煤气化渣脱除燃煤烟气中汞的性能研究

高春新; 井云环; 陈慧君; 樊盼盼; 王建成; 常丽萍; 鲍卫仁

doi:10.1016/S1872-5813(21)60041-5

煤气化渣脱除燃煤烟气中汞的性能研究

doi: 10.1016/S1872-5813(21)60041-5

高春新^{1, 2, #,},
井云环³,
陈慧君^{1, 2},
樊盼盼^{1, 2},
王建成^{1, 2, ,},
常丽萍^{1, 2},
鲍卫仁^{1, 2}

1.
太原理工大学省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
2.
煤科学与技术教育部重点实验室，山西太原 030024
3.
国家能源集团宁夏煤业有限责任公司，宁夏银川 750011

基金项目: 国家能源集团煤制油研究院技术([2020]010)和国家重点研发项目（2019YFC1904300）资助

详细信息

作者简介:
高春新：(18395588663@163.com)

通讯作者:
Tel: 13834629730，E-mail: wangjiancheng@tyut.edu.cn

#: 高春新和井云环贡献相同
中图分类号: X511
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- 被引次数: 0
出版历程
- 收稿日期: 2020-11-30
- 修回日期: 2021-01-21
- 网络出版日期: 2021-03-30
- 刊出日期: 2021-04-10

Performance of Hg⁰ removal from coal-fired flue gas over coal gasification slag

GAO Chun-xin^{1, 2, #
,},
JING Yun-huan³,
CHEN Hui-jun^{1, 2},
FAN Pan-pan^{1, 2},
WANG Jian-cheng^{1, 2
, ,},
CHANG Li-ping^{1, 2},
BAO Wei-ren^{1, 2}

1.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
2.
Key Laboratory of Coal Science and Technology, Ministry of Education, Taiyuan 030024, China
3.
CHN Energy Ningxia Coal Industry Co., Ltd., Yinchuan 750011, China

Funds: The project was supported by the CHN Energy Coal-to-oil Research Institute Technology ([2020]010) and the National Key Research and Development Program of China (2019YFC1904300)

摘要

摘要: 汞作为一种重金属污染物，对环境和人体健康影响很大，如何对其高效脱除已引起了研究者的广泛关注。本研究使用煤气化渣及其分选后样品作为脱汞吸附剂，通过固定床和气流床脱汞实验考察了吸附剂的脱汞性能，利用N₂吸附-脱附、X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电镜（SEM）等表征手段分析了吸附剂的物化特性。固定床脱汞评价结果显示，OS和HCS在60−120 ℃保持91%以上的脱汞效率；HAS在60 ℃有最高97%的脱汞效率，HAS的脱汞活性受脱汞温度影响较大。Hg-TPD和XPS表征结果表明，吸附剂中的化学吸附氧参与了汞的氧化，在吸附剂表面生成HgO。气流床脱汞评价结果表明，OS和HCS在碳汞比为40000，脱汞温度为60 ℃时，脱汞效率分别为56%、57%；当碳汞比为80000，脱汞温度为60 ℃时，脱汞效率分别为100%、82%。
- 汞 /
- 煤气化渣 /
- 燃煤烟气 /
- 喷射脱汞
Abstract: Mercury (Hg), a kind of heavy metal pollutant, has a great impact on the environment and human health. The highly efficient technology for Hg removal has attracted widespread attention from researchers. In this study, the coal gasification slag (CGS) and the slag after sorting were used as sorbents, and the Hg⁰ removal performance of the sorbents were investigated through the fixed-bed reactor and entrained flow reactor. The characterization methods such as N₂ adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) were performed to analyze the physical and chemical characteristics of the sorbents. According to the results of fixed-bed Hg⁰ removal experiment, the Hg⁰ removal efficiency of the origin slag (OS) and high carbon slag (HCS) could maintain more than 91% at 60−120 ℃. The high ash slag (HAS) showed the highest Hg⁰ removal efficiency of 97% at 60 ℃, which was greatly affected by the Hg⁰ removal temperature. The Hg-TPD (Hg-temperature program desorption) and XPS results indicated that the chemisorbed oxygen on the sorbent participated in the Hg⁰ oxidation process with HgO formed on the surface of the sorbent. According to the results of entrained flow Hg⁰ removal experiments, the Hg⁰ removal efficiencies of OS and HCS were 56% and 57% at C/Hg ratio of 40000 and the Hg⁰ removal temperature of 60 ℃, respectively. When the C/Hg ratio was 80000 and the Hg⁰ removal temperature was 60 ℃, the Hg⁰ removal efficiencies of OS and HCS were 100% and 82%, respectively.
- mercury /
- coal gasification slag /
- coal-fired flue gas /
- injecting mercury removal
注释:

1) #: 高春新和井云环贡献相同

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FIG. 609. FIG. 609.

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图 1 气流床脱汞活性评价装置示意图

Figure 1 Schematic of entrained bed system for Hg⁰ removal

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图 2 N₂吸附-脱附曲线和孔径分布

Figure 2 N₂ adsorption-desorption curves and pore size distributions of samples

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图 3 样品的XRD谱图

Figure 3 XRD patterns of samples

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图 4 样品的SEM照片和能谱谱图

Figure 4 SEM image and EDS of samples (a): OS; (b): HCS; (c): HAS

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图 5 温度对吸附剂脱汞活性的影响

Figure 5 Effect of temperature on Hg⁰ removal efficiency over sorbents

(N₂ + 4% O₂, GHSV = 1.0 × 10⁵ h⁻¹, (a): t = 60 ℃; (b): t = 90 ℃; (c): t = 120 ℃; (d): t = 150 ℃)

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图 6 吸附剂脱汞前后O 1s 及吸附剂脱汞后Hg 4f XPS谱图

Figure 6 O 1s XPS spectra of fresh and used sorbents and Hg 4f XPS spectra of used sorbents

(conditions for removal of Hg⁰: N₂ + 4% O₂, GHSV = 1.0 × 10⁵ h⁻¹, t = 60 ℃)

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图 7 使用后吸附剂的Hg-TPD谱图

Figure 7 Hg-TPD curves of used sorbents

(conditions for removal of Hg⁰: N₂ + 4% O₂, GHSV = 1.0 × 10⁵ h⁻¹, t = 60 ℃)

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图 8 吸附剂的脱汞活性

Figure 8 Hg⁰ removal efficiency of sorbents

(initial Hg⁰ concentration: 9.5 μg/m³, air + 25 L/min N₂, θ = 40000, (a): OS; (b): HCS)

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图 9 吸附剂脱汞活性

Figure 9 Hg⁰ removal efficiency of sorbents

(initial Hg⁰ concentration: 9.5 μg/m³, air + 25 L/min N₂, θ = 80000, (a): OS; (b): HCS)

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图 10 不同反应器下的脱汞效率

Figure 10 Hg⁰ removal efficiency at different reactors

(reaction conditions of the fix-bed reactor: t = 120 ℃, N₂ + 4% O₂, GHSV = 1.0 × 10⁵ h⁻¹; the reaction conditions of entrained flow reactor: t = 120 ℃, initial Hg⁰ concentration: 9.5 μg/m³, air + 25 L/min N₂, θ = 40000, the residence time is 2.0 s)

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表 1 样品的工业分析和元素分析

Table 1 Proximate and ultimate analyses of samples

Sample	Proximate analysis w/%				Ultimate analysis w_ad/%
Sample	M_ad	A_ad	V_ad	V_daf	C	H	O*	N	S
OS	0.47	72.36	2.65	9.75	24.22	0.32	1.98	0.13	0.52
HCS	0.71	12.66	2.99	3.45	82.44	0.29	3.06	0.54	0.30
HAS	0.15	93.44	1.46	22.77	4.17	0.05	−	0.03	0.40
*：by difference

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表 2 样品的孔结构参数

Table 2 Surface areas and pore structure parameters of samples

Sample	BET surface area /(m²·g⁻¹)	t-plot micropore area /(m²·g⁻¹)	Total pore volume /(cm³·g⁻¹)	t-plot micropore volume /(cm³·g⁻¹)	Average pore diameter /nm
OS	223.1	79.9	0.3	0.1	4.5
HCS	787.8	439.9	0.9	0.2	5.5
HAS	3.5	2.2	−	−	7.9

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表 3 基于XPS光谱计算的吸附剂表面元素含量

Table 3 Content of surface elements of sorbents calculated based on the XPS spectra

Sample	Atomic content w/%					Relative content w/%
Sample	C	O	Fe	S	Hg	O_α	O_β	O_γ
Fresh OS	28.32	69.89	1.31	0.48	−	13.73	64.33	21.94
Used OS	30.26	67.84	1.23	0.45	0.22	15.88	58.54	25.58
Fresh HCS	84.14	14.74	0.70	0.42	−	3.17	6.78	90.05
Used HCS	86.42	12.25	0.65	0.43	0.25	4.96	3.73	91.31
Fresh HAS	9.44	88.42	1.53	0.61	−	6.51	23.92	69.57
Used HAS	13.88	83.84	1.46	0.69	0.13	6.09	20.58	73.33

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