Mn-Fe改性碳基磁性吸附剂去除Hg<sup>0</sup>性能及机制

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摘要采用溶胶凝胶法制备了一系列Mn-Fe改性碳基磁性吸附剂(Mn_xFe_y/C),并评价了其对气态单质汞(Hg⁰)的脱除性能及抗SO₂中毒性能.采用SEM、TEM、BET、XRD、H₂-TPR、Raman、XPS等方法对吸附剂理化结构进行了分析,以此探讨了不同Mn_xFe_y/C吸附剂性能差异的内在原因.结果表明,在反应温度150℃,Hg⁰浓度250μg/m³条件下,Mn₂Fe₁/C的Hg⁰脱除性能最好,达到99.99%.适当含量Fe的加入会引起Mn-Fe间强相互作用,发生Mn³⁺+Fe³⁺↔Mn⁴⁺+Fe²⁺的氧化还原循环,促进Mn⁴⁺的生成,同时降低Mn-O-Mn的化学键强度,增加氧空位(O_v)、活性氧物种(O_α)浓度,从而增强Hg⁰的吸附脱除性能.此外,Mn₂Fe₁/C具有良好的抗SO₂性能,在2000×10^-6SO₂浓度下其Hg⁰脱除率依然保持在80%以上.XPS表明Fe能保护大部分Mn活性位点免受SO₂中毒,同时抑制了吸附剂表面硫酸盐的形成与沉积.Mn₂Fe₁/C可以通过磁分离从粉煤灰中分离出来,其经4次吸附再生循环后仍有95.69%的Hg⁰脱除效率,具备优越的再生能力,是一种具有应用前景的燃煤烟气汞吸附剂.

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关键词 ：氧空位, 过渡金属, 吸附剂, 气态单质汞, SO₂抗性

Abstract：In this study, a series of Mn-Fe modified carbon-based magnetic sorbents (Mn_xFe_y/C) were prepared by the sol-gel method and further evaluated for gaseous elemental mercury (Hg⁰) removal and anti-SO₂ poisoning. SEM, TEM, BET, XRD, H₂-TPR, Raman and XPS were employed to analyze the physicochemical structure of sorbents. According to the characterization results, the inherent reasons for the performance differences of Mn_xFe_y/C sorbents were clarified. The results indicated that Mn₂Fe₁/C achieved best Hg⁰ removal performance (99.99%) under 150℃ and 250μg/m³ Hg⁰. The addition of an appropriate amount of Fe could cause strong interaction between Mn and Fe. It led to an oxidation-reduction cycle of Mn³⁺+Fe³⁺↔Mn⁴⁺+Fe²⁺, thus promoting the generation of Mn⁴⁺ and weakening the chemical bond strength of Mn-O-Mn. Resultantly, the concentration of oxygen vacancies (O_v) and reactive oxygen species (O_α) was increased, which facilitated Hg⁰ removal over Mn₂Fe₁/C. In addition, Mn₂Fe₁/C showed good resistance to SO₂. Its Hg⁰removal efficiency remained above 80% at a concentration of 2000×10^-6 SO₂. XPS showed that Fe could protect most of the Mn active sites from SO₂ poisoning, thus inhibiting the formation and deposition of sulfate on the sorbent surface. Mn₂Fe₁/C could be separated from fly ash through magnetic separation. After four cycles of adsorption and regeneration, Mn₂Fe₁/C still exhibited a Hg⁰removal efficiency of 95.69%. It showed superior regeneration ability and might be a promising mercury sorbent for coal-fired flue gas.

Key words： oxygen vacancy transition metal sorbent gaseous elemental mercury SO₂ resistance

收稿日期: 2024-05-08

PACS:

X701.7

基金资助:国家自然科学基金青年项目(52100134);中南财经政法大学中央高校基本科研业务费专项资金资助项目(2722024EJ024,2722023BY020);中国博士后科学基金面上项目(2022M721284)

通讯作者: 李鸿鹄,副教授,lhhsam@outlook.com;张敬东,教授,jdzhang@zuel.edu.cn E-mail: lhhsam@outlook.com;jdzhang@zuel.edu.cn

作者简介: 张敬东(1966-),女,湖北枝江人,教授,博士,主要从事环境污染修复治理技术研究.发表论文100余篇.jdzhang@zuel.edu.

引用本文:

张敬东, 杨娇羽, 揭翠, 李鸿鹄, 彭喜燕, 安淼. Mn-Fe改性碳基磁性吸附剂去除Hg⁰性能及机制[J]. 中国环境科学, 2024, 44(12): 6628-6640. ZHANG Jing-dong, YANG Jiao-yu, JIE Cui, LI Hong-hu, PENG Xi-yan, AN Miao. The performance and mechanism of Hg⁰ removal by Mn-Fe modified magnetic carbon sorbent. CHINA ENVIRONMENTAL SCIENCECE, 2024, 44(12): 6628-6640.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2024/V44/I12/6628

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