以ZSM-5/MCM-48为载体制备新型高容量CO2吸附剂的性能及机理研究

doi:10.15541/jim20240403

无机材料学报 ›› 2025, Vol. 40 ›› Issue (7): 833-839.DOI: 10.15541/jim20240403

以ZSM-5/MCM-48为载体制备新型高容量CO₂吸附剂的性能及机理研究

魏建文¹^,²^,³(), 张丽娟¹^,²^,³, 耿琳琳¹^,²^,³, 李誉¹^,²^,³, 廖雷¹^,²^,³, 王敦球¹^,²^,³

1.广西岩溶地区水污染控制与用水安全保障协同创新中心, 桂林理工大学, 桂林 541006
2.广西生态环保现代产业学院, 桂林理工大学, 桂林 541006
3.广西环境污染控制理论与技术重点实验室, 桂林理工大学, 桂林 541006

收稿日期:2024-09-06 修回日期:2024-12-05 出版日期:2025-07-20 网络出版日期:2024-12-11
作者简介:魏建文(1975-), 男, 教授. E-mail: jianwen988@126.com

Novel CO₂ Adsorbent Prepared with ZSM-5/MCM-48 as Support: High Adsorption Property and Its Mechanism

WEI Jianwen¹^,²^,³(), ZHANG Lijuan¹^,²^,³, GENG Linlin¹^,²^,³, LI Yu¹^,²^,³, LIAO Lei¹^,²^,³, WANG Dunqiu¹^,²^,³

1. Collaborative Innovation Center for Water Pollution Control and Water Safety in Karst Area, Guilin University of Technology, Guilin 541006, China
2. Modern Industry College of Ecology and Environmental Protection, Guilin University of Technology, Guilin 541006, China
3. Guangxi Key Laboratory of Environmental Pollution Control Theory and Technology, Guilin University of Technology, Guilin 541006, China

Received:2024-09-06 Revised:2024-12-05 Published:2025-07-20 Online:2024-12-11
About author:WEI Jianwen (1975-), male, professor. E-mail: jianwen988@126.com
Supported by:
National Natural Science Foundation of China(51966002);Natural Science Foundation of Guangxi Province(2020GXNSFAA159144)

摘要/Abstract

摘要：

固体胺吸附法是一种极具发展前景的烟气脱碳技术, 但该技术中吸附剂的CO₂吸附性能不高, 且吸附机理研究亦不深入。以微介孔复合分子筛ZSM-5/MCM-48为载体, 通过先接枝3-氨基丙基三乙氧基硅烷(APTES), 再将接枝后的样品浸渍四乙烯五胺(TEPA)或聚乙烯亚胺(PEI), 从而得到一种CO₂吸附性能优异的新型材料。当TEPA的负载量为60%(质量分数)时, APTES-ZSM-5/MCM-48-TEPA-60(A-ZM-T60)在60 ℃和15%(体积分数)CO₂环境下对CO₂的最大吸附量为5.82 mmol·g^-1。吸附过程以化学吸附为主, 吸附剂表面胺基与CO₂反应生成了氨基甲酸酯、氨基甲酸烷基铵和碳酸盐, 同时伴有较弱的物理吸附。该复合材料吸附性能优异, 可用于捕集脱硫后烟气中的CO₂。

关键词: ZSM-5/MCM-48, 胺双功能化, CO₂吸附, 吸附动力学, 吸附机理

Abstract:

Adsorption by solid amine adsorbent is a promising technology for decarbonization of flue gas. However, adsorption properties of many solid amine adsorbents need to be enhanced, and it is necessary to further study the CO₂ adsorption mechanism. A novel CO₂ adsorbent with high capacity was obtained by grafting 3-aminopropyltriethoxysilane (APTES) on a micro-mesoporous composite molecular sieve ZSM-5/MCM-48 as the support, and then impregnated with tetraethylenepentamine (TEPA) or polyethyleneimine (PEI). The maximum adsorption capacity of APTES-ZSM-5/MCM-48-TEPA-60 (A-ZM-T60), loaded with 60% (in mass) TEPA, for CO₂ reaches 5.82 mmol·g^-1 at 60 ℃ in 15% (in volume) CO₂. Carbamate, alkyl ammonium carbamate and carbonate are generated during the chemical adsorption, which is dominant for CO₂ adsorption because of the reaction between CO₂ and amino groups on the adsorbent, simultaneously accompanied by weak physical adsorption. All above data confirm that these composites display an outstanding adsorption performance with a bright future for CO₂ capture from flue gas after desulfurization.

Key words: ZSM-5/MCM-48, amino-bifunctionalization, CO₂ capture, adsorption kinetics, adsorption mechanism

中图分类号:

TQ424

魏建文, 张丽娟, 耿琳琳, 李誉, 廖雷, 王敦球. 以ZSM-5/MCM-48为载体制备新型高容量CO₂吸附剂的性能及机理研究[J]. 无机材料学报, 2025, 40(7): 833-839.

WEI Jianwen, ZHANG Lijuan, GENG Linlin, LI Yu, LIAO Lei, WANG Dunqiu. Novel CO₂ Adsorbent Prepared with ZSM-5/MCM-48 as Support: High Adsorption Property and Its Mechanism[J]. Journal of Inorganic Materials, 2025, 40(7): 833-839.

图/表 10

参考文献 34

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Adsorbent	S_BET/ (m²·g^-1)	V_t/ (cm³·g^-1)	N₂ content/ (mmol·g^-1)	CO₂ adsorption capacity/ (mmol·g^-1)
A-ZM-1	237.0	0.52	4.97	1.71
A-ZM-T50	111.2	0.21	8.94	5.04
A-ZM-T60	13.0	0.04	11.89	5.82
A-ZM-T70	5.8	0.02	14.85	4.51
A-ZM-P50	91.5	0.20	8.52	3.53
A-ZM-P60	12.3	0.03	11.17	3.96
A-ZM-P70	-	-	14.06	3.05

Adsorbent	S_BET/ (m²·g^-1)	V_t/ (cm³·g^-1)	N₂ content/ (mmol·g^-1)	CO₂ adsorption capacity/ (mmol·g^-1)
A-ZM-1	237.0	0.52	4.97	1.71
A-ZM-T50	111.2	0.21	8.94	5.04
A-ZM-T60	13.0	0.04	11.89	5.82
A-ZM-T70	5.8	0.02	14.85	4.51
A-ZM-P50	91.5	0.20	8.52	3.53
A-ZM-P60	12.3	0.03	11.17	3.96
A-ZM-P70	-	-	14.06	3.05

Support	Modifier	Condition (CO₂, in volume)	CO₂ adsorption capacity/(mmol·g^-1)	Ref.
MCF	APTMS+PEI	75 ℃/10.5% CO₂	2.36	[25]
SBA-15	APTES+TEPA	75 ℃/20% CO₂	5.68	[26]
HNTS	APTES+PEI	50 ℃/50% CO₂	1.03	[27]
PE-SBA-15	APTES+TEPA	40 ℃/15% CO₂	5.50	[28]
PE-SBA-15	DT+TEPA	40 ℃/15% CO₂	4.20	[28]
Beta/KIT-6	APTMS+TEPA	60 ℃/15% CO₂	5.12	[29]
ZSM-5/MCM-48	APTES+TEPA	60 ℃/15% CO₂	5.82	This work

Support	Modifier	Condition (CO₂, in volume)	CO₂ adsorption capacity/(mmol·g^-1)	Ref.
MCF	APTMS+PEI	75 ℃/10.5% CO₂	2.36	[25]
SBA-15	APTES+TEPA	75 ℃/20% CO₂	5.68	[26]
HNTS	APTES+PEI	50 ℃/50% CO₂	1.03	[27]
PE-SBA-15	APTES+TEPA	40 ℃/15% CO₂	5.50	[28]
PE-SBA-15	DT+TEPA	40 ℃/15% CO₂	4.20	[28]
Beta/KIT-6	APTMS+TEPA	60 ℃/15% CO₂	5.12	[29]
ZSM-5/MCM-48	APTES+TEPA	60 ℃/15% CO₂	5.82	This work

Model	Kinetics parameter	30 ℃	45 ℃	60 ℃	75 ℃	90 ℃
Pseudo-first-order	q_e/(mmol·g^-1)	4.21	4.49	5.68	5.13	3.95
	k₁/min^-1	0.062	0.083	0.062	0.089	0.080
	R²	0.989	0.966	0.989	0.973	0.987
Pseudo-second-order	q_e/(mmol·g^-1)	4.83	5.06	5.70	6.51	4.48
	k₂/(g·mmol^-1·min^-1)	0.017	0.021	0.022	0.012	0.023
	R²	0.997	0.988	0.991	0.997	0.987
Avrami	q_e/(mmol·g^-1)	4.37	4.75	5.89	5.34	4.00
	k_A/min^-1	0.109	0.153	0.109	0.167	0.099
	n_A	0.776	0.696	0.776	0.704	0.901
	R²	0.998	0.991	0.998	0.990	0.998

以ZSM-5/MCM-48为载体制备新型高容量CO₂吸附剂的性能及机理研究

Novel CO₂ Adsorbent Prepared with ZSM-5/MCM-48 as Support: High Adsorption Property and Its Mechanism

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