燃煤烟气中SO3与NH4HSO4生成特性及其控制方法研究进展

doi:10.16085/j.issn.1000-6613.2020-1049

摘要/Abstract

摘要：

在燃煤烟气中选择性催化还原（SCR）技术由于脱硝效率高、选择性好被广泛应用，然而SCR催化剂的催化作用会使烟气中的SO₂氧化成SO₃，SO₃会与NH₃等反应生成硫酸氢铵（ABS）和硫酸铵（AS），当烟气温度低于硫酸铵盐的凝结温度时，其会沉积在催化剂、空预器及其附属设备上，引发诸多严重的问题，对电厂的运行和环境造成了不利影响。本文综述了燃煤烟气中SO₃与硫酸氢铵的生成特性及其控制方法最新进展，分析了SO₃在锅炉和SCR系统中的形成机理、迁徙转化特性，阐述了控制SO₃与硫酸氢铵生成的方法，介绍了不同活性组分对催化剂表面SO₃和硫酸氢铵生成的影响。最后提出了开发新型催化剂是燃煤烟气中SO₃与硫酸氢铵生成控制的重点研究方向。

关键词: 三氧化硫, 氮氧化物, 选择性催化还原催化剂, 硫酸氢铵

Abstract:

SCR technology is widely used in treating coal-fired flue gas due to its high denitrification efficiency and good selectivity. However, SCR catalyst will oxidize the SO₂in flue gas to SO₃, which will subsequently react with NH₃ to generate ammonium bisulfate (ABS) and ammonium sulfate (AS). When the flue gas temperature is lower than the precipitation temperature of ammonium sulfate, it will deposit on the catalyst, air preheater and other attached equipment, which has caused many serious problems and brought a negative impact on the operation and environment of power plant. In this paper, the characteristics and control methods of SO₃ and ammonium bisulfate formation in coal-fired flue gas are reviewed. The formation mechanism and migration transformation characteristics of SO₃ in boiler and SCR system are analyzed. The effects of different active components on the generation of SO₃ and ammonium bisulfate on catalyst’s surface are introduced. Finally, it is proposed that the development of new catalysts is the key research direction for the control of SO₃and ammonium bisulfate formation in coal-fired flue gas.

Key words: sulfur trioxide, nitrogen oxide, selective catalytic reduction catalyst, ammonium hydrogen sulfate

中图分类号:

X511

尹子骏, 苏胜, 王中辉, 王乐乐, 安晓雪, 赵志刚, 陈逸峰, 刘涛, 汪一, 胡松, 向军. 燃煤烟气中SO₃与NH₄HSO₄生成特性及其控制方法研究进展[J]. 化工进展, 2021, 40(4): 2328-2337.

YIN Zijun, SU Sheng, WANG Zhonghui, WANG Lele, AN Xiaoxue, ZHAO Zhigang, CHEN Yifeng, LIU Tao, WANG Yi, HU Song, XIANG Jun. Research progress on the characteristics and control methods of SO₃and NH₄HSO₄ formation in coal-fired flue gas[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2328-2337.

图/表 14

参考文献 44

1	李高磊, 郭沂权, 张世博, 等. 超低排放燃煤电厂SO₃生成及控制的试验研究[J]. 中国电机工程学报, 2019, 39(4): 1079-1086.
	LI G L, GUO Y Q, ZHANG S B, et al. Experimental research on SO₃ generation and control in ultra-low emission coal-fired power plant[J]. Proceedings of the CSEE, 2019, 39(4): 1079-1086.
2	束航, 张玉华, 范红梅, 等. SCR脱硝中催化剂表面NH₄HSO₄生成及分解的原位红外研究[J]. 化工学报, 2015, 66(11): 4460-4468.
	SHU H, ZHANG Y H, FAN H M, et al. FT-IR study of formation and decomposition of ammonium bisulfates on surface of SCR catalyst for nitrogen removal[J]. CIESC Journal, 2015, 66(11): 4460-4468.
3	唐昊, 李慧, 杨江毅, 等. NH₃-SCR工艺中硫酸铵盐的生成与分解机理研究进展[J]. 化工进展, 2018, 37(3): 822-831.
	TANG H, LI H, YANG J Y, et al. Research progress on the formation and decomposition mechanism of ammonium-sulfate salts in NH₃-SCR technology[J]. Chemical Industry and Engineering Progress, 2018, 37(3): 822-831.
4	景有志, 杨丽, 朱淑维, 等. 锰钛系低温选择性催化还原催化剂的抗SO₂和抗H₂O性能研究进展[J]. 化工进展, 2018, 37(1): 105-111.
	JING Y Z, YANG L, ZHU S W, et al. Research progress on the SO₂ and H₂O resistance of Mn-Ti catalysts for low-temperature SCR[J]. Chemical Industry and Engineering Progress, 2018, 37(1): 105-111.
5	HUANG R, ZHANG Y, BOZZETTI C, et al. High secondary aerosol contribution to particulate pollution during haze events in China[J]. Nature, 2014, 514: 218-222.
6	CHENG Y, ZHENG G, WEI C, et al. Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China[J]. Science Advances, 2016, 2(12): e1601530.
7	蒋海涛, 蔡兴飞, 付玉玲, 等. 燃煤电厂SO₃形成、危害及控制技术[J]. 发电设备, 2013, 27(5): 366-368.
	JIANG H T, CAI X F, FU Y L, et al. Formation, harms and control technology of SO₃ in coal-fired power plants[J]. Power Equipment, 2013, 27(5): 366-368.
8	QING M, SU S, WANG L, et al. Effects of H₂O and CO₂ on the catalytic oxidation property of V/W/Ti catalysts for SO₃ generation[J]. Fuel, 2019, 237(1): 545-554.
9	LI X, WU Z, ZHANG L, et al. An updated acid dew point temperature estimation method for air-firing and oxy-fuel combustion processes[J]. Fuel Processing Technology, 2016, 154: 204-209.
10	HINDIYARTI L, GLARBORG P, MARSHALL P. Reactions of SO₃ with the O/H radical pool under combustion conditions[J]. The Journal of Physical Chemistry A, 2007, 111(19): 3984-3991.
11	FLEIG D, ANDERSSON K, NORMANN F, et al. SO₃ Formation under oxyfuel combustion conditions[J]. Industrial & Engineering Chemistry Research, 2011, 50(14): 8505-8514.
12	SARBASSOV Y, DUAN L, MANOVIC V, ANTHONY E J. Sulfur trioxide formation/emissions in coal-fired air-and oxy-fuel combustion processes: a review[J]. Greenhouse Gases-Sci Technol., 2018, 8(3): 402-428.
13	SCHLESINGER R B, ZELIKOFF J T, CHEN L C, et al. Assessment of toxicologic interactions resulting from acute inhalation exposure to sulfuric acid and ozone mixtures[J]. Toxicology and Applied Pharmacology, 1992, 115(2): 183-190.
14	SARBASSOV Y, DUAN L, JEREMIAS M, et al. SO₃ formation and the effect of fly ash in a bubbling fluidised bed under oxy-fuel combustion conditions[J]. Fuel Processing Technology, 2017, 167: 314-321.
15	GALLOWAY B, PADAK B. Effect of flue gas components on the adsorption of sulfur oxides on CaO[J]. Fuel, 2017, 197: 541-550.
16	唐昊, 李文艳, 王琦, 等. 商用选择性催化还原催化剂SO₂氧化率控制研究进展[J]. 化工进展, 2017, 36(6): 2143-2149.
	TANG H, LI W Y, WANG Q, et al. Research progress on the control of SO₂ oxidation by commercial SCR catalyst[J]. Chemical Industry and Engineering Progress, 2017, 36(6): 2143-2149.
17	QING M, SU S, WANG L, et al. Getting insight into the oxidation of SO₂to SO₃ over V₂O₅-WO₃/TiO₂ catalysts: reaction mechanism and effects of NO and NH₃[J]. Chemical Engineering Journal, 2019, 361: 1215-1224.
18	KAMATA H, OHARA H, TAKAHASHI K, et al. SO₂ oxidation over the V₂O₅/TiO₂ SCR catalyst[J]. Catalysis Letters, 2001, 73(1): 79-83.
19	JI P, GAO X, DU X, et al. Relationship between the molecular structure of V₂O₅/TiO₂ catalysts and the reactivity of SO₂ oxidation[J]. Catalysis Science & Technology, 2016, 6:1187-1194.
20	DUNN J P, KOPPULA P R, STENGER H G, et al. Oxidation of sulfur dioxide to sulfur trioxide over supported vanadia catalysts[J]. Applied Catalysis B: Environmental, 1998, 19(2): 103-117.
21	XIONG J, LI Y, LIN Y, et al. Formation of sulfur trioxide during the SCR of NO with NH₃ over a V₂O₅/TiO₂ catalyst[J]. RSC Adv., 2019, 9: 38952-38961.
22	ZHENG C, WANG Y, LIU Y, et al. Formation, transformation, measurement, and control of SO₃ in coal-fired power plants[J]. Fuel, 2019, 241: 327-346.
23	杨用龙, 苏秋凤, 张杨, 等. 燃煤电站典型超低排放工艺的SO₃脱除性能及排放特性[J]. 中国电机工程学报, 2019, 39(10): 2962-2969.
	YANG Y L, SU Q F, ZHANG Y, et al. Removal performance and emission characteristics of SO₃ by typical ultra-low emission technologies in coal-fired power plants[J]. Proceedings of the CSEE, 2019, 39(10): 2962-2969.
24	RHUDY R. Sulfuric acid removal process evaluation: short-term results[R]. California: Electric Power Research Institute, 2001.
25	卿梦霞. 燃煤烟气SO₃与硫酸氢铵生成机理研究[D]. 武汉: 华中科技大学, 2019.
	QING M X. Study on generation mechanism of SO₃ and ammounium hydrogen sulfate in coal-fired flue gas[D]. Wuhan: Huazhong University of Science and Technology, 2019.
26	XI Y, OTTINGER N A, LIU Z G. New insights into sulfur poisoning on a vanadia SCR catalyst under simulated diesel engine operating conditions[J]. Applied Catalysis B: Environmental, 2014, 160/161: 1-9.
27	SHI Y, SHU H, ZHANG Y, et al. Formation and decomposition of NH₄HSO₄ during selective catalytic reduction of NO with NH₃ over V₂O₅-WO₃/TiO₂ catalysts[J]. Fuel Processing Technology, 2016, 150: 141-147.
28	LI C X, SHEN M Q, YU T, et al. The mechanism of ammonium bisulfate formation and decomposition over V/WTi catalysts for NH₃-selective catalytic reduction at various temperatures[J]. Physical Chemistry Chemical Physics, 2017, 19(23): 15194-15206.
29	WANG X, DU X, LIU S, et al. Understanding the deposition and reaction mechanism of ammonium bisulfate on a vanadia SCR catalyst: a combined DFT and experimental study[J]. Applied Catalysis B: Environmental, 2019, 260: 118168.
30	CHEN P, WANG Z, CHANG J, et al. Experimental study of the reactivity of Ca-based matters with SO₃[C]//2011 Asia-Pacific Power and Energy Engineering Conference, IEEE, 2011.
31	陈晓露, 赵钦新, 鲍颖群, 等. SO₃脱除技术实验研究[J]. 动力工程学报, 2014, 34(12): 966-971.
	CHEN X L, ZHAO Q X, BAO Y Q, et al. Experimental research on SO₃ removal[J]. Journal of Chinese Society of Power Engineering, 2014, 34(12): 966-971.
32	WILHELM J H. SBS injection fights off SO₃[J]. Power Eng. Int., 2014, 12(12): 28-30.
33	MORETTI A L, TRISCORI R J, RITZENTHALER D P． A system approach to SO₃ mitigation[C]//Combined Power Plant Air Pollutant Control Mega Symposium, Baltimore, Maryland. USA, 2006.
34	高智溥, 胡冬, 张志刚, 等. 碱性吸附剂脱除 SO₃ 技术在大型燃煤机组中的应用[J]. 中国电力, 2017, 50(7): 102-108.
	GAO Z B, HU D, ZHANG Z G, et al. Application of alkaline adsorbent removal SO₃ technology in large coal-fired units[J]. Electric Power, 2017, 50(7): 102-108.
35	BLYTHE G, DOMBROWSKI K. SO₃ mitigation guide update[R]. Palo Alto, California, USA: Electric Power Research Institute, 2004: 31-43.
36	LIU Z, WOO S I. Recent advances in catalytic DeNO_x science and technology[J]. Catal. Rev.: Sci. Eng., 2006, 48(1): 43.
37	BALTIN G, KÖSER H, WENDLANDT K. Reactive desorption of sulfuric acid from ammonium sulfate loaded V₂O₅-WO₃/TiO₂DeNO_x‐catalysts[J]. Chemie Ingenieur Technik, 2001, 73(6): 605.
38	YE D, QU R, SONG H, et al. Investigation of the promotion effect of WO₃ on the decomposition and reactivity of NH₄HSO₄ with NO on V₂O₅-WO₃/TiO₂SCR catalysts[J]. RSC Advances, 2016, 6: 55584-55592.
39	QIAO J, WANG N, WANG Z, et al. Porous bimetallic Mn₂Co₁O_x catalysts prepared by a one-step combustion method for the low temperature selective catalytic reduction of NO_x with NH₃[J]. Catal. Commun., 2015, 72: 111-115.
40	WANG F, SHEN B, ZHU S, et al. Promotion of Fe and Co doped Mn-Ce/TiO₂ catalysts for low temperature NH₃-SCR with SO₂ tolerance[J]. Fuel, 2019, 249(1): 54-60.
41	LIU Z, YI Y, ZHANG S, et al. Selective catalytic reduction of NO_x with NH₃ over Mn-Ce mixed oxide catalyst at low temperatures[J]. Catalysis Today, 2013, 216: 76-81.
42	JIN R, LIU Y, WANG Y, et al. The role of cerium in the improved SO₂ tolerance for NO reduction with NH₃ over Mn-Ce/TiO₂ catalyst at low temperature[J]. Applied Catalysis B: Environmental, 2014, 148/149: 582-588.
43	KWON D W, PARK K H, HONG S C. Enhancement of SCR activity and SO₂ resistance on VO_x/TiO₂ catalyst by addition of molybdenum[J]. Chemical Engineering Journal, 2016, 284: 315-324.
44	XU Y, WU X, LIN Q, et al. SO₂ promoted V₂O₅-MoO₃/TiO₂ catalyst for NH₃-SCR of NO, at low temperatures[J]. Applied Catalysis A: General, 2019, 570: 42-50.

机组编号	装机容量/MW	SO₃质量浓度/mg·m^-3
机组编号	装机容量/MW	SCR入口	SCR出口	空预器出口	电除尘器出口	脱硫装置出口	湿式电除尘器出口
A	600	19.82	30.61	28.54	24.73	18.00	—
B	600	33.14	67.45	62.62	50.61	30.65	8.22
C	600	16.61	32.52	30.21	22.69	16.68	—
D	660	34.55	74.23	70.22	53.41	40.88	—
E	660	29373	68.66	65.76	50.91	33.76	—

机组编号	装机容量/MW	SO₃质量浓度/mg·m^-3
机组编号	装机容量/MW	SCR入口	SCR出口	空预器出口	电除尘器出口	脱硫装置出口	湿式电除尘器出口
A	600	19.82	30.61	28.54	24.73	18.00	—
B	600	33.14	67.45	62.62	50.61	30.65	8.22
C	600	16.61	32.52	30.21	22.69	16.68	—
D	660	34.55	74.23	70.22	53.41	40.88	—
E	660	29373	68.66	65.76	50.91	33.76	—

吸附剂	锅炉内		SCR		空预器
吸附剂	优点	缺点	优点	缺点	优点	缺点
石灰石	可同时脱除SO₂和SO₃	导致催化剂中毒，影响ESP除尘效率	—	—	—	—
Ca(OH)₂	可同时脱除SO₂和SO₃	易结焦	延缓空预器堵塞，对飞灰质量影响小	SO₃脱除效率低，影响ESP除尘效率	SO₃脱除效率高	SO₃脱除效率低，影响ESP除尘效率
MgO	SO₃脱除产物可通过吹灰设备去除	脱除效率低于Na基和Ca基吸附剂	对ESP除尘效率影响小，延缓空预器堵塞	脱除效率低于Na基和Ca基吸附剂	—	—
Mg(OH)₂	不结焦，对催化剂影响小	吸附剂用量大，成本高	—	—	—	—
天然碱 NaHCO₃	可同时脱除SO₂和SO₃	易结焦，导致催化剂中毒	对ESP除尘效率影响小	需增加研磨设备，成本高	避免NaHSO₄在空预器沉积	与上游相比脱除效率降低
SBS Na₂CO₃	SCR宽负荷运行，脱出效率高	导致催化剂中毒	对ESP除尘效率影响小，SO₃脱除效率高	NaHSO₄会在空预器和烟道沉积	避免NaHSO₄在空预器沉积	NaHSO₄会烟道沉积，对飞灰质量影响大

吸附剂	锅炉内		SCR		空预器
吸附剂	优点	缺点	优点	缺点	优点	缺点
石灰石	可同时脱除SO₂和SO₃	导致催化剂中毒，影响ESP除尘效率	—	—	—	—
Ca(OH)₂	可同时脱除SO₂和SO₃	易结焦	延缓空预器堵塞，对飞灰质量影响小	SO₃脱除效率低，影响ESP除尘效率	SO₃脱除效率高	SO₃脱除效率低，影响ESP除尘效率
MgO	SO₃脱除产物可通过吹灰设备去除	脱除效率低于Na基和Ca基吸附剂	对ESP除尘效率影响小，延缓空预器堵塞	脱除效率低于Na基和Ca基吸附剂	—	—
Mg(OH)₂	不结焦，对催化剂影响小	吸附剂用量大，成本高	—	—	—	—
天然碱 NaHCO₃	可同时脱除SO₂和SO₃	易结焦，导致催化剂中毒	对ESP除尘效率影响小	需增加研磨设备，成本高	避免NaHSO₄在空预器沉积	与上游相比脱除效率降低
SBS Na₂CO₃	SCR宽负荷运行，脱出效率高	导致催化剂中毒	对ESP除尘效率影响小，SO₃脱除效率高	NaHSO₄会在空预器和烟道沉积	避免NaHSO₄在空预器沉积	NaHSO₄会烟道沉积，对飞灰质量影响大

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燃煤烟气中SO₃与NH₄HSO₄生成特性及其控制方法研究进展

Research progress on the characteristics and control methods of SO₃and NH₄HSO₄ formation in coal-fired flue gas

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