粉煤灰制备A、H型分子筛及其吸附SO<sub>2</sub>、CO<sub>2</sub>和NO的机制

代芮嘉; 赵永奇; 窦金孝; 余江龙

doi:10.13205/j.hjgc.202604023

粉煤灰制备A、H型分子筛及其吸附SO₂、CO₂和NO的机制

doi: 10.13205/j.hjgc.202604023

1. 辽宁科技大学化学工程学院辽宁先进煤焦化省重点实验室, 辽宁鞍山 114051;
2. 中国科学院过程研究所, 北京 100190

基金项目:

国家自然科学基金项目（22378180）；辽宁省教育厅面上项目（JYTMS20230960）

详细信息

作者简介:
代芮嘉(1999—),女,硕士研究生,主要研究方向为大气污染控制。ruijiadai999@163.com

通讯作者:
窦金孝(1986—),男,副教授,博士生导师,主要研究方向为大气污染控制。doujx123@163.com

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出版历程
- 收稿日期: 2025-06-06
- 网络出版日期: 2026-06-06
- 刊出日期: 2026-04-01

Synthesis of A- and H-type zeolites from fly ash and their adsorption mechanisms for SO₂， CO₂， and NO

1. Key Laboratory for Advanced Coal and Coking Technology of Liaoning Province, School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China;
2. Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

摘要

摘要: 粉煤灰富含高比例的硅和铝，将其合成高附加值的分子筛并用于吸附有害气体已成为研究热点之一。目前，粉煤灰基分子筛主要用于吸附高浓度的气体污染物，对低浓度气体污染物，尤其是对酸性气体的吸附研究较少。针对烟气中低浓度酸性气体SO₂、CO₂、NO，利用粉煤灰基分子筛（A型、H型）进行吸附并对其吸附性能进行探究。采用固定红外联用测试平台在低浓度气氛（1000 mg/m³）、不同分子筛类型和不同温度条件下，探究A、H型分子筛对SO₂、CO₂、NO不同气体的饱和吸附量。利用in-situ DRIFTS光谱并结合动力学模型，探究A型和H型分子筛对SO₂、CO₂、NO的吸附机制。实验结果表明：分子筛的比表面积、孔结构是影响其吸附性能的主要因素，A型分子筛对SO₂、CO₂、NO的吸附能分别为-5.11，-4.07，-1.41 kJ/mol，其吸附能力明显强于H型分子筛。A型和H型分子筛表面上的T-O（T=Si/Al）基团是吸附酸性气体的关键活性位点，且A型分子筛具有更大的比表面积以及更多的硅羟基活性位点。实验结果为粉煤灰基分子筛吸附酸性气体提供理论依据。
- 粉煤灰 /
- 分子筛 /
- 吸附 /
- 酸性气体 /
- 动力学
Abstract: Fly ash， with its high content of silicon and aluminum， has become a hot topic for synthesizing high-value-added zeolites and absorbing harmful gases. However， current research primarily focuses on using fly ash-based zeolites to adsorb high-concentration gas pollutants， with few studies addressing low-concentration gas pollutants， especially acidic gases. In this study， the adsorption performance of fly ash-based zeolites （A- and H-type） for low-concentration acidic gases （SO₂， CO₂， and NO） in flue gas was investigated. The saturated adsorption capacities of A- and H-type zeolites for SO₂， CO₂， and NO were evaluated using a fixed bed infrared combined test platform under low-concentration conditions （1000 mg/m³）， for different zeolite types， and at varying temperatures. The adsorption mechanisms of SO₂， CO₂， and NO by A- and H-type zeolites were studied using in-situ DRIFTS spectroscopy combined with kinetic modeling. The experimental results showed that the specific surface area and pore structure of the zeolites were the main factors affecting their adsorption performance. The adsorption energies of A-type zeolite for SO₂， CO₂， and NO were -5.11 kJ/mol， -4.07 kJ/mol， and -1.41 kJ/mol， respectively， indicating a significantly stronger adsorption capacity compared to H-type zeolite. The T-O （T=Si/Al ） groups on the surface of A- and H-type zeolites were identified as the key active sites for acid gas adsorption， with A-type zeolite possessing a larger specific surface area and more silanol active sites. The experimental results provide a theoretical basis for the adsorption of acidic gases by fly ash-based zeolites.
- fly ash /
- zeolite /
- adsorption /
- acidic gas /
- kinetics

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参考文献(37)

[1]	WANG F Q，YUAN Y T，DU Y G，et al. Experimental study on comprehensive utilization of desulfurization gypsum and fly ash in thermal power plant［J］. Environmental Engineering，2008，26（1）：64- 67. 王方群，原永涛，杜云贵，等. 火电厂脱硫石膏和粉煤灰综合利用的实验研究［J］. 环境工程，2008，26（1）：64- 67.
[2]	WANG Q，HAN L，WANG Y T，et al. Conversion of coal into N-doped porous carbon for high-performance SO₂ adsorption［J］. RSC Advances，2022，12（32）：20640- 20648.
[3]	ZHAO Y Y，CHENG Y P，ZHANG T T，et al. Bipolar membrane electrodialysis combined with ozone oxidation wet scrubbing to remove SO₂ and NOx from flue gas and achieve CO₂ mineralization［J］. Fuel，2023，340：127436.
[4]	WANG C Q，CHENG L X，YING Y，et al. Utilization of all components of waste concrete：Recycled aggregate strengthening，recycled fine powder activity，composite recycled concrete and life cycle assessment［J］. Journal of Building Engineering，2024，82：108255.
[5]	CHEN Y G，XU T T，HAN H J，et al. Research development of zeolites preparation from coal fly ash by microwave-hydrothermal synthesis［J］. Chemical Industry and Engineering Progress，2015，34（8）：2916- 2924. 陈彦广，徐婷婷，韩洪晶，等. 粉煤灰微波-水热合成法制备分子筛的研究进展［J］. 化工进展，2015，34（8）：2916- 2924.
[6]	KO D. Comparison of carbon molecular sieve and zeolite 5A for CO₂ sequestration from CH₄/CO₂ mixture gas using vacuum pressure swing adsorption［J］. Korean Journal of Chemical Engineering，2021，38（5）：1- 9.
[7]	ZHANG Q D，YE M，LEI Y Y，et al. Additive-free synthesis of house-of-card NaX zeolite for supporting amine：An efficient adsorbent for SO₂ removal［J］. Separation and Purification Technology，2025，354（P8）：129481- 129481.
[8]	LIU G Q，LIN Y X，ZHANG L L，et al. Preparation of NaA zeolite molecular sieve based on solid waste fly ash by high-speed dispersion homogenization-assisted alkali fusion-hydrothermal method and its performance of ammonia-nitrogen adsorption［J］. Journal of Science：Advanced Materials and Devices，2024，9（1）：100673.
[9]	LIU D，QI J W，XU Z Z，et al. Adsorption performance of toluene on hydrophobic modified molecular sieves under high humidity［J］. Environmental Engineering，2023，41（2）：66- 72. 刘东，齐俊文，徐遵主，等. 疏水改性分子筛在高湿度环境下对甲苯的吸附性能［J］. 环境工程，2023，41（2）：66- 72.
[10]	GAO Y N，ZHOU L T，WANG J，et al. Treatment of ammonia nitrogen in micro-polluted water by chitosan coated zeolite molecular sieve［J］. Environmental Engineering，2018，36（12）：108- 112. 郜玉楠，周历涛，王静，等. 壳聚糖包覆沸石分子筛处理微污染水中的氨氮［J］. 环境工程，2018，36（12）：108- 112.
[11]	DENG K，SONG R J，LOU B，et al. Improving the strength and reliability of mortar composites with zeolite substitution［J］. Case Studies in Construction Materials，2024，21：e04037.
[12]	SHEN Z M，WEI Q S，FU Y F，et al. Synthesization and characterizations of coal fly ash-coffee grounds-based composite as super-absorbent for application in soil［J］. Journal of Cleaner Production，2024，475：143568.
[13]	LIU Q，YU Y T，ZHU G L，et al. Hybrid super absorbent resin based on waste slag modified zeolite：A potential component adopted to agricultural water retention［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2024，699：134732.
[14]	NI X M，ZHENG Z，WANG X S，et al. Fabrication of hierarchical zeolite 4A microspheres with improved adsorption capacity to bromofluoropropene and their fire suppression performance［J］. Journal of Alloys and Compounds，2014，592：135- 139.
[15]	GANJI F，MOHAMMADI K，ROOZBEHANI B. Efficient synthesis of 4A zeolite based-NiCo₂O₄（NiCo₂O₄@4A）nanocomposite by using hydrothermal method［J］. Journal of Solid State Chemistry，2020，282：121111.
[16]	WEI C，XIE Z Q，GU J R，et al. High-volume utilization of circulating fluidized bed fly ash for the production of autoclaved aerated concrete：Performance optimization and hydration characteristics［J］. Construction and Building Materials，2024，448：138305.
[17]	GUO J Q，FAN Y P，DONG X S，et al. Study on preparation of UV-CDs/Zeolite-4A/TiO₂ composite photocatalyst coupled with ultraviolet-irradiation and their application of photocatalytic degradation of dyes［J］. Journal of Environmental Management，2024，354：120342.
[18]	LIU J，ZHONG X，GAO L，et al. Hierarchical porous Pd/HS-1 zeolite as an efficient and reusable catalysts for Suzuki-Miyaura reaction［J］. Applied Surface Science，2024，659：159904.
[19]	APONTE Y，LASA D H. The effect of Zn on offretite zeolite properties. acidic characterizations and NH₃-TPD desorption models［J］. Industrial& Engineering Chemistry Research，2017，56（8）：1948- 1960.
[20]	FU T J，ZHOU H，LI Z. Effect of particle morphology for ZSM-5 zeolite on the catalytic conversion of methanol to gasoline-range hydrocarbons［J］. Catalysis Letters，2016，146：1973- 1983.
[21]	CHEN Z，LI X G，LIU H H，et al. A novel and cost-effective synthesis of magnetic zeolite 4A using kaolinite and red mud for Sr（II）removal［J］. Microporous and Mesoporous Materials，2024，370：113069.
[22]	CHENG M，LUO Y，GENG J X，et al. Adsorption behavior of iodide ion by silver-doped zeolite 4A in LiCl-KCl molten salt［J］. Advanced Powder Technology，2022，33：103415.
[23]	SUN H M，ZHAO S L，MA Y G，et al. Effective and regenerable Ag/4A zeolite nanocomposite for Hg⁰ removal from natural gas［J］. Journal of Alloys and Compounds，2018，762：520- 527.
[24]	ZHANG Q D，WEI J X，GAO C B，et al. Highly selective capture of SO₂ with supported micro-mesoporous silica sphere from CO₂-rich environment［J］. Journal of Cleaner Production，2024，436：140633.
[25]	ZHANG L，YANG L B，YI F T，et al. Experimental and theoretical study of multiple active site-functionalized spirulina residue-based porous carbon as an economical adsorbent for NH₃ and SO₂ adsorption：Micro- and macro-mechanistic investigations［J］. Journal of Cleaner Production，2024，469：143167.
[26]	DENG H，YI H H，TANG X L，et al. Adsorption equilibrium for sulfur dioxide，nitric oxide，carbon dioxide，nitrogen on 13X and 5A zeolites［J］. Chemical Engineering Journal，2012，188：77- 85.
[27]	SADEGHI P，MYERS M B，PAREEK V，et al. Temperature-regulated gas adsorption on LTA zeolites:observation of sorption isotherms for methane，hydrogen，nitrogen and carbon dioxide［J］. Applied Surface Science，2024，678：161037.
[28]	LIU F Y，WANG Z Q，ZHAO W H，et al. Hierarchical porous nanosilica derived from coal gasification fly ash with excellent CO₂ adsorption performance［J］. Chemical Engineering Journal，2025，455：140622.
[29]	CUI Z G，LIU W S，TAN L，et al. Evidence for non-Arrhenius behavior of EPDM rubber by combining Arrhenius and time-temperature superposition（TTS）extrapolations［J］. RSC Advances，2024，14（8）：5216- 5221.
[30]	WANG J，LIANG Q，LI Y. The flow stress prediction of TiB₂/2024 aluminum matrix composites based on modified Arrhenius model and gene expression programming model［J］. Journal of Science：Advanced Materials and Devices，2024，9（4）：100777.
[31]	HE H Y，LIU Y，YIN J L，et al. Introducing effective temperature into Arrhenius equation with Meyer-Neldel rule for describing both Arrhenius and non-Arrhenius dependent drain current of amorphous InGaZnO TFTs［J］. Solid-State Electronics，2021，181-182：108011.
[32]	LI L，WANG C，WANG F，et al. Application progress of in situ infrared technology in the study of zeolite catalyst［J］. Chemical World，2022，63（6）：411- 418. 李丽，王闯，王凤，等. 原位红外技术在分子筛催化剂研究中的应用进展［J］. 化学世界，2022，63（6）：411- 418.
[33]	JIANG X Y，YANG J，LIANG Y，et al. In situ DRIFTS and DFT studies of SO₂ poisoning over Cu-exchanged X zeolite catalyst for NH₃-SCR［J］. Journal of Environmental Chemical Engineering，2023，11（3）：109822.
[34]	LIN B L，TANG J L，YANG J H，et al. Insight to the cooperation between electronic unsaturated metal sites and hydroxyl species improves the SO₂ resistance of Fe-MnO₂@TiO₂ for simultaneous removal of toluene and NO［J］. Applied Catalysis B：Environment and Energy，2025，361：124619.
[35]	MA Y Y，FENG Z D，LIU T F，et al. First-principle molecular dynamics and in situ DRIFTS study the stability of the intermediates of CO₂ hydrogenation to methanol on ZnZrO_x solid solution catalyst［J］. Applied Surface Science，2024，668：160385.
[36]	ZHANG L T，ZHAO R，LI H X，et al. Enhanced NO _x reduction on CePO₄ catalysts:Cu-loading，phosphotungstic acid，and insights from in-situ DRIFTs and DFT［J］. Journal of Hazardous Materials，2024，476：135023.
[37]	WANG J Y，FAN C G，GLARBORG P，et al. Exploration of the NO-char reaction pathway by in-situ DRIFTS and isotope gas tracing techniques［J］. Fuel，2024，361：130634.