不同烟气组分对粉状活性焦吸附汞的影响机理

doi:10.11949/j.issn.0438-1157.20181278

化工学报 ›› 2019, Vol. 70 ›› Issue (4): 1575-1582.DOI: 10.11949/j.issn.0438-1157.20181278

不同烟气组分对粉状活性焦吸附汞的影响机理

安东海¹(),韩晓林³,程星星¹(),周滨选¹,郑瑛²,董勇¹()

1. 山东大学燃煤污染物减排国家工程实验室，山东济南250061
2. 华中科技大学煤燃烧国家重点实验室,湖北武汉430074
3. 神华新疆能源有限责任公司，新疆乌鲁木齐 830027

收稿日期:2018-10-31 修回日期:2018-12-22 出版日期:2019-04-05 发布日期:2019-04-05
通讯作者: 程星星,董勇
作者简介:<named-content content-type="corresp-name">安东海</named-content>（1988—），男，博士研究生， <email>adhcjxy@163.com</email>|程星星（1984—），女，博士，副教授，<email>xcheng@sdu.edu.cn</email>|董勇（1967—），男，博士，教授，<email>dongy@sdu.edu.cn</email>
基金资助:
国家重点研发计划项目(2017YFF0209803)

Effect mechanisms of different flue gas on adsorption of mercury by powder activated coke

Donghai AN¹(),Xiaolin HAN³,Xingxing CHENG¹(),Binxuan ZHOU¹,Ying ZHENG²,Yong DONG¹()

1. National Engineering Laboratory of Coal-Fired Pollution Reduction, Shandong University, Jinan 250061, Shandong, China
2. State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
3. Shenhua Xinjiang Energy Company Limited, Urumqi 830027, Xinjiang, China

Received:2018-10-31 Revised:2018-12-22 Online:2019-04-05 Published:2019-04-05
Contact: Xingxing CHENG,Yong DONG

摘要/Abstract

摘要：

在模拟燃煤热烟气为热源和介质条件下，以准东褐煤为原料，通过一维沉降炉进行炭化活化（一步法）制备粉状活性焦，考察了活性焦对Hg⁰的吸附能力，探索了SO₂、H₂O、O₂、CO₂、H₂O+O₂、SO₂+O₂及H₂O+SO₂+O₂气氛对活性焦吸附Hg⁰的影响机理。结果表明：一步法获得的活性焦对Hg⁰具有较高的吸附性能。N₂气氛作对比，H₂O、H₂O+O₂、CO₂和SO₂气氛下抑制活性焦对Hg⁰的吸附；O₂、SO₂+O₂和H₂O+SO₂+O₂促进活性焦对Hg⁰的吸附。通过Hg 4f的XPS分析证明了不同气氛组成对活性焦吸附Hg⁰的抑制和促进机理。H₂O覆盖在活性焦活性位上和堵塞孔隙而抑制活性焦对Hg⁰的吸附；SO₂与Hg⁰在活性焦上发生竞争吸附而抑制对Hg⁰的吸附；CO₂ 吸附在活性焦微孔上而抑制对Hg⁰的吸附；O₂气氛下主要形成了HgO, SO₂+O₂气氛下Hg⁰被氧化成HgSO₃，进一步氧化成HgSO₄； H₂O+SO₂+O₂气氛下，Hg⁰被氧化成HgO和HgSO₄。

关键词: 粉状活性焦, 一步法, 汞吸附, 影响机理

Abstract:

Under the condition of simulating coal-fired hot flue gas as heat source and medium, quasi-east lignite was used as raw material to carry out carbonization activation (one-step method) to prepare powdery activated coke by one-dimensional settling furnace, and the adsorption capacity of activated coke to Hg⁰ was investigated. Further, the effects of SO₂, H₂O, O₂, CO₂, H₂O+O₂, SO₂+O₂ and H₂O+SO₂+O₂ on Hg⁰ removal efficiency were examined in flue gas. The results indicate that the coke has high adsorption performance for Hg⁰ removal. The N₂ atmosphere was used as comparison, the O₂, SO₂+O₂ and H₂O+SO₂+O₂ are beneficial for Hg⁰ removal, while the H₂O, CO₂, SO₂ and H₂O+O₂ have inhibiting effect on Hg⁰ removal. Furthermore, the spectra of Hg 4f were determined by XPS, in order to explore the mechanism of inhibition and promotion of Hg⁰ adsorption by activated coke under different flue gas. H₂O can inhibit the adsorption of active coke on Hg⁰via covering the active coke sites and blocking the pores, SO₂ can inhibit the adsorption through the competitive adsorption of SO₂ and HgO on the active coke, and CO₂ that adsorbed on the active coke micropore also can inhibit the adsorption of active coke on Hg⁰. In the atmosphere of O₂ and SO₂+O₂, the Hg⁰ is oxidized into HgO and HgSO₃, separately. And the HgSO₃ further oxidized into HgSO₄ by O₂. Besides, in the atmosphere of H₂O+SO₂+O₂, Hg⁰ is oxidized into HgO and HgSO₄.

Key words: powder activated coke, one-step method, mercury adsorption, effect mechanism

中图分类号:

TQ 028.8

安东海, 韩晓林, 程星星, 周滨选, 郑瑛, 董勇. 不同烟气组分对粉状活性焦吸附汞的影响机理[J]. 化工学报, 2019, 70(4): 1575-1582.

Donghai AN, Xiaolin HAN, Xingxing CHENG, Binxuan ZHOU, Ying ZHENG, Yong DONG. Effect mechanisms of different flue gas on adsorption of mercury by powder activated coke[J]. CIESC Journal, 2019, 70(4): 1575-1582.

图/表 13

图1 粉焦制备实验装置系统

Fig.1 System of powder activated coke preparation

表1 样品的工业分析、元素分析及原煤烧失率

Table 1 Proximate and ultimate analyses of coke and burn-off of coal

工业分析/%				元素分析/%					烧失率/%
M_ad	V_ad	A_ad	FC_ad	C_ad	H_ad	O_ad	N_ad	S_ad	烧失率/%
0.88	4.56	33.87	60.69	60.74	0.96	2.09	0.84	0.62	28.7

图2 Hg0吸附系统

Fig.2 Experimental system of Hg0 adsorption

图3 原煤（a）、活性焦（b）样品的扫描电镜图

Fig.3 SEM images of raw coal (a) and coke (b)

图4 活性焦的N2吸附-脱附等温线

Fig.4 N2 adsorption-desorption isotherm of coke

表2 活性焦的孔隙结构参数

Table 2 Structure parameters of coke

总比表面积/

(m²/g)

微孔比表面积/

(m²/g)

总孔容/

(cm³/g)

微孔孔容/

(cm³/g)

图5 活性焦的孔径分布

Fig.5 Pore size distribution of coke

图6 N2和N2+6%O2气氛下Hg0的吸附曲线（a）及吸附机理（b）

Fig.6 Hg0 adsorption curves under N2 and N2 +6%O2 (a) and adsorption mechanism (b) of coke

图7 N2和N2+6%O2气氛下乏焦的Hg 4f的XPS谱图

Fig.7 XPS analysis of Hg 4f for used coke under N2 (a) and N2 +6%O2 (b)

图8 N2和N2+0.06% SO2+6%O2气氛下汞的吸附曲线(a)及反应机理（b）

Fig.8 Hg0 adsorption curves under N2 and N2+0.06% SO2+6%O2 (a) and adsorption mechanism (b) of coke

图10 N2+SO2+O2和N2+0.06% SO2+6% O2+6% H2O气氛下Hg 4f的XPS谱图

Fig.10 XPS spectra of Hg 4f under N2+SO2+O2 (a) and N2+0.06% SO2+6% O2+6% H2O (b)

图9 N2和N2+0.06% SO2+6%O2+6%H2O气氛下汞的吸附曲线(a)及反应机理（b）

Fig.9 Hg0 adsorption curves under N2 and N2+0.06% SO2+6%O2+6%H2O (a) and adsorption mechanism (b) of coke

图11 N2、N2+0.06% SO2、N2 +6% H2O和N2 +6% H2O+6% O2气氛下汞的吸附曲线

Fig.11 Hg0 adsorption curves under N2, N2+0.06% SO2, N2+6% H2O and N2 +6% H2O+6% O2 of coke

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不同烟气组分对粉状活性焦吸附汞的影响机理

Effect mechanisms of different flue gas on adsorption of mercury by powder activated coke

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