MnOx改性活性炭用于模拟烟气中Hg0的脱除

doi:10.11949/0438-1157.20190323

摘要/Abstract

摘要：

采用浸渍法制备了MnO_x改性活性炭（MnO_x/AC），用于模拟煤燃烧烟气中的元素态汞的脱除。实验研究了吸附剂的Mn负载量、吸附温度和烟气组分对所制备的改性活性炭的脱汞性能的影响，以及SO₂对活性炭脱汞的抑制作用机理。研究结果表明，当模拟烟气中含有5%（体积）O₂，Mn负载量为14%（质量），吸附温度为150℃时，改性活性炭的平均脱汞效率为97.0%（3 h）。模拟烟气中少量的O₂和微量的HCl、NO均对汞的脱除起促进作用，而微量的SO₂则对汞的脱除有抑制作用。通过吸附后的MnO_x改性活性炭的TG/DTG、XPS和Hg-TPD分析，推测SO₂对改性活性炭脱汞的抑制作用是由于其消耗MnO_x中的晶格氧，形成的硫酸盐占据了14Mn/AC表面上的活性位点所致。模拟烟气中微量的NO可以有效降低SO₂对脱汞的抑制作用。

关键词: 活性炭, 吸附, 烟道气, 元素汞, MnO_x, SO₂

Abstract:

The MnO_x modified activated carbon (MnO_x/AC) was prepared by impregnation method to simulate the removal of elemental mercury in coal combustion flue gas. The effects of Mn loading on sorbent, sorption temperature and flue gas composition on removal performance of elemental mercury in simulated flue gas were investigated. Mechanism of SO₂ inhibition on mercury removal was revealed. The average Hg⁰ removal efficiency on MnO_x/AC is 97.0% at 150℃ in 3 hours when Mn loading is 14% (mass) with 5% (vol) O₂ in simulated flue gas. A small amount of O₂ and trace amounts of HCl and NO promoted the removal of mercury in gas phase, while trace amount of SO₂ inhibited it. TG/DTG, XPS and Hg-TPD analyses of spent MnO_x modified activated carbon indicated that the inhibition of SO₂ on Hg⁰ removal of modified activated carbon is due to the consumption of lattice oxygen in MnO_x by formation of sulfate that occupies active sites on the surface of 14Mn/AC. This inhibition of SO₂ on removal of elemental mercury could be effectively reduced by adding trace amount of NO.

Key words: activated carbon, sorption, flue gas, elemental mercury, MnO_x, SO₂

中图分类号:

X 511

李向阳, 李扬, 靳立军, 杨赫, 王德超, 胡浩权. MnO_x改性活性炭用于模拟烟气中Hg⁰的脱除[J]. 化工学报, 2019, 70(8): 3078-3085.

Xiangyang LI, Yang LI, Lijun JIN, He YANG, Dechao WANG, Haoquan HU. Removal of Hg⁰ from simulated flue gas by MnO_x modified activated carbon[J]. CIESC Journal, 2019, 70(8): 3078-3085.

图/表 12

表1 晋城无烟煤工业分析和元素分析

Table 1 Proximate and ultimate analysis of Jincheng anthracite

工业分析/%（mass）			元素分析/%（mass, daf）
M_ad	A_d	V_daf	C	H	N	S	O^①
0.11	10.37	10.23	87.91	4.04	1.42	0.66	5.97

图1 汞吸附实验装置

Fig.1 Schematic diagram of mercury sorption system

图2 Mn负载量对脱汞性能的影响

Fig.2 Effect of Mn loading on AC on removal of Hg0

图3 吸附温度对14Mn/AC脱汞性能的影响

Fig.3 Effect of sorption temperature on Hg0 removal on 14Mn/AC

图4 烟气组分对14Mn/AC脱汞性能的影响

Fig.4 Effect of flue gas composition on Hg0 removal on 14Mn/AC

图5 14Mn/AC在不同气氛下吸附后的Hg-TPD曲线

Fig.5 Hg-TPD profiles of 14Mn/AC after sorption in different atmospheres

表2 MnOx/AC的比表面积及孔结构Table 2 Specific surface area and pore structure parameters of MnOx/AC

样品	比表面积/ （m²/g）	孔容/（cm³/g）	平均孔径/nm
AC	1983	0.96	1.92
8Mn/AC	1664	0.81	1.97
10Mn/AC	1598	0.79	1.98
12Mn/AC	1531	0.76	2.01
14Mn/AC	1481	0.73	2.04
16Mn/AC	1397	0.71	2.03
20Mn/AC	1250	0.64	2.01
24Mn/AC	1109	0.56	2.02

图6 MnOx/AC的XRD谱图

Fig.6 XRD patterns of MnOx/AC

图7 14Mn/AC和14Mn/AC-S(SO2)的TG（a）和DTG（b）曲线

Fig.7 TG (a) and DTG (b) curves of 14Mn/AC and 14Mn/AC-S(SO2)

图8 14Mn/AC中Mn 2p的XPS谱图

Fig.8 Mn 2pXPS spectra of 14Mn/AC

图9 14Mn/AC及在不同气氛下吸附后的O 1 s的XPS谱图

Fig.9 O 1sXPS spectra of 14Mn/AC and its spent samples in different atmospheres

表3 14Mn/AC及在不同气氛下吸附后表面氧物种的含量

Table 3 Concentration of surface oxygen in 14Mn/AC and spent samples in different atmospheres

样品	O_α/%	O_β/%	O_γ/%
14Mn/AC	32.3	61.0	6.7
14Mn/AC-S	32.0	61.4	6.6
14Mn/AC-S(W O₂)	29.6	63.9	6.5
14Mn/AC-S(SO₂)	20.2	73.2	6.6

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MnO_x改性活性炭用于模拟烟气中Hg⁰的脱除

Removal of Hg⁰ from simulated flue gas by MnO_x modified activated carbon

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