活性炭类和磁性金属类吸附剂喷射脱汞技术应用对比及最新进展

doi:10.16085/j.issn.1000-6613.2024-0103

化工进展 ›› 2025, Vol. 44 ›› Issue (1): 513-524.DOI: 10.16085/j.issn.1000-6613.2024-0103

活性炭类和磁性金属类吸附剂喷射脱汞技术应用对比及最新进展

倪鹏¹(), 王先泓², 黄钰涵², 马晓彤¹, 马子轸², 谈琰², 张华伟², 刘亭²()

^1.山东科技大学储能技术学院，山东青岛 266590
^2.青岛理工大学环境与市政工程学院，山东青岛 266520

收稿日期:2024-01-14 修回日期:2024-05-22 出版日期:2025-01-15 发布日期:2025-02-13
通讯作者: 刘亭
作者简介:倪鹏（1988－），男，讲师，博士，研究方向为燃煤烟气中重金属控制和垃圾焚烧烟气污染物控制。E-mail: nipeng198802@163.com。
基金资助:
山东省自然科学基金(ZR2022QB084);国家自然科学基金(22078168);山东省泰山学者专家人才工程(taqn202211178)

Latest progress and comparison of the injection demercuration application of activated carbon and magnetic metals adsorbents

NI Peng¹(), WANG Xianhong², HUANG Yuhan², MA Xiaotong¹, MA Zizhen², TAN Yan², ZHANG Huawei², LIU Ting²()

^1.College of Energy Storage Technology, Shandong University of Science and Technology, Qingdao 266590, Shandong, China
^2.School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266520, Shandong, China

Received:2024-01-14 Revised:2024-05-22 Online:2025-01-15 Published:2025-02-13
Contact: LIU Ting

摘要/Abstract

摘要：

吸附剂喷射脱汞技术是一项除现有设备协同脱汞外的单项脱汞技术，本文主要回顾了现有的活性炭类和磁性金属类两类吸附剂在喷射脱汞应用研究中的问题和优点，介绍了两类材料的性能特征，阐述了喷射位置应用差异，总结了脱汞后样品的性能和回收处置差异。重点讲述了活性炭类吸附剂脱汞的理论和实验研究发展，以及脱汞后汞的化合物稳定性分析；详细介绍了磁性金属类吸附剂的发展、实际应用和磁选回收汞的流程及参数。结果表明，硫化物和硒化物类的吸附剂展现出了优越的能力和低的浸出性，是一项非常有前景的吸附剂。最后对单项脱汞技术在应用中需要解决的问题、不足和技术应用前景进行了展望。

关键词: 吸附剂, 催化剂, 环境, 燃煤烟气, 喷射脱汞, 反应机理

Abstract:

Adsorbent injection demercuration is an independent mercury removal technology besides the synergistic removal of mercury by existing equipment. This paper mainly reviewed the problems and advantages of two kinds of adsorbents of activated carbon and magnetic metals in the actual application, compared the characteristics and performance of the two types of materials, elaborated the difference on the injection position and concluded the recovery of elemental mercury and the disposal of mercury compounds. The development of theoretical and experimental research on mercury removal on activated carbon-based adsorbents and the stability analysis of mercury compounds were highlighted, meanwhile, the development on magnetic metal-based adsorbents, their practical applications and the process and operation parameters of mercury recovery by magnetic separation were described in detail. The discussion indicated that the sulfur and selenide-based adsorbents were very promising adsorbents with superior ability, high stability and low leachability on mercury compounds. Finally, an outlook on the problems and prospects for the application of individual mercury removal technologies was presented.

Key words: adsorbent, catalyst, environment, coal-fired flue gas, injection demercuration, reaction mechanism

中图分类号:

倪鹏, 王先泓, 黄钰涵, 马晓彤, 马子轸, 谈琰, 张华伟, 刘亭. 活性炭类和磁性金属类吸附剂喷射脱汞技术应用对比及最新进展[J]. 化工进展, 2025, 44(1): 513-524.

NI Peng, WANG Xianhong, HUANG Yuhan, MA Xiaotong, MA Zizhen, TAN Yan, ZHANG Huawei, LIU Ting. Latest progress and comparison of the injection demercuration application of activated carbon and magnetic metals adsorbents[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 513-524.

图/表 6

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91	WANG Chang, QIN Ruiyang, ZHANG Xufan, et al. Safe disposal of deactivated commercial selective catalytic reduction catalyst (V₂O₅-MoO₃/TiO₂) as a low-cost and regenerable sorbent to recover gaseous elemental mercury in smelting flue gas[J]. Journal of Hazardous Materials, 2021, 406: 124744.
92	WANG Chang, HU Qixing, ZHANG Qi, et al. Novel synergetic effect of Fe and W in FeWS _x /TiO₂ on Capturing high concentrations of gaseous Hg⁰ from smelting flue gas: adsorption kinetics and structure-activity relationship[J]. Industrial & Engineering Chemistry Research, 2020, 59(7): 2745-2753.

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样品	反应气氛	初始Hg⁰浓度 /μg·m^-3	最优反应温度/℃	样品量	流量 /L·min^-1	Hg⁰脱除效率 /%	吸附容量 /μg·g^-1	吸附速率 /μg·g^-1·min^-1
NH₄Br-AC^[39]	216.1mg/m³ NO，51319mg/m³ O₂，1845.0mg/m³ SO₂，0~152130mg/m³ CO₂，0～51919.3mg/m³ H₂O	18～76.8	150	50mg 吸附剂+ 500mg SiO₂	2.0	80	11491	—
E₈Fe₃^[43]	752.8mg/m³ NO，48387.1~135161.3mg/m³ O₂，1162.5mg/m³ SO₂，41536.8mg/m³ H₂O	50	90~150 (130)	300mg 吸附剂+ 4g QZ	0.85	76.9	—	—
S₈KI₃^[44]	337.7mg/m³ NO，54041.6mg/m³ O₂，1082.2mg/m³ SO₂，7608.0mg/m³ H₂O	60	80~160 (160)	80mg+920mg QZ	0.85	96	—	—
SAC-800^[26]	253.3mg/m³ NO，45035mg/m³ O₂，901.7mg/m³ SO₂，15216mg/m³ H₂O	80	80~160 (160)	50mg+950mg QZ	1	90.8	2382.6	—
EAC-800	253.3mg/m³ NO，45035mg/m³ O₂，901.7mg/m³ SO₂，15216mg/m³ H₂O	80	80~160 (160)	50mg+950mg QZ	1	92.8	2909.5	—
Co_0.4-Fe₁₂ /RSWU(500)^[20]	362.9mg/m³ NO，58065mg/m³ O₂，1162.6mg/m³ SO₂，8174.4mg/m³ H₂O	65	70~160 (160)	60mg+500mg QZ	0.8	89	4833.3	—
g-C₃N₄^[28]	93.0/186.1mg/m³ NO，49618mg/m³ O₂，596.0/1192.1mg/m³ SO₂， 55883mg/m³ H₂O	55	20~1000 (160)	—	1.2	50	＞116	1.29
B₁C₂^[19]	36459mg/m³ O₂，N₂	33±1	80~180(80)	30mg+200mg QZ	1.5	60	584.2	0.18
Fe-5%Ce-1%Mn/BC^[38]	N₂	100	50	1000mg	1.4	97	24	0.144
BC/MBC^[45]	39694.7/59542.0mg/m³ O₂，163750.7/955212.5mg/m³ CO₂，22353.0/67059.2mg/m³ H₂O	85	120	50mg	1.2	90	—	—
MSC^[40]	N₂	65/700	50~125(100)	10mg	0.3	90	7828.39	28.67
E8B5^[46]	7608mg/m³ H₂O，45035mg/m³O₂，1082mg/m³ SO₂，337. mg/m³ NO	50	130	300mg+4g QZ	0.8	94.6	326.46	—

样品	反应气氛	初始Hg⁰浓度 /μg·m^-3	最优反应温度/℃	样品量	流量 /L·min^-1	Hg⁰脱除效率 /%	吸附容量 /μg·g^-1	吸附速率 /μg·g^-1·min^-1
NH₄Br-AC^[39]	216.1mg/m³ NO，51319mg/m³ O₂，1845.0mg/m³ SO₂，0~152130mg/m³ CO₂，0～51919.3mg/m³ H₂O	18～76.8	150	50mg 吸附剂+ 500mg SiO₂	2.0	80	11491	—
E₈Fe₃^[43]	752.8mg/m³ NO，48387.1~135161.3mg/m³ O₂，1162.5mg/m³ SO₂，41536.8mg/m³ H₂O	50	90~150 (130)	300mg 吸附剂+ 4g QZ	0.85	76.9	—	—
S₈KI₃^[44]	337.7mg/m³ NO，54041.6mg/m³ O₂，1082.2mg/m³ SO₂，7608.0mg/m³ H₂O	60	80~160 (160)	80mg+920mg QZ	0.85	96	—	—
SAC-800^[26]	253.3mg/m³ NO，45035mg/m³ O₂，901.7mg/m³ SO₂，15216mg/m³ H₂O	80	80~160 (160)	50mg+950mg QZ	1	90.8	2382.6	—
EAC-800	253.3mg/m³ NO，45035mg/m³ O₂，901.7mg/m³ SO₂，15216mg/m³ H₂O	80	80~160 (160)	50mg+950mg QZ	1	92.8	2909.5	—
Co_0.4-Fe₁₂ /RSWU(500)^[20]	362.9mg/m³ NO，58065mg/m³ O₂，1162.6mg/m³ SO₂，8174.4mg/m³ H₂O	65	70~160 (160)	60mg+500mg QZ	0.8	89	4833.3	—
g-C₃N₄^[28]	93.0/186.1mg/m³ NO，49618mg/m³ O₂，596.0/1192.1mg/m³ SO₂， 55883mg/m³ H₂O	55	20~1000 (160)	—	1.2	50	＞116	1.29
B₁C₂^[19]	36459mg/m³ O₂，N₂	33±1	80~180(80)	30mg+200mg QZ	1.5	60	584.2	0.18
Fe-5%Ce-1%Mn/BC^[38]	N₂	100	50	1000mg	1.4	97	24	0.144
BC/MBC^[45]	39694.7/59542.0mg/m³ O₂，163750.7/955212.5mg/m³ CO₂，22353.0/67059.2mg/m³ H₂O	85	120	50mg	1.2	90	—	—
MSC^[40]	N₂	65/700	50~125(100)	10mg	0.3	90	7828.39	28.67
E8B5^[46]	7608mg/m³ H₂O，45035mg/m³O₂，1082mg/m³ SO₂，337. mg/m³ NO	50	130	300mg+4g QZ	0.8	94.6	326.46	—

名称	机组	效率/%	喷射量/g·h^-1	用过的吸附剂处理
商用活性炭^[82]	480MW	90^①	25000	允许灰分销售，C/Hg比^②未知，成本包括喷射装置和飞灰无害化处理等
CuCl₂/磁珠^[6]	570MW	89.8^①	560000	磁选分离吸附剂，吸附剂回收比例未知，成本包括喷射装置、磁选组合机构和加热脱附汞装置等
CuCl₂/磁珠^[6]	实验室喷射台架	80.6	3.79	磁选分离吸附剂，吸附剂回收比例未知，成本包括喷射装置、磁选组合机构和加热脱附汞装置等
溴化稻壳活性炭^[18,24]	实验室喷射台架	70.6	7.3	C/Hg比：未知
溴化稻壳活性炭^[18,24]	循环流化床	82.9	未知	C/Hg比：20000

名称	机组	效率/%	喷射量/g·h^-1	用过的吸附剂处理
商用活性炭^[82]	480MW	90^①	25000	允许灰分销售，C/Hg比^②未知，成本包括喷射装置和飞灰无害化处理等
CuCl₂/磁珠^[6]	570MW	89.8^①	560000	磁选分离吸附剂，吸附剂回收比例未知，成本包括喷射装置、磁选组合机构和加热脱附汞装置等
CuCl₂/磁珠^[6]	实验室喷射台架	80.6	3.79	磁选分离吸附剂，吸附剂回收比例未知，成本包括喷射装置、磁选组合机构和加热脱附汞装置等
溴化稻壳活性炭^[18,24]	实验室喷射台架	70.6	7.3	C/Hg比：未知
溴化稻壳活性炭^[18,24]	循环流化床	82.9	未知	C/Hg比：20000

名称	初始汞浓度/μg·m^-3	反应温度/℃	脱汞产物	花费	产物稳定性/℃
商用活性炭	5.8	154	HgO	500USD/h	400~600
CuCl₂/磁珠^[84]	10	150	HgCl₂	第一次循环花费117USD/h；随着循环次数增加，费用增加	100~150
溴化稻壳活性炭Br-RHC	12.3	120	HgO	未知	400~600

活性炭类和磁性金属类吸附剂喷射脱汞技术应用对比及最新进展

Latest progress and comparison of the injection demercuration application of activated carbon and magnetic metals adsorbents

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文献中样品	温度/℃	脱汞效率/%	吸附容量/mg·g^-1	吸附速率/μg·g^-1·min^-1	产物
MoSe₃^[87]	50	100	1000	240	HgSe
RT-CuSe^[11]	60	99.2	345	42.5	HgO/HgSe
xSe-FeS^[30]	60	90	2.45	0.43	HgS/HgSe
改性Fe-Ti尖晶石^[89]	60	100	0.69	1.92	HgO/HgSO₄/HgS
CuFeS₂^[22]	80	100	37.24	63.40	β-HgS
(Fe_2.3Ti_0.7)_1-_δ O₄^[72]	250	87～99	3.94	6.57	HgO
g-C₃N₄^[28]	160	50	＞0.12	1.29	π-/σ-汞-三嗪化合物
MoS₃/TiO₂^[90]	80	100	28.1	34.8	HgS
Co₉S₈-PC^[54]	100	100	43.18	11.4	HgS
Fe _x Co_1-_x S _y @CF^[86]	150	99	45.6	>2.5	HgS
ZnO@CuS^[13]	75	89	60.53	16.81	Hg-OM/HgS
载硫V₂O₅-MoO₃/TiO₂^[91]	60	100	20.7	35.4	HgS
载硫MoO₃/Fe-Ti尖晶石^[21]	60	100	66.3	93.3	HgS
FeWS _x /TiO₂^[92]	100	100	9.0	25.0	HgS

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