张承昕， 王余莲， 宋金泽， 辜骏泽， 王彬彦， 肖坤富， 张焱， 王艺涵， 胡芳， 马瑞廷
沈阳理工大学 材料科学与工程学院， 辽宁 沈阳 110159
引用格式：
张承昕， 王余莲， 宋金泽， 等. 球磨法制备石油沥青基多孔碘蒸气吸附材料［J］. 中国粉体技术， 2026， 32（1）： 1-12.
ZHANG Chengxin， WANG Yulian， SONG Jinze， et al. Preparation of petroleum asphalt-based porous materials for iodine vapor adsorption via ball-milling method［J］. China Powder Science and Technology， 2026， 32（1）： 1-12.
DOI：10.13732/j.issn.1008-5548.2026.01.015
收稿日期： 2025-04-27， 修回日期： 2025-07-11， 上线日期： 2025-09-23。
基金项目： 国家自然科学基金项目，编号：52374271； “兴辽英才计划”青年拔尖人才项目，编号：XLYC2403010；辽宁省菱镁矿高值利用工程研究中心开放基金资助项目，编号：LMKK20240101；辽宁省教育厅项目，编号：SYLUGXRC+12 & LJMKZ20220585；沈阳理工大学2021年引进高层次人才科研支持经费项目，编号：1010147001011。
第一作者简介： 张承昕（1989—），男，讲师，博士，研究方向为有机多孔材料的制备及应用。E-mail： zhcx1989@sylu.edu.cn。
通信作者简介： 王余莲（1986—），女，教授，博士，博士生导师，“兴辽英才计划”青年拔尖人才，研究方向为功能矿物材料、 碳基复合材料。E-mail： ylwang0908@163.com。
摘要： 【目的】 为实现固体废弃物石油沥青的回收再利用，以石油沥青为原料制备具有丰富孔道结构的有机多孔聚合物（porous organic polymers，POPs），并用于高效碘蒸气吸附研究。【方法】 利用球磨法简便、快捷、高效的优点，以石油沥青（petroleum asphalt，PA）为原料，采用高能行星式球磨机球磨2 h成功制备3种具有丰富连续纳米级孔道且比表面积大的有机多孔聚合物PA-POP-A、PA-POP-B和PA-POP-C，在75 ℃密闭体系内通过碘单质升华模仿放射性碘蒸气环境，分别测试多孔材料的碘蒸气吸附性能。【结果】 3种多孔材料的碘蒸气吸附质量分数分别可达623%、652%和582%，均在约8 h后达到饱和吸附量，且经5次循环使用后，各材料的吸附性能仅出现轻微下降。【结论】 以廉价易得的石油沥青为原料，可通过球磨法制备有机多孔材料，材料具有优良的碘蒸气吸附性能。
关键词： 石油沥青； 球磨法； 有机多孔材料； 碘蒸气吸附
Abstract
Objective Among various clean energy sources， nuclear energy is one of the most widely used and technologically advanced options， offering significant advantages such as high energy density， large output power， environmental cleanliness， and economic efficiency. However， nuclear power generation releases energy from atomic nuclei through nuclear fission， inevitably producing radioactive pollutants. Radioactive iodine isotopes （such as 129I and 131I） are typical gaseous radionuclides that readily diffuse in the air， causing serious pollution to the atmosphere， water systems， and ecosystems. Therefore， the safe and effective capture of radioactive iodine is a significant concern. Recently， porous materials have been utilized to adsorb iodine vapor due to their excellent adsorption properties， achieving promising results. Compared to traditional inorganic porous materials （e.g.， activated carbon， zeolites）， porous organic polymers （POPs） offer advantages such as low density， high physical and chemical stability， large specific surface area， excellent adsorption performance， and good recyclability， making them suitable for radioactive iodine capture.
Methods In this study， three novel POPs， i.e.， PA-POP-A， PA-POP-B， and PA-POP-C， were prepared using petroleum asphalt （PA） as the raw material and three different crosslinking agents， 1，4-bis（chloromethyl）benzene， 4，4′-bis（chloromethyl）biphenyl， and 9，10-bis（chloromethyl）anthracene. The materials were prepared using a fast and efficient ball-milling method. The reagents and catalyst were loaded into a 250 mL zirconia grinding jar with 50 zirconia spheres （10 mm diameter） under an argon atmosphere. The planetary high-energy ball mill was operated at 400 r/min for 2 hours at room temperature. After milling， 100 mL of anhydrous methanol was added to quench the reaction. Subsequently， the mixture was filtered using a Buchner funnel， washed repeatedly with methanol and chloroform， and then dried under vacuum at 60 ℃ for 24 hours， yielding three dark brown powder products. For iodine adsorption experiments， 0.20 g of each porous material was accurately weighed and placed into a pre-weighed cylindrical sample bottle. Then， 2.0 g of solid iodine was added to an identical sample bottle. Both sample bottles were placed in a sealed 250 mL glass container and then heated in a 75 ℃ drying oven to simulate a saturated iodine vapor environment. At fixed time intervals （1， 2， 3， 4， 5， 6， 8， 12， 16， 20， and 24 hours）， samples were removed， cooled down， and weighed to calculate iodine uptake. Each iodine adsorption experiment was conducted in triplicate to evaluate reproducibility and experimental error.
Results and Discussion Under mechanical ball-milling conditions， the raw materials underwent Friedel-Crafts alkylation reaction to form porous polymers with stable chemical structures and well-developed pore channels， as confirmed by Fourier transform infrared spectroscopy （FTIR）， solid-state nuclear magnetic resonance （NMR）， and N2 adsorption characterization. The specific surface areas of PA-POP-A， PA-POP-B， and PA-POP-C were 1 048， 1 700， and 843 m2/g， respectively. N2 adsorption-desorption isotherms indicated that all three porous materials contained abundant micropores （< 2 nm）， mesopores （2-50 nm）， and a small amount of macropores. Iodine adsorption reached equilibrium after 8 hours， with maximum mass uptakes of 623%， 652%， and 582% for PA-POP-A， PA-POP-B， and PA-POP-C， respectively. After 5 adsorption-desorption experiments， only slight decreases in iodine uptake were observed. After 10 days of storage at room temperature and atmospheric pressure， the residual iodine contents were 568%， 612%， and 510%， respectively， indicating excellent retention performance and minimal iodine loss.
Conclusion In this study， three novel organic porous materials （PA-POP-A， PA-POP-B， and PA-POP-C） were prepared using low-cost PA as the raw material through a simple and feasible mechanical ball-milling method. The resulting materials exhibit high specific surface areas and abundant microporous structures， with excellent iodine vapor adsorption and retention performance. After multiple reuse cycles and prolonged exposure under ambient conditions， the materials maintained high adsorption capacity with minimal iodine loss. This preparation method offers notable advantages such as high efficiency， operational simplicity， and feasibility， as well as low energy and organic solvent consumption. These features provide significant benefits in energy conservation and environmental sustainability， demonstrating potential for large-scale industrial applications.
Keywords： petroleum asphalt； ball-milling method； porous organic materials； iodine vapor adsorption
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