Mn活化铁盐絮凝污泥制备磁性吸附剂脱除烟气中Hg<sup>0</sup>

汪远; 郭华军; 邵雁; 刘子豪; 向浩; 胡国峰; 李鸿鹄; 胡将军

doi:10.13205/j.hjgc.202303010

Mn活化铁盐絮凝污泥制备磁性吸附剂脱除烟气中Hg⁰

doi: 10.13205/j.hjgc.202303010

1. 中冶南方都市环保工程技术股份有限公司, 武汉 430200;
2. 中南财经政法大学信息与安全工程学院, 武汉 430073;
3. 武汉大学资源与环境科学学院, 武汉 430079

基金项目:

国家自然科学基金青年基金(52100134)

详细信息

作者简介:
汪远(1990-),男,博士,主要研究方向为大气污染控制。Wangyuanwhuu163.com

通讯作者:
李鸿鹄(1991-),男,博士,副教授,主要研究方向为大气污染控制。448657141@qq.com

计量
- 文章访问数: 147
- HTML全文浏览量: 31
- PDF下载量: 5
- 被引次数: 0
出版历程
- 收稿日期: 2022-04-21
- 网络出版日期: 2023-05-26
- 刊出日期: 2023-03-01

REMOVAL OF ELEMENTAL MERCURY USING MAGNETIC ADSORBENT PREPARED FROM SLUDGE FLOCCULATED WITH FERROUS SULFATE BY Mn ACTIVATION

1. WISDRI City Environment Protection Engineering Co., Ltd, Wuhan 430200, China;
2. School of Information and Safety Engineering, Zhongnan University of Economics and Law, Wuhan 430073, China;
3. School of Resource and Environmental Sciences, Wuhan University, Wuhan 430079, China

摘要

摘要: 采用Mn(NO₃)₂活化铁盐絮凝污泥制备磁性吸附剂用于烟气中Hg⁰的脱除。结果表明:1)Mn(NO₃)₂热分解产生的O₂促进了污泥一次热解过程中产生的FeC_<em>x分解,并有利于Mn⁴⁺与Fe³⁺等高价态金属氧化物的生成;Mn(NO₃)₂分解产生的气体有扩孔作用,在其掺杂量为10%时,吸附剂比表面积达到最大(88.5 m²/g),但Mn(NO₃)₂的掺杂量过高时会产生较多的晶相物质,并导致吸附剂的比表面积降低。2)当Mn掺杂量为10%(记为Mn₁₀-SFS),反应温度为150℃时,吸附剂脱汞效率最高(92.7%)。3)烟气中的O₂可对吸附剂中的活性氧进行有效补充,促进Hg⁰的脱除;NO以及低浓度的SO₂对Hg⁰脱除有一定的促进作用,而H₂O与高浓度的SO₂则由于竞争吸附对Hg⁰脱除抑制作用明显。吸附再生试验表明:Mn₁₀-SFS吸附剂具有良好的可再生循环利用性能及稳定性,5次Hg⁰的吸附脱附循环试验后,其脱汞性能无明显降低。
- 污泥 /
- 吸附剂 /
- 燃煤烟气 /
- 汞的脱除REMOVAL
Abstract: In this work, ferrous sulfate-flocculated sewage sludge (SFS) was activated by Mn(NO₃)₂ and then pyrolyzed to obtain magnetic adsorbent, which was adopted to remove elemental mercury (Hg⁰) from flue gas. Results showed that 1) O₂ produced by the thermal decomposition of Mn(NO₃)₂ promoted the decomposition of FeC_<em>x during primary pyrolysis of sludge, and that was conducive to the formation of high-valent metal oxides such as Mn⁴⁺and Fe³⁺. The gas produced by the decomposition of Mn(NO₃)₂ also showed the effect of pore expansion. With the addition of 10% Mn(NO₃)₂, the specific surface area of the adsorbent reached the maximum (88.5 m²/g), but when the Mn(NO₃)₂ amount continued to rise, it would produce many crystalline substances and then decreased the specific surface area of the adsorbent. 2) Mn₁₀-SFS showed a maximum mercury removal efficiency of 92.7% at the reaction temperature of 150 ℃. 3) O₂ could effectively supplement the active oxygen in the adsorbent, promoting the removal of Hg⁰, and presence of NO and a low SO₂ concentration enhanced Hg⁰ removal, while H₂O vapor and a high concentration of SO₂ inhibited it. The Hg⁰ adsorption and desorption experiment showed that the adsorbent of Mn₁₀-SFS exhibited good renewable recycling performance and stability. After Hg⁰ capture and regeneration for 5 cycles, the removal efficiency of the adsorbent was not notably degraded.
- sludge /
- adsorbent /
- coal-fired flue gas /
- mercury removal

HTML全文

参考文献(29)

[1]	YANG Y J, LIU J, WANG Z. Reaction mechanisms and chemical kinetics of mercury transformation during coal combustion[J]. Progress in Energy and Combustion Science, 2020, 79:100844.
[2]	YANG S J, GUO Y F, YAN N Q, et al. Remarkable effect of the incorporation of titanium on the catalytic activity and SO₂ poisoning resistance of magnetic Mn-Fe spinel for elemental mercury capture[J]. Applied Catalysis B:Environmental, 2011, 101(3/4):698-708.
[3]	姬丽琴, 齐永新, 周林成, 等. 磁性微/纳米材料吸附环境污染物的研究进展[J]. 化工新型材料, 2011, 39(11):32-35.
[4]	DONG L, HUANG Y J, CHEN H, et al. Magnetic γFe₂O₃loaded attapulgite sorbent for Hg⁰ removal in coal-fired flue gas[J]. Energy & Fuels, 2019, 33(8):7522-7533.
[5]	ZENG X B, XU Y, ZHANG B, et al. Elemental mercury adsorption and regeneration performance of sorbents FeMnO_x enhanced via non-thermal plasma[J]. Chemical Engineering Journal, 2017, 309:503-512.
[6]	YANG S J, GUO Y F, YAN N Q, et al. Nanosized cation-deficient Fe-Ti spinel:a novel magnetic sorbent for elemental mercury capture from flue gas[J]. ACS Applied Materials & Interfaces, 2011, 3(2):209-217.
[7]	YANG S J, GUO Y F, YAN N Q, et al. Capture of gaseous elemental mercury from flue gas using a magnetic and sulfur poisoning resistant sorbent Mn/γ-Fe₂O₃ at lower temperatures[J]. Journal of Hazardous Materials, 2011, 186(1):508-515.
[8]	YANG S J, YAN N Q, GUO Y F, et al. Gaseous elemental mercury capture from flue gas using magnetic nanosized (Fe_3-xMn_x)_1-δO₄[J]. Environmental Science & Technology, 2011, 45(4):1540-1546.
[9]	ZHANG Z H, WU J, LI B, et al. Removal of elemental mercury from simulated flue gas by ZSM-5 modified with Mn-Fe mixed oxides[J]. Chemical Engineering Journal, 2019, 375:121946.
[10]	林子增,黄瑛,乔红杰,等. 城市污水厂污泥化学调理深度脱水技术述评[J]. 应用化工, 2016, 45(6):1159-1162.
[11]	YANG X, XU G R, YU H R, et al. Preparation of ferric-activated sludge-based adsorbent from biological sludge for tetracycline removal[J]. Bioresource Technology, 2016, 211:566-573.
[12]	WANG Y, LI H H, HE Z, et al. Removal of elemental mercury from flue gas using the magnetic Fe-containing carbon prepared from the sludge flocculated with ferrous sulfate[J]. Environmental Science and Pollution Research, 2020, 27:30254-30264.
[13]	WANG Y, LI H H, SHAO Y, et al. Removal of elemental mercury using magnetic Fe-containing carbon prepared from sludge flocculated with ferrous sulfate by zinc chloride activation[J]. Journal of the Energy Institute, 2021, 98:98-106.
[14]	YANG Y J, LIU J, WANG Z, et al. Interface reaction activity of recyclable and regenerable Cu-Mn spinel-type sorbent for Hg⁰ capture from flue gas[J]. Chemical Engineering Journal, 2019, 372:697-707.
[15]	吕浩. 活性炭喷射耦合除尘器协同脱除燃煤烟气有机污染物/汞/CPM研究[D]. 南京:东南大学,2021.
[16]	LIAO Y, CHEN D, ZOU S J, et al. A recyclable naturally derived magnetic pyrrhotite for elemental mercury recovery from the flue gas[J]. Environmental Science & Technology, 2016, 50:10562-10569.
[17]	杨建平. 可循环再生磁珠吸附剂脱汞及其反应机理研究[D]. 武汉:华中科技大学, 2017.
[18]	LI H H, WANG S K, WANG X, et al. FeCl₃-modified Co-Ce oxides catalysts for mercury removal from coal-fired flue gas[J]. Chemical Papers, 2017, 71(12):2545-2555.
[19]	XU Y, LUO G Q, PANG Q C, et al. Adsorption and catalytic oxidation elemental mercury over regenerable magnetic Fe-Ce mixed oxides modified by non-thermal plasma treatment[J]. Chemical Engineering Journal, 2019, 358:1454-1463.
[20]	TAO S S, LI C T, FAN X P, et al. Activated coke impregnated with cerium chloride used for elemental mercury removal from simulated flue gas[J]. Chemical Engineering Journal, 2012. 210, 547-56.
[21]	LI H L, WU C Y, LI Y, et al. Impact of SO₂ on elemental mercury oxidation over CeO₂-TiO₂ catalyst[J]. Chemical Engineering Journal, 2013, 219:319-326.
[22]	LI H H, WANG S K, WANG X, et al. Catalytic oxidation of Hg⁰ in flue gas over Ce modified TiO₂ supported Co-Mn catalysts:characterization, the effect of gas composition and co-benefit of NO conversion[J]. Fuel, 2017, 202:470-482.
[23]	SHAN Y, YANG W, LI Y, et al. Reparation of microwave-activated magnetic bio-char adsorbent and study on removal of elemental mercury from flue gas[J]. Science of the Total Environment, 2019, 697:134049.
[24]	YANG J P, ZHAO Y C, LIANG S F, et al. Magnetic iron-manganese binary oxide supported on carbon nanofiber (Fe_3-xMn_xO₄/CNF) for efficient removal of Hg⁰ from coal combustion flue gas[J]. Chemical Engineering Journal, 2018, 334:216-224.
[25]	ZHANG A C, ZHANG Z H, CHEN J J, et al. Effect of calcination temperature on the activity and structure of MnO_x/TiO₂ adsorbent for Hg⁰ removal[J]. Fuel Processing Technology, 2015, 135:25-33.
[26]	YANG J P, ZHAO Y, MA S, et al. Mercury removal by magnetic biochar derived from simultaneous activation and magnetization of sawdust[J]. Environmental Science & Technology 2016, 50(21):12040-12047.
[27]	DUAN X L, YUAN C G, JING T T, et al. Removal of elemental mercury using large surface area micro-porous corn cob activated carbon by zinc chloride activation[J]. Fuel, 2019, 239:830-840.
[28]	ZOU S J, LIAO Y, XIONG S, et al. H₂S-modified Fe-Ti spinel:a recyclable magnetic sorbent for recovering gaseous elemental mercury from flue gas as a co-benefit of wet electrostatic precipitators[J]. Environment Science & Technology, 2017, 51(6):3426-3434.
[29]	ZHOU F S, DIAO Y F, Magnetic copper-ferrosilicon composites as regenerable sorbents for Hg⁰ removal[J]. Colloids and Surface A, 2020, 590:124447.