商用SCR催化剂催化生成SO3特性

doi:10.16085/j.issn.1000-6613.2023-0052

化工进展 ›› 2023, Vol. 42 ›› Issue (12): 6354-6362.DOI: 10.16085/j.issn.1000-6613.2023-0052

• 工业催化 • 上一篇

商用SCR催化剂催化生成SO₃特性

张雪伟¹(), 黄亚继¹(), 程好强¹, 王圣², 朱志成¹, 李金壘¹, 丁雪宇¹, 李雨欣¹, 魏泽坤¹, 张荣初³

^1.东南大学能源与环境学院，能源热转换及其过程测控教育部重点实验室，江苏南京 210096
^2.清洁高效燃煤发电与污染控制国家重点实验室，江苏南京 210023
^3.南京常荣声学股份有限公司，江苏南京 210018

收稿日期:2023-01-11 修回日期:2023-05-15 出版日期:2023-12-25 发布日期:2024-01-08
通讯作者: 黄亚继
作者简介:张雪伟（1999—），男，硕士研究生，研究方向为大气污染物控制。E-mail：2282779298@qq.com。
基金资助:
江苏省科技计划(BA2020001);清洁高效燃煤发电与污染控制国家重点实验室开放课题（1804）

On the catalytic performance of commercial SCR catalyst for SO₃ generation

ZHANG Xuewei¹(), HUANG Yaji¹(), CHENG Haoqiang¹, WANG Sheng², ZHU Zhicheng¹, LI Jinlei¹, DING Xueyu¹, LI Yuxin¹, WEI Zekun¹, ZHANG Rongchu³

^1.Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China
^2.State Key Laboratory of Clean and Efficient Coal-fired Power Generation and Pollution Control, Nanjing 210023, Jiangsu, China
^3.Changrong Acoustic Limited Liability Company, Nanjing 210018, Jiangsu, China

Received:2023-01-11 Revised:2023-05-15 Online:2023-12-25 Published:2024-01-08
Contact: HUANG Yaji

摘要/Abstract

摘要：

选择性催化还原（SCR）设备可以有效脱除烟气污染物NO _x，但也会催化生成SO₃，从而危害设备安全和大气环境。本研究在模拟SCR实验台基础上考察了温度、烟气气氛和催化剂组分对SCR催化剂催化生成SO₃的影响，并采用X射线荧光光谱（XRF）和X射线光电子能谱（XPS）分析了催化剂在反应前后的变化。结果表明：温度升高会提高SO₃的生成率；O₂含量对SO₃的生成产生影响，但是O₂含量超过2%后影响微小；增大SO₂浓度会降低SO₃生成率，但SO₃总量仍不断提升；一定浓度的NH₃显著抑制了SO₃的生成，同时产生大量硫铵盐沉积物，而NO _x 中的氧化性气体NO₂会提高催化剂中V⁵⁺的比例，促进SO₃生成；实际反应过程中脱硝与SO₂氧化存在竞争，降低烟气中NO₂浓度会提升脱硝效率且减少SO₃生成；催化剂中的钒和钛会提高SO₃生成率，而硅对SO₃的生成有抑制作用。本研究为SCR的实际运行优化提供了一定的理论基础和参考。

关键词: 选择性催化还原催化剂, 催化氧化, SO₃生成, 烟气气氛, 活性组分

Abstract:

Selective catalytic reduction (SCR) can effectively remove pollutant NO _x from flue gas, but it also catalyzes the generation of SO₃, endangering equipment safety and atmospheric environment. In this study, the effects of temperature, flue gas atmosphere and catalyst components on the catalytic production of SO₃ by SCR catalyst were investigated on a simulated SCR equipment. The changes of the catalyst before and after reaction were analyzed by X-ray fluorescence spectroscopy (XRF) and X-ray photoelectron spectroscopy (XPS). The results showed that the yield of SO₃ increased with temperature and O₂ content could affect the SO₃ production, but the effect was minimal with O₂ content over 2%. Increasing SO₂ concentration decreased SO₃ production rate, but total SO₃ amounts still increased. At a certain concentration of NH₃, the formation of SO₃ was significantly inhibited, and a large amount of sulfur and ammonium salt deposition was produced. However, the oxidizing gas NO₂ in NO _x could increase the proportion of V⁵⁺ in the catalyst and promote the formation of SO₃. In the actual reaction process, denitrification competes with SO₂ oxidation. Reducing the NO₂ concentration in flue gas could improve the denitrification efficiency and reduce the generation of SO₃. The vanadium and titanium in the catalyst could increase the formation rate of SO₃, while the silicon could inhibit the formation of SO₃. This study provides a theoretical basis and reference for the operation optimization of actual SCR.

Key words: selective catalytic reduction (SCR) catalyst, catalytic oxidation, SO₃ generation, flue gas atmosphere, active component

中图分类号:

X511

张雪伟, 黄亚继, 程好强, 王圣, 朱志成, 李金壘, 丁雪宇, 李雨欣, 魏泽坤, 张荣初. 商用SCR催化剂催化生成SO₃特性[J]. 化工进展, 2023, 42(12): 6354-6362.

ZHANG Xuewei, HUANG Yaji, CHENG Haoqiang, WANG Sheng, ZHU Zhicheng, LI Jinlei, DING Xueyu, LI Yuxin, WEI Zekun, ZHANG Rongchu. On the catalytic performance of commercial SCR catalyst for SO₃ generation[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6354-6362.

图/表 17

表1 江苏某电厂SCR催化剂化学组分及其质量分数（%）

TiO₂	V₂O₅	WO₃	SiO₂	CaO	Al₂O₃	总计
85.77	0.79	4.72	4.26	1.39	0.89	97.82

图1 SO2/SO3转化体系实验装置1—N2储罐；2—O2储罐；3—SO2储罐；4—NO储罐；5—NH3储罐；6—质量流量计；7—混气瓶；8—注射泵；9—水蒸气发生器；10—伴热带； 11—阀门；12—变色硅胶；13—烟气分析仪；14—恒温水浴锅；15—蛇形冷凝管；16—H2O2溶液；17—NaOH溶液

表2 实验工况

工况	温度/℃	SO₂浓度 /μg·g^-1	O₂体积分数/10^-6	NO浓度 /μg·g^-1	NH₃浓度 /μg·g^-1	H₂O体积分数/10^-6
1	250~500	2000	6	0	0	9
2	350	1200~2800	6	0	0	9
3	350	2000	0~8	0	0	9
4	350	2000	6	0	800	9
5	350	2000	6	800	0	9
6	350	2000	6	0~3200	0	9
7	350	2000	6	800	800	9

图2 温度对均相反应中SO2/SO3转化率的影响

图3 温度对催化反应中SO2/SO3转化率的影响

图4 SO2浓度对SO2/SO3转化率的影响

图5 O2浓度对SO2/SO3转化率的影响

图6 NH3对SO2/SO3转化率的影响

图7 NO x 对SO2/SO3转化率的影响

图8 NO x 气氛下催化剂形貌

图9 不同气氛下产物V 2p的XPS曲线

表3 不同气氛中催化剂的钒价态分布（%）

气氛	空白样	SO₂	SO₂+NO _x	SO₂+NH₃
V⁵⁺/(V⁵⁺+V⁴⁺+V³⁺)	43	10	53	4
V⁴⁺/(V⁵⁺+V⁴⁺+V³⁺)	46	75	42	81
V³⁺/(V⁵⁺+V⁴⁺+V³⁺)	11	15	5	15

图10 脱硝与SO2氧化的相互作用

图11 SCR催化剂上脱硝与SO2氧化的相互作用示意图

图12 不同气氛下产物S 2p的XPS曲线

表4 不同SCR催化剂化学组分及其质量分数（%）

催化剂类型	TiO₂	V₂O₅	WO₃	SiO₂	CaO	Al₂O₃	总计
SCR-J	85.77	0.79	4.72	4.26	1.39	0.89	97.82
SCR-S	87.28	0.73	5.04	3.12	1.15	0.73	98.05
SCR-H	87.07	1.54	4.90	2.88	1.15	0.62	98.16
SCR-Q	87.38	0.90	4.86	2.96	1.20	0.68	97.98
SCR-F	87.63	0.57	4.97	2.83	1.12	0.61	97.73

图13 温度对不同SCR催化剂SO2/SO3转化率的影响

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商用SCR催化剂催化生成SO₃特性

On the catalytic performance of commercial SCR catalyst for SO₃ generation

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