Relationship Between Cation Exchange Time and CO2 Adsorption Performance

doi:10.12422/j.issn.1672-6952.2026.01.003

Abstract

Abstract:

The regulation of metal cations in zeolites via ion exchange to enhance CO₂ adsorption performance holds significant potential for the efficient industrial capture of CO₂. To investigate the correlation between metal cation exchange time and CO₂ adsorption performance of zeolites, four adsorbent samples (e.g. Ca?LTA?30) were prepared with exchange time as the independent variable. The textural properties, thermal stability, CO₂temperature?programmed desorption (CO₂?TPD), and CO₂ adsorption performance of these samples were characterized. Furthermore, the IAST (Ideal Adsorbed Solution Theory) selectivity of these samples for CO₂/N₂ gas mixtures with different volume ratios (20∶80, 50∶50, 80∶20) was compared. The results indicate that the CO₂ adsorption performance of LTA can be increased from 5.02 mmol/g to 6.05 mmol/g, while the S_CO $2$ _/N $2$ can be improved from 59.7 to 118.5. In addition, through comparing the fitting performance of four adsorption models on the adsorption isotherms of CO₂ and N₂ on LTA and Ca?LTA series samples, it is found that the Langmuir?Freundlich model exhibits the best consistency with the experimental data and can effectively evaluate the CO₂ adsorption behavior of the Ca?LTA series samples.

Key words: Exchange time, CO₂ adsorption performance, LTA zeolite, Metal cation, Adsorption model

摘要：

采用离子交换法调控分子筛中的金属阳离子，可优化其对CO₂的吸附性能，为实现分子筛在工业领域高效捕集CO₂提供巨大的潜力。为研究金属阳离子交换时长与分子筛吸附CO₂性能的关联性，以交换时长为变量，制备了Ca?LTA?30等四种吸附剂样品，并通过织构特征分析和热稳定性测试、CO₂程序升温脱附（CO₂?TPD）及CO₂吸附性能表征，对比了其对不同CO₂/N₂混合气（体积比分别为20∶80、50∶50、80∶20）的理想吸附溶液理论（IAST）选择性。结果表明，选择合适的金属阳离子交换时长，可在增加LTA样品表面弱碱性位点数量的同时，将其对CO₂的吸附容量由5.02 mmol/g提高至6.05 mmol/g，对CO₂吸附选择性由59.7提高至118.5。此外，通过对比四种吸附模型对LTA及Ca?LTA系列样品的CO₂和N₂吸附等温线的拟合效果发现，Langmuir?Freundlich吸附模型的拟合曲线与实验数据一致性最佳，能更精准地描述Ca?LTA系列样品对CO₂的吸附行为。

关键词: 交换时长, CO₂吸附性能, LTA分子筛, 金属阳离子, 吸附模型

CLC Number:

TE991

Zhiqi LIU, Yucai QIN, Xiaoxin ZHANG, Jingsa JIA, Yilong TAN, Hongchi LI, Xiaosong ZHANG. Relationship Between Cation Exchange Time and CO₂ Adsorption Performance[J]. Journal of Liaoning Petrochemical University, 2026, 46(1): 19-28.

刘祉琦, 秦玉才, 张晓欣, 贾晶萨, 谭溢龙, 李宏池, 张晓松. 阳离子交换时长与CO₂吸附性能的关联性[J]. 辽宁石油化工大学学报, 2026, 46(1): 19-28.

Figures/Tables 19

Table 1 Elemental analysis results of LTA and Ca?LTA series samples

吸附剂	w（Na）/%	w（Si）/%	w（Al）/%	w（Ca）/%	w（K）/%	硅铝比
LTA	7.36	42.17	66.10	20.93	0.46	0.64
Ca⁃LTA⁃2	6.18	41.66	66.10	22.03	0.44	0.63
Ca⁃LTA⁃10	5.44	41.87	65.32	22.44	0.42	0.64
Ca⁃LTA⁃30	5.12	41.55	66.28	22.53	0.40	0.63
Ca⁃LTA⁃60	4.12	41.47	64.92	23.84	0.38	0.64

Fig.1 N2 adsorption?desorption isotherms of LTA and Ca?LTA series samples (-196 ℃)

Table 2 Textural properties of LTA and Ca?LTA series samples

吸附剂	S_BET/（m²·g^-1）	S_微孔/（m²·g^-1）	S_介孔/（m²·g^-1）	V_总/（cm³·g^-1）	V_微孔/（cm³·g^-1）	V_介孔/（cm³·g^-1）
LTA	115	110	5	0.05	0.04	0.004
Ca⁃LTA⁃2	702	682	20	0.28	0.26	0.020
Ca⁃LTA⁃10	698	671	27	0.28	0.26	0.020
Ca⁃LTA⁃30	720	698	22	0.29	0.27	0.020
Ca⁃LTA⁃60	732	707	25	0.29	0.27	0.020

Fig.2 Pore size distribution profiles of LTA and Ca?LTA series samples

Fig.3 SEM images of LTA and Ca?LTA series samples

Fig.4 XRD patterns of LTA and Ca?LTA series samples

Fig.5 Thermogravimetric curves of LTA and Ca?LTA series samples

Fig.6 CO2?TPD profiles of LTA and Ca?LTA series samples

Fig.7 Comparison of CO2 adsorption performance of LTA and Ca?LTA series samples at different temperatures

Fig.8 CO2 and N2 adsorption isotherms and model fitting curves for LTA sample (25 ℃)

Fig.9 CO2 and N2 adsorption isotherms and model fitting curves for Ca?LTA?30 sample (25 ℃)

Table 3 Fitting parameters of adsorption isotherm L model for CO2 and N2 on LTA and Ca?LTA?30 (25 ℃)

样品	吸附质	q_c	k_c	R²/%
LTA	CO₂	5.00	0.41	99.84
LTA	N₂	1.00	1.00	100.00
Ca⁃LTA⁃30	CO₂	5.99	0.41	99.73
Ca⁃LTA⁃30	N₂	1.00	1.00	81.59

Table 4 Fitting parameters of adsorption isotherm LF model for CO2 and N2 on LTA and Ca?LTA?30 (25 ℃)

样品	吸附质	q_c	k_c	n	R²/%
LTA	CO₂	5.16	0.42	0.88	99.96
LTA	N₂	3.43	0	0.91	100.00
Ca⁃LTA⁃30	CO₂	6.27	0.44	0.82	99.96
Ca⁃LTA⁃30	N₂	2.14	0	0.96	100.00

Table 5 Fitting parameters of adsorption isotherm DL model for CO2 and N2 on LTA and Ca?LTA?30 (25 ℃)

样品	吸附质	q_c	k_c	q_i	k_i	R²/%
LTA	CO₂	2.50	0.41	2.50	0.41	99.84
LTA	N₂	0.74	0.01	0.74	0.01	99.81
Ca⁃LTA⁃30	CO₂	3.00	0.41	4.00	0.41	99.73
Ca⁃LTA⁃30	N₂	0.29	0.02	0.29	0.02	96.14

Table 6 Fitting parameters of adsorption isotherm DLF model for CO2 and N2 on LTA and Ca?LTA?30 (25 ℃)

样品	吸附质	q_c	k_c	q_i	k_i	R²/%
LTA	CO₂	4.61	0.49	1.21	0.01	100.00
LTA	N₂	4.44	0	0.18	0.02	99.99
Ca⁃LTA⁃30	CO₂	3.00	0.41	3.00	0.41	99.73
Ca⁃LTA⁃30	N₂	0.50	0.01	0.50	0.01	99.58

Table 7 Fitting parameters of the LF adsorption model for CO2 and N2 adsorption isotherms (25 ℃)

样品	吸附质	q_c	k_c	n	R²/%
Ca⁃LTA⁃2	CO₂	5.18	0.44	0.83	100.00
Ca⁃LTA⁃2	N₂	3.36	0	0.94	100.00
Ca⁃LTA⁃10	CO₂	5.15	0.43	0.81	99.96
Ca⁃LTA⁃10	N₂	6.20	0	0.80	99.16
Ca⁃LTA⁃60	CO₂	6.11	0.45	0.79	100.00
Ca⁃LTA⁃60	N₂	2.33	0	0.95	100.00

Fig.10 CO2 and N2 adsorption isotherms and LF model fitting curves for Ca?LTA series samples (25 ℃)

Fig.11 CO2 adsorption heat of LTA and Ca?LTA series samples

Fig.12 IAST selectivity comparison of LTA and Ca?LTA series samples for mixed gas (CO2/N2)

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Relationship Between Cation Exchange Time and CO₂ Adsorption Performance

阳离子交换时长与CO₂吸附性能的关联性

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