肖峥媛1， 吕超杰1， 王中慧1， 吴俊书1， 王金淑1， 吕派2
1.北京工业大学 材料科学与工程学院，材料循环低碳再生全国重点实验室，北京100124；2. Department of Microsystems， University of South-Eastern Norway， Campus Vestfold， Raveien 215， 3184， Horten， Norway
引用格式：
肖峥媛， 吕超杰， 王中慧， 等. 硫代铁酸钠改性钢渣的制备及其总铬去除性能［J］. 中国粉体技术， 2026， 32（6）： 1-12.
Xiao Zhengyuan， Lyu Chaojie， Wang Zhonghui， et al. Preparation of sodium iron thiosulfate-modified steel slag and its total chromium removal performance［J］. China Powder Science and Technology， 2026， 32（6）： 1-12.
DOI：10.13732/j.issn.1008-5548.2026.06.013
收稿日期： 2026-05-18， 修回日期： 2026-07-13， 上线日期： 2026-09-09。
基金项目： 京津冀环境综合治理国家科技重大专项项目，编号：2026ZD1212800。
第一作者： 肖峥媛（2001—），女，硕士生，研究方向为环境功能材料。E-mail：1355103165@qq.com。
通信作者： 吴俊书（1982—），男，副研究员，博士，博士生导师，研究方向为环境功能材料、固废利用。E-mail：junshuwu@bjut.edu.cn。
摘要： 【目的】 为了一体化实施高毒性Cr（VI）的还原脱毒与Cr（III）产物的协同吸附净化，可将钢渣进行表面硫化，实现含铬污水的总铬（Cr（VI）与Cr（III））去除。【方法】 以钢渣（RSS）为原料，充分利用其残余的铁组分，采用乙酸活化-Na2S改性两步法对钢渣进行表面硫化，制备出负载NaFeS2·2H2O的钢渣材料（30HRSSS）。使用X射线衍射仪、扫描电子显微镜、透射电子显微镜、X射线光电子能谱仪等表征手段，分别探讨钢渣转化过程中的晶相结构、微观形貌以及表面化学态的变化，并考察30HRSSS样品的Cr（VI）还原与Cr（III）吸附固定性能，以及使用后30HRSSs粉体表面Cr（III）产物的环境稳定性。【结果】 钢渣表面的硫化过程优化钢渣表面积和孔结构，且表面原位生长的NaFeS2·2H2O棒状颗粒有效促进Fe3+向Fe2+的转换，从而在较宽泛的pH范围内（pH=3~10）实现Cr（VI）的还原以及总铬去除；模拟自然氧化条件下的稳定性评估证实，除铬后30HRSSS仍具有较好的环境稳定性，避免Cr（III）产物再氧化的二次污染风险。【结论】 钢渣表面的铁组分经醋酸活化以后，可经Na2S硫化制备出NaFeS2·2H2O改性的钢渣基功能材料，实现污水中的总铬去除，为钢渣再利用和Cr（VI）深度治理提供一种有效方法。
关键词： 钢渣； 表面活化； 总铬去除
Abstract
Objective A large amount of steel slag （SS） is generated annually. This type of solid waste is rich in metallic components， yet its resource utilization efficiency remains to be improved. In addition， after the reductive detoxification of highly toxic Cr（VI）， the slow re-oxidation of the resulting Cr（III） products often leads to pollution rebound—commonly known as “yellowing back.” Therefore， the simultaneous removal of Cr（III） products is one of the key challenges in the deep treatment of Cr-containing wastewater.
Methods A two-step “acetic acid activation-Na₂S treatment” method was employed to sulfurize the SS surface.Pre-treatment of the raw steel slag （RSS） material began with mechanical ballmilling at a ball-to-slag mass ratio of 7：3， followed by sieving through a 300-mesh sieve to eliminate oversized particles. The obtained slag underwent three cycles of cleaning with deionized water to remove surface impurities， and was then dried at 60 ℃ for 12 h to obtain the RSS powder. Subsequently， 3 g of RSS powder was dispersed in 60 mL of aqueous solution containing 30 mL of acetic acid. The homogeneous suspension was transferred to a thermostatic water bath shaker maintained at 60 ℃ for continuous reaction over 5 h. The resultant brown suspension was filtered without any post-washing treatment and dried at 60 ℃ for 12 h， ultimately yielding the acetic acid-activated SS designated as 30HRSS（where “30” indicates the volume of acetic acid used）. Finally， 2.2 g of Na2S was dissolved in 5 mL water， and then 55 mL ethanol was mixed with the Na2S aqueous solution. 0.3 g of 30HRSS was added to the prepared Na2S solution， and the mixture was reacted in a thermostatic water bath shaker maintained at 60 ℃ for 5 h， yielding the NaFeS2-modified SS product designated as 30HRSSs.
Results and Discussion The pristine RSS displayed irregular bulk granular morphology with coarse particles. After sulfuration， 30HRSSs exhibited a denser internal structure and consolidated solid particles. This process resulted in the enhancement of specific surface area （22.4 m2/g， 30HRSSs）， which was nearly 10 times higher than that of RSS.30HRSSS had both Cr（VI） reduction and Cr（III） adsorption capabilities.Under the optimal conditions （30HRSSS dosage： 30 mg； initial Cr（VI） mass concentration： 10 mg/L in 60 mL； time： 60 min； temperature： room temperature）， when the initial solution pH was 3~5， the residual Cr（VI） mass concentration was below the detection limit （0.01 mg/L）， and the removal efficiency of totalchromium （Cr（T）） reached 100% within 60 min. Under neutral to alkaline conditions （pH=7~10）， the Cr（T） removal efficiency remained above 82% after 90 min of reaction.30HRSSS also exhibited good anti-interference ability against common coexisting ions（NO3⁻， SO42⁻，CO32⁻， Ca2+， and Mg2+）in polluted water.
Conclusion This study realizes the efficient resource reuse of the endogenous residual iron components in SS，and the developed material for SS-based Cr（T） removal provides an effective technical scheme for the deep and long-term treatment of Cr-containing wastewater.Stability assessments under simulated natural oxidative conditions（e.g.，δ-MnO₂， light irradiation）confirm that the Cr removal product exhibits high environmental stability，effectively avoiding the risk of secondary pollution caused by the re-oxidation of Cr（III） products.Therefore，the obtained material has good environmental benefits and application potential.
Keywords： steel slag； surface activation； total chromium removal
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