含钛渣制备Ca-LTA沸石及其CO2吸附性能

doi:10.12141/j.issn.1000-565X.240417

华南理工大学学报(自然科学版) ›› 2025, Vol. 53 ›› Issue (3): 139-148.doi: 10.12141/j.issn.1000-565X.240417

• 化学化工 • 上一篇

含钛渣制备Ca-LTA沸石及其CO₂吸附性能

皇甫林¹(), 贺政卿²(), 赵世民², 周新涛³, 罗中秋³, 祖运³, 尚波³, 李方园³

^1.钒钛资源综合利用国家重点实验室，四川攀枝花 617000
^2.云南省生态环境科学研究院，云南昆明 650034
^3.昆明理工大学化学工程学院，云南昆明 650500

收稿日期:2024-08-23 出版日期:2025-03-10 发布日期:2024-10-11
通信作者: 贺政卿 E-mail:l_huangfu@163.com;he163xin@163.com
作者简介:皇甫林（1992—），男，博士，工程师，主要从事CO₂捕集及转化研究。E-mail： l_huangfu@163.com
基金资助:
钒钛资源综合利用国家重点实验室开放课题(2022P4FZG03A);云南省科技厅昆明理工大学“双一流”创建联合专项(202101BE070001-031);昆明理工大学分析测试基金项目(2022T20160009);云南省基础研究计划项目(202401AT070384)

Preparation and CO₂ Adsorption Performance of Ca-LTA Zeolite Derived From Titanium-Containing Slag

HUANGFU Lin¹(), HE Zhengqing²(), ZHAO Shimin², ZHOU Xintao³, LUO Zhongqiu³, ZU Yun³, SHANG Bo³, LI Fangyuan³

^1.State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization，Panzhihua 617000，Sichuan，China
^2.Yunnan Institute of Environmental Science Research，Kunming 650034，Yunnan，China
^3.Faculty of Chemical Engineering，Kunming University of Science and Technology，Kunming 650500，Yunnan，China

Received:2024-08-23 Online:2025-03-10 Published:2024-10-11
Contact: HE Zhengqing E-mail:l_huangfu@163.com;he163xin@163.com
Supported by:
the Open Project of State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(2022P4FZG03A);the Basic Research Planning Program of Yunnan Province(202401AT070384)

摘要/Abstract

摘要：

LTA沸石因其优异的孔隙结构和较高的CO₂吸附选择性，被认为是极具潜力的CO₂捕获材料。该文提出了一种以工业固废含钛渣为原料的绿色可持续合成策略，先制备Na-LTA沸石母体，再通过常规液相离子交换法（LPIE）调控钙负载量，制备出xCa-LTA沸石系列，以提升其CO₂吸附性能；然后通过动态吸附法对样品的吸附性能进行评价。实验结果表明：xCa-LTA沸石不仅显著提高了CO₂的捕集能力，还在CO₂/N₂和CO₂/CH₄分离过程中表现出优异的选择性，尤其是0.05Ca-LTA样品的吸附性能最为突出；在25 ℃、10⁵ Pa条件下，0.05Ca-LTA的CO₂吸附速率为Na-LTA的4.95倍，最大吸附容量达到4.02 mmol/g。动力学分析结果表明：0.05Ca-LTA对CO₂的吸附行为符合拟二级动力学模型，吸附过程由物理吸附和化学吸附协同主导，这种协同作用不仅加快了吸附速率，还提高了吸附效率；经过5次吸附/脱附循环后，0.05Ca-LTA仍保持高效稳定的吸附性能，展现了优异的循环再生能力。该研究遵循“以废治废”的环保理念，不仅为固废的高值化利用提供了新路径，也为CO₂捕集与环境污染治理的协同优化提供了重要的理论参考和应用潜力。

关键词: 含钛渣, LTA沸石, 钙离子交换, CO₂捕集, 吸附机理

Abstract:

LTA-type zeolites is considered a highly promising CO₂ capture material due to their excellent pore structures and high selectivity for CO₂ adsorption. This study presented a green and sustainable synthesis approach using industrial titanium-containing slag waste as a raw material to prepare Na-LTA zeolite precursors. Calcium loading was adjusted via a conventional liquid-phase ion exchange (LPIE) method to produce a series of xCa-LTA zeolites, specifically designed to enhance CO₂ adsorption performance. The adsorption properties of the xCa-LTA zeolites were systematically evaluated through dynamic adsorption experiments. Results show that xCa-LTA zeolites not only significantly enhances CO₂ capture capacity, but also exhibits excellent selectivity in CO₂/N₂ and CO₂/CH₄ separation processes, with the 0.05Ca-LTA sample demonstrating the most outstanding adsorption performance. Under conditions of 25 ℃ and 105 Pa, the CO₂ adsorption rate of 0.05Ca-LTA is 4.95 times that of Na-LTA, with a maximum adsorption capacity of 4.02 mmol/g. Kinetic analysis indicates that the CO₂ adsorption behavior of 0.05Ca-LTA follows a pseudo-second-order kinetic model, where the adsorption process is synergistically dominated by both physisorption and chemisorption. This synergy not only accelerated adsorption rates but also improved overall efficiency. After five adsorption/desorption cycles, 0.05Ca-LTA maintains highly efficient and stable adsorption performance, demonstrating excellent cyclic regeneration capability. This study follows the ecofriendly concept of “treating waste with waste” providing a new approach for the high-value utilization of solid waste while offering important theoretical and application potential for the synergistic optimization of CO₂ capture and environmental pollution control.

Key words: titanium-containing slag, Na-LTA zeolite, calcium ion exchange, CO₂ capture, adsorption mechanism

中图分类号:

X701

皇甫林, 贺政卿, 赵世民, 周新涛, 罗中秋, 祖运, 尚波, 李方园. 含钛渣制备Ca-LTA沸石及其CO₂吸附性能[J]. 华南理工大学学报(自然科学版), 2025, 53(3): 139-148.

HUANGFU Lin, HE Zhengqing, ZHAO Shimin, ZHOU Xintao, LUO Zhongqiu, ZU Yun, SHANG Bo, LI Fangyuan. Preparation and CO₂ Adsorption Performance of Ca-LTA Zeolite Derived From Titanium-Containing Slag[J]. Journal of South China University of Technology(Natural Science Edition), 2025, 53(3): 139-148.

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样品	质量分数/%		比表面积/ （m²‧g^-1）		孔容/ （cm³‧g^-1）		介孔孔径/nm
样品	Ca	Na	BET	微孔	总孔	微孔	介孔孔径/nm
Na-LTA	0.16	14.72	14.8	7.8	0.026	0.004	8.411
0.01Ca-LTA	1.51	11.86	14.7	5.1	0.030	0.002	9.392
0.02Ca-LTA	1.66	10.75	11.9	6.5	0.031	0.003	12.414
0.05Ca-LTA	6.84	4.79	537.7	486.0	0.243	0.186	4.698
0.10Ca-LTA	7.51	4.45	520.4	484.6	0.240	0.184	6.920

样品	拟一级动力学模型			拟二级动力学模型
样品	q_e/（mmol‧g^-1）	k₁/min^-1	R²	q_e/（mmol‧g^-1）	k₂/（mmol‧（g·min）^-1）	R²
Na-LTA	1.939	1.540	0.674	1.964	1.416	0.916
0.01Ca-LTA	2.497	4.706	0.934	2.508	3.971	0.995
0.02Ca-LTA	2.892	2.280	0.986	2.915	1.609	0.945
0.05Ca-LTA	3.297	7.674	0.986	3.304	7.015	0.998
0.10Ca-LTA	3.346	7.674	0.987	3.353	6.375	0.995
0.25Ca-LTA	3.312	6.395	0.993	3.319	5.948	0.990

名称	吸附条件		吸附量/ （mmol‧g^-1）	来源
名称	压力/kPa	温度/K	吸附量/ （mmol‧g^-1）	来源
CaA	15.00	313	3.72	文献［28］
Ca-LTA-3	0.04	298	1.12	文献［18］
Micro-LTA	100.00	298	1.94	文献［29］
Meso-LTA	100.00	298	3.63	文献［29］
5A	100.00	298	3.68	文献［30］
5A@ZIF-8	100.00	298	0.31	文献［30］
Na-A	15.00	298	1.40	文献［28］
Mg-A	15.00	298	1.80	文献［28］
Ca-A	15.00	298	3.81	文献［28］
K-LTA	100.00	298	2.11	文献［28］
Ce-LTA	100.00	298	3.76	文献［28］
0.05Ca-LTA	100.00	298	4.02	文中

含钛渣制备Ca-LTA沸石及其CO₂吸附性能

Preparation and CO₂ Adsorption Performance of Ca-LTA Zeolite Derived From Titanium-Containing Slag

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