical looping combustion

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表 1 不同改性方法下钙铜复合吸收剂的CO₂捕集性能

Table 1. The CO₂ capture performance of CaO/CuO composite sorbent using different modification approaches

改性方法	反应器	反应条件^a	循环次数	CO₂吸附率		文献
改性方法	反应器	反应条件^a	循环次数	首次	末次	文献
载体负载法(MgO/Al₂O₃)和结构改性(核壳结构)	热重分析仪	煅烧/还原：750 ℃，15%CH₄，8 min 碳酸化：750 ℃，15%CO₂，10 min	30	0.05	0.08	[12]
载体负载法(水泥)	热重分析仪	煅烧/还原：875 ℃，CH₄，10 min 碳酸化：650 ℃，20%CO₂，15 min	16	0.06	0.02	[15]
载体负载法(MgO)	热重分析仪	煅烧/还原：750 ℃，10%CH₄，20 min 碳酸化：750 ℃，40%CO₂，40 min	15	0.15	0.10	[13]
载体负载法(MgO)	热重分析仪	煅烧/还原：800 ℃，15%CH₄，10 min 碳酸化：650 ℃，15%CO₂，10 min	4	0.26	0.20	[14]
载体负载法(MgO)	热重分析仪	煅烧/还原：950 ℃，15%CH₄，10 min 碳酸化：750 ℃，15%CO₂，10 min	4	0.11	0.09	[14]
载体负载法(Al₂O₃)	热重分析仪	煅烧/还原：850 ℃，10%CH₄，10 min 碳酸化：750 ℃，15%CO₂，30 min	35	0.18	0.11	[11]
载体负载法(Al₂O₃)和水蒸气活化(全过程通入水蒸气)	热重分析仪	煅烧/还原：850 ℃，10%CH₄，2%H₂O，10 min 碳酸化：750 ℃，15%CO₂，2%H₂O，30 min	10	0.18	0.16	[11]
载体负载法(MgO)和水蒸气活化(全过程通入水蒸气)	热重分析仪	煅烧/还原：750 ℃，15%CH₄，13.6%H₂O，10 min 碳酸化：750 ℃，15%CO₂，13.6%H₂O，10 min	10	0.08	0.075	[28]
载体负载法(MgO)和水蒸气活化(仅碳酸化反应通入水蒸气)	热重分析仪	煅烧/还原：750 ℃，15%CH₄，10 min 碳酸化：750 ℃，15%CO₂，13.6%H₂O，10 min	10	0.08	0.068	[28]
载体负载法(MgO)和高温热预处理	热重分析仪	煅烧/还原：750 ℃，15%CH₄，10 min 碳酸化：750 ℃，15%CO₂，10 min	40	0.07	0.05	[28]
载体负载法(水泥)和高温热预处理	热重分析仪	煅烧：650~875 ℃升温，N₂，22.5 min 还原：875 ℃，CH₄，10 min 碳酸化：650 ℃，20%CO₂，15 min	15	0.02	0.01	[15]
载体负载法(水泥)和水蒸气活化(仅碳酸化反应通入水蒸气)	热重分析仪	煅烧：650~875 ℃升温，N₂，22.5 min 还原：875 ℃，CH₄，10 min 碳酸化：650 ℃，20%CO₂，10%水蒸气，15 min	10	0.10	0.06	[15]
结构改性(纳米结构)	热重分析仪	煅烧/还原：650~800 ℃升温，15%CH₄，15 min 碳酸化：650 ℃，15%CO₂，30 min	40	0.11	0.17	[26]
结构改性(核壳结构)	固定床反应器	煅烧/还原：850 ℃，66.5% H₂，15 min 碳酸化：650 ℃，15%CO₂，15 min	12	0.11	0.07	[29]
结构改性(中空微球结构)	固定床反应器	煅烧/还原：850 ℃，20%CH₄，10 min 碳酸化：650 ℃，15%CO₂，5 min	20	0.21	0.15	[27]
结构改性(中空微球结构)	固定床反应器	煅烧/还原：940 ℃，20%CH₄(CO₂作为平衡气)，10 min 碳酸化：650 ℃，15%CO₂，5 min	10	0.19	0.12	[27]
结构改性(纳米结构)	固定床反应器	煅烧/还原：800~850 ℃升温并保温10 min，1%CH₄，15 min 碳酸化：650 ℃，15%CO₂，10 min	19	0.13	0.10	[30]
注：CO₂吸附率为吸附的CO₂质量与吸附剂质量之比；a表示无特别说明，都选用N₂作为平衡气。

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表 2 普遍使用的载体的塔曼温度

Table 2. The Tammann temperatures of commonly used stabilizers

物质	塔曼温度/℃	文献	物质	塔曼温度/℃	文献
Al₂O₃	900	[31]	MgO	1 276	[32]
Ca₃Al₂O₆	771	[32]	Y₂O₃	1 083	[33]
Ca1₂Al1₄O₃₃	725	[31]	CeO₂	1 064	[34]
TiO₂	785	[31]	Nd₂O₃	1 049	[35]
CaTiO₃	851	[31]	Yb₂O₃	1 094	[36]
SiO₂	664	[31]	La₂O₃	1 021	[37]
Ca₂SiO₄	929	[38]	WO₃	600	[37]
ZrO₂	1 221	[31]	HfO₂	1 250	[37]
CaZrO₃	1 036	[31]

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