燃煤电厂SCR催化剂的失活及再生实验研究

张萼松; 于洁; 王乐乐; 王贲; 孙路石

燃煤电厂SCR催化剂的失活及再生实验研究

张萼松¹,
于洁^1, ,,
王乐乐^{1, 2},
王贲¹,
孙路石¹

1.
华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074
2.
西安热工研究院有限公司苏州分公司, 江苏苏州 215153

详细信息

中图分类号: O643.36⁺2;TQ032.4
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- 被引次数: 0
出版历程
- 收稿日期: 2018-06-12
- 修回日期: 2018-07-23
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-10-10

Deactivation and regeneration of commercial SCR catalysts used in coal fired power plant

ZHANG E-song¹,
YU Jie^{1
, ,},
WANG Le-le^{1, 2},
WANG Ben¹,
SUN Lu-shi¹

1.
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China
2.
Xi'an Thermal Power Research Institute Co. Ltd., Suzhou branch, Suzhou 215153, China

More Information

Corresponding author: YU Jie, E-mail:yujie@hust.edu.cn

摘要

摘要: 对某燃煤电站脱硝系统已运行24000 h的SCR催化剂进行活性测试，利用XRD、BET、XRF、FT-IR和XPS等表征手段分析发现，催化剂出现微、中孔堵塞及活性物质氧化等问题，导致催化剂失活。采用水洗和酸洗方法清除催化剂孔道中的堵塞物，发现水洗能还原部分V物质而酸洗能恢复催化剂表面的活性位并均匀负载具有提高活性位酸性作用的硫物种。对水洗后的催化剂进行SO₂硫化处理，发现相比酸洗Brønsted和Lewis酸性位强度提高的同时Lewis酸性位密度也提高。再生处理后，酸洗在250 ℃以上活性恢复到新鲜催化剂水平，450 ℃硫化催化剂活性在380 ℃达到新鲜催化剂活性的104.6%。
- SCR催化剂 /
- 脱硝 /
- 失活 /
- 再生 /
- 硫化
Abstract: The activity of SCR catalyst used in a coal-fired power plant for 24000 h was tested. With the help of XRD, BET, XRF, FT-IR and XPS, it is found that the catalyst has some problems such as micropore and mesopore plugging and the oxidation of active substances, which leads to the deactivation of the catalyst. Water washing and H₂SO₄ washing were used to remove plugs in the pores of the catalyst. The result shows that water washing can resume part of vanadium species and H₂SO₄ washing can renew the active sites on the surface of catalyst and uniformly load the sulfur species which can increase the acidity of active site. The SO₂ sulphation treatment was performed on the catalyst after water washing. It is indicated that the Brønsted acid and the Lewis acid sites have higher strength and the Lewis acid has higher density than that by H₂SO₄ washing. After the regeneration treatment, H₂SO₄ washed catalyst activity is restored to the level of fresh catalyst above 250 ℃. And the activity of SO₂ sulphation catalyst at 450 ℃ reaches 104.6% of the fresh catalyst activity at 380 ℃.
- SCR catalysts /
- denitrification /
- deactivation /
- regeneration /
- sulphation

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图 1 失活催化剂

Figure 1 Deactivated catalysts

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图 2 实验台架示意图

Figure 2 System for SCR de-NO_x

1: pressure regulating valve; 2: mass flow meter; 3: mixed gas cylinders; 4: three-way valve; 5: square reactor; 6: heating furnace; 7: catalysts; 8: thermocouple; 9: flue gas analyzer; 10: frequency converter; 11: vacuum pump; 12: drying tube

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图 3 新鲜和失活催化剂的孔径分布

Figure 3 Pore size distribution of fresh and deactivated catalysts

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图 4 新鲜和失活催化剂的XRD谱图

Figure 4 XRD patterns of fresh and deactivated catalysts

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图 5 傅里叶红外光谱谱图

Figure 5 FT-IR spectra of the catalysts

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图 6 V 2p的XPS谱图

Figure 6 V 2p spectra of the catalysts

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图 7 水洗和酸洗催化剂的活性评价

Figure 7 NO conversion of water and H₂SO₄ washed catalysts

(space velocity 1418 h^-1, NH₃/NO=1.0)

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图 8 不同温度硫化催化剂的活性评价

Figure 8 NO conversion of catalysts sulphated at different temperatures

(space velocity 1418 h^-1, NH₃/NO=1.0)

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图 9 不同方式再生后催化剂的傅里叶红外光谱谱图

Figure 9 FT-IR spectra of catalysts after regeneration in different ways

a: water washing; b: H₂SO₄ washing;
c: water washing + sulphated at 350 ℃;
d: water washing + sulphated at 400 ℃;
e: water washing + sulphated at 450 ℃

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图 10 催化剂的NH₃-TPD谱图

Figure 10 NH₃-TPD patterns of several catalysts

a: fresh; b: deactivated; c: water washing; d: H₂SO₄ washing

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图 11 不同温度硫化后催化剂的NH₃-TPD谱图

Figure 11 NH₃-TPD patterns of catalysts sulphated at different temperatures

a: water washing+sulphated at 350 ℃;
b: water washing+sulphated at 400 ℃;
c: water washing+sulphated at 450 ℃;
d: water washing

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表 1 失活前后催化剂的XRF分析

Table 1 Chemical composition of the catalysts

Element	Fresh catalyst w/%	Deactivated catalyst w/%
Ti	87.35	77.89
V	1.61	1.51
W	4.84	4.64
Si	3.50	10.55
S	1.01	2.00
Al	0.83	1.31
Fe	0.15	0.24
K	0.09	0.14
Ca	0.62	1.71

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表 2 催化剂的XPS分析

Table 2 XPS analysis of catalyst sample

	Fresh	Deactivated	Water washing	H₂SO₄ washing	S350	S400	S450
V/(kg·m^-3)	2.47	2.36	2.32	1.41	2.21	2.31	2.22
S/(kg·m^-3)	2.24	4.75	2.35	6.17	2.96	3.11	4.42
V⁵⁺ /%	57.3	75.5	64.2	76.1	56.2	68.5	64.9
V⁴⁺ /%	42.7	24.5	35.8	23.9	43.8	31.5	35.1

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