超低温（< 150℃）SCR脱硝技术研究进展

doi:10.11949/0438-1157.20200785

摘要/Abstract

摘要：

以氨为还原剂的选择性催化还原（SCR）技术是工业脱硝的主流技术。我国已形成在180~420℃（包含低温和中高温）范围内具有良好应用效果的SCR技术及其催化剂体系，但超低温段（< 150℃）仍有待突破。超低温SCR脱硝通常位于“除尘-脱硫”工艺之后，具有烟气组成简单、能耗少、改造成本低等优点，吸引了研究人员的广泛关注。在简要分析不同行业烟气排放特征及治理现状的基础上，总结了150℃以下具有良好SCR活性的催化剂体系（锰基、钒基、铬基和活性炭基），重点对催化剂的抗水、硫、碱金属和硝铵中毒性能进行了探讨，并介绍了该领域最近的一些中试/侧线试验研究进展情况，最后对这一技术的未来发展方向进行了展望。

关键词: 大气污染治理, 烟道气, 脱硝, 超低温, 选择性催化还原, 煤燃烧

Abstract:

Selective catalytic reduction of NO with NH₃ (NH₃-SCR) is a well-established technology for eliminating NO_x from stationary source. Over the past decades, great progress has been achieved in China in developing practical SCR catalysts that can work well in power plant and other fields like coking industry at low and medium temperature range (180 — 420℃). However, the extension of SCR technology to ultra-low temperatures (e.g., < 150℃), which can meet the requirement of flue gas treatment from diverse non-electricity fields like cement kiln and industrial boiler, is still a big challenge. Ultra-low temperature SCR denitrification is usually located after the “dust removal-desulfurization” process. It has the advantages of simple flue gas composition, low energy consumption, and low transformation cost, which has attracted wide attention from researchers. In this mini-review, we first give a brief introduction on the current status of flue gas control from different industrial fields. Then, the catalyst systems (MnO_x, VO_x, CrO_x, activated carbon) that can provide good deNO_x performance under 150℃ are summarized, and the resistance property to H₂O, SO₂, alkali metals and ammonium nitrate species is emphasized. As well, the recent progress over pilot experiments for industrial application is introduced. Lastly, the prospect of ultra-low temperature SCR denitrification is discussed.

Key words: air pollution control, flue gas, denitration, ultra-low temperature, selective catalytic reduction, coal combustion

中图分类号:

TQ 028.8

汤常金,孙敬方,董林. 超低温（< 150℃）SCR脱硝技术研究进展[J]. 化工学报, 2020, 71(11): 4873-4884.

Changjin TANG,Jingfang SUN,Lin DONG. Recent progress on elimination of NO_x from flue gas via SCR technology under ultra-low temperatures (< 150℃)[J]. CIESC Journal, 2020, 71(11): 4873-4884.

图/表 7

图1 2011~2015年我国氮氧化物排放情况[3]

Fig.1 Annual report for NOx emission from different sources in China during 2011—2015[3]

表1 常用烟气脱硝方法比较

Table 1 The comparison of different technologies for industrial denitration

脱硝工艺	脱硝率/%	还原/氧化剂	反应温度/℃	催化剂	存在的风险
低氮燃烧	30~60	无	无要求	不使用催化剂	无
SNCR	40～70	NH₃或尿素	800～1250	不使用催化剂	氨逃逸
氧化吸收法	50～85	氧化剂，碱液	<100	不使用催化剂	二次水、臭氧污染等；易产生白烟
活性焦脱硝	50～80	NH₃或尿素	130~200	活性焦	自燃隐患
SCR	75～90	NH₃或尿素	100~500	使用催化剂	无

表2 一些代表性行业的烟气组成、目前使用的脱硝技术与NOx排放限值情况

Table 2 The flue gas composition, adopted denitration technique and emission limit for NOx in some typical industries

行业	烟气组成				目前使用的脱硝技术	NO_x排放限值/(mg/m³)
行业	NO_x/(mg/m³)	SO_x/(mg/m³)	粉尘/(mg/m³)	其他	目前使用的脱硝技术	NO_x排放限值/(mg/m³)
火电	100~1000	500~4000	30~100	Hg，Pb等	SCR	50
焦化	200~800	100~500	50~85	H₂S等	SCR	150
钢铁	200~310	400~1500	30~80	CO，二英等	活性焦、臭氧氧化、SCR	50
水泥	800~1200	30~100	80000~120000	CaO等	SNCR	320
玻璃	1200~3000	300~3300	300~1200	Na盐，CaO等	SNCR	700
陶瓷	200~1100	500~3500	50~200	HCl，Pb、Cd等	SNCR	180
垃圾焚烧	400~1000	200~1200	1000~10000	HCl，二英等	SNCR	300
燃气锅炉	100~400	0~20	—	H₂O，CO等	低氮燃烧	200

图2 MnO2(110)催化剂表面SCR反应各过程势能曲线[7]

Fig.2 Energy profile for the complete NH3-SCR process on MnO2(110)[7]

图3 基于毛细作用调控的MnOx/TiO2催化剂抗水性能提高示意图

Fig.3 Schematic illustration of the strategy to improve H2O resistance of MnOx/TiO2 catalyst via controlled capillary condensation

图4 基于牺牲剂策略调控的MnOx-CeO2/TiO2催化剂抗硫性能提升示意图

Fig.4 Schematic illustration of the strategy to improve SO2 resistance of MnOx-CeO2/TiO2 catalyst via adding sacrificial agent

图5 “除尘-脱硫-脱硝”工艺路线示意图（对应超低温脱硝）[102]

Fig.5 Schematic illustration of flue gas treatment via “dedusting-desulfation-denitration” route (corresponding to ultra-low temperature SCR) [102]

参考文献 103

1	Huang R J, Zhang Y L, Bozzetti C, et al. High secondary aerosol contribution to particulate pollution during haze events in China[J]. Nature, 2014, 514(7521): 218-222.
2	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 Advance, 2017, 2(12): e1601530.
3	中国环境监测总站. 中国环境统计年报: 2013—2017[M]. 北京: 中国环境科学出版社, 2014—2018.
	China National Environmental Monitoring Centre. Annual Statistic Report on Environment in China: 2013—2017[M]. Beijing: China Environmental Science Press, 2014—2018.
4	江苏省环境保护厅. 关于开展全省非电行业氮氧化物深度减排的通知[Z]. 2017.
	Environmental Protection Department of Jiangsu Province. Deployment of NO_x emission control from non-electric industries in Jiangsu province [Z]. 2017.
5	王修文, 李露露, 孙敬方, 等. 我国氮氧化物排放控制及脱硝催化剂研究进展[J]. 工业催化, 2019, 27(2): 1-23.
	Wang X W, Li L L, Sun J F, et al. Analysis of NO_x emission and control in China and research progress in denitration catalysts[J]. Industrial Catalysis, 2019, 27(2): 1-23.
6	Tang C J, Zhang H L, Dong L. Ceria-based catalysts for low-temperature selective catalytic reduction of NO with NH₃[J]. Catalysis Science & Technology, 2016, 6(5): 1248-1264.
7	Yuan H, Sun N, Chen J, et al. Insight into the NH₃-assisted selective catalytic reduction of NO on β-MnO₂ (110): reaction mechanism, activity descriptor, and evolution from a pristine state to a steady state[J]. ACS Catalysis, 2018, 8(10): 9269-9279.
8	Liu C, Shi J W, Gao C, et al. Manganese oxide-based catalysts for low-temperature selective catalytic reduction of NO_x with NH₃: a review[J]. Applied Catalysis A: General, 2016, 522: 54-69.
9	Kang M, Yeon T H, Park E D, et al. Novel MnO_x catalysts for NO reduction at low temperature with ammonia[J]. Catalysis Letters, 2006, 106(1/2): 77-80.
10	Kang M, Park E D, Kim J M, et al. Manganese oxide catalysts for NO_x reduction with NH₃ at low temperatures[J]. Applied Catalysis A: General, 2007, 327(2): 261-269.
11	唐晓龙, 郝吉明, 徐文国, 等. 新型MnO_x催化剂用于低温NH₃选择性催化还原NO_x[J]. 催化学报, 2006, 27(10): 843-848.
	Tang X L, Hao J M, Xu W G, et al. Novel MnO_x catalyst for low-temperature selective catalytic reduction of NO_x with NH₃[J]. Chinese Journal of Catalysis, 2006, 27(10): 843-848.
12	戴韵, 李俊华, 彭悦,等. MnO₂的晶相结构和表面性质对低温NH₃-SCR反应的影响[J]. 物理化学学报, 2012, 28(7):1771-1776.
	Dai Y, Li J H, Peng Y, et al. Effects of MnO₂ crystal structure and surface property on the NH₃-SCR reaction at low temperature[J]. Acta Physico-Chimica Sinica, 2012, 28(7):1771-1776.
13	Gong P J, Xie J L, Fang D, et al. Effects of surface physicochemical properties on NH₃-SCR activity of MnO₂ catalysts with different crystal structures[J]. Chinese Journal of Catalysis, 2017, 38(11): 1925-1934.
14	Andreoli S, Deorsola F A, Galletti C, et al. Nanostructured MnO_x catalysts for low-temperature NO_x SCR[J]. Chemical Engineering Journal, 2015, 278: 174-182.
15	孙梦婷, 黄碧纯, 马杰文,等. 二氧化锰在低温NH₃-SCR催化反应上的形貌效应[J]. 物理化学学报, 2016, 32(6):1501-1510.
	Sun M T, Huang B C, Ma J W, et al. Morphological effects of manganese dioxide on catalytic reactions for low-temperature NH₃-SCR[J]. Acta Physico-Chimica Sinica, 2016, 32(6):1501-1510.
16	Shi J W, Gao C, Liu C, et al. Porous MnO_x for low-temperature NH₃-SCR of NO_x: the intrinsic relationship between surface physicochemical property and catalytic activity[J]. Journal of Nanoparticle Research, 2017, 19(6): 194.
17	Xu T, Wang C, Wu X, et al. Modification of MnCo₂O_x catalysts by NbO_x for low temperature selective catalytic reduction of NO with NH₃[J]. RSC Advances, 2016, 6(99): 97004-97011.
18	Liu J, Wei Y, Li P Z, et al. Experimental and theoretical investigation of mesoporous MnO₂ nanosheets with oxygen vacancies for high-efficiency catalytic deNO_x[J]. ACS Catalysis, 2018, 8(5): 3865-3874.
19	Zhan S, Zhu D, Qiu M, et al. Highly efficient removal of NO with ordered mesoporous manganese oxide at low temperature[J]. RSC Advances, 2015, 5(37): 29353-29361.
20	Tian W, Yang H, Fan X, et al. Catalytic reduction of NO_x with NH₃ over different-shaped MnO₂ at low temperature[J]. Journal of Hazardous Materials, 2011, 188(1/2/3): 105-109.
21	Yao X, Kong T, Yu S, et al. Influence of different supports on the physicochemical properties and denitration performance of the supported Mn-based catalysts for NH₃-SCR at low temperature[J]. Applied Surface Science, 2017, 402: 208-217.
22	Kijlstra W S, Daamen J C M L, van de Graaf J M, et al. Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnO_x/Al₂O₃[J]. Applied Catalysis B: Environmental, 1996, 7(3/4): 337-357.
23	Yang G, Zhao H, Luo X, et al. Promotion effect and mechanism of the addition of Mo on the enhanced low temperature SCR of NO_x by NH₃ over MnO_x/γ-Al₂O₃ catalysts[J]. Applied Catalysis B: Environmental, 2019, 245: 743-752.
24	Qu L, Li C, Zeng G, et al. Support modification for improving the performance of MnO_x–CeO_y/γ-Al₂O₃ in selective catalytic reduction of NO by NH₃[J]. Chemical Engineering Journal, 2014, 242: 76-85.
25	Zhao W, Li C, Lu P, et al. Iron, lanthanum and manganese oxides loaded on γ-Al₂O₃ for selective catalytic reduction of NO with NH₃ at low temperature[J]. Environmental Technology, 2013, 34(1): 81-90.
26	Wang X, Wu S, Zou W, et al. Fe-Mn/Al₂O₃ catalysts for low temperature selective catalytic reduction of NO with NH₃[J]. Chinese Journal of Catalysis, 2016, 37(8): 1314-1323.
27	Smirniotis P G, Sreekanth P M, Peña D A, et al. Manganese oxide catalysts supported on TiO₂, Al₂O₃, and SiO₂: a comparison for low-temperature SCR of NO with NH₃[J]. Industrial & Engineering Chemistry Research, 2006, 45(19): 6436-6443.
28	Jiang B, Liu Y, Wu Z. Low-temperature selective catalytic reduction of NO on MnO_x/TiO₂ prepared by different methods[J]. Journal of Hazardous Materials, 2009, 162(2/3): 1249-1254.
29	Wu Z, Jiang B, Liu Y, et al. Experimental study on a low-temperature SCR catalyst based on MnO_x/TiO₂ prepared by sol–gel method[J]. Journal of Hazardous Materials, 2007, 145(3): 488-494.
30	黄海凤, 张峰, 卢晗锋, 等. 制备方法对低温 NH₃-SCR 脱硝催化剂MnO_x/TiO₂结构与性能的影响[J]. 化工学报, 2010, 61(1): 80-85.
	Huang H F, Zhang F, Lu H F, et al. Effect of preparation methods on structures and performance of MnO_x/TiO₂ catalyst for low-temperature NH₃-SCR[J]. CIESC Journal, 2010, 61(1): 80-85.
31	Li J, Chen J, Ke R, et al. Effects of precursors on the surface Mn species and the activities for NO reduction over MnO_x/TiO₂ catalysts[J]. Catalysis Communications, 2007, 8(12): 1896-1900.
32	Deng S, Meng T, Xu B, et al. Advanced MnO_x/TiO₂ catalyst with preferentially exposed anatase {001} facet for low-temperature SCR of NO[J]. ACS Catalysis, 2016, 6(9): 5807-5815.
33	Liu X, Yu Q, Chen H, et al. The promoting effect of S-doping on the NH₃-SCR performance of MnO_x/TiO₂ catalyst[J]. Applied Surface Science, 2020, 508: 144694.
34	Kim Y J, Kwon H J, Nam I S, et al. High deNO_x performance of Mn/TiO₂ catalyst by NH₃[J]. Catalysis Today, 2010, 151(3/4): 244-250.
35	Qi G, Yang R T. Low-temperature selective catalytic reduction of NO with NH₃ over iron and manganese oxides supported on titania[J]. Applied Catalysis B: Environmental, 2003, 44(3): 217-225.
36	Wu S, Yao X, Zhang L, et al. Improved low temperature NH₃-SCR performance of FeMnTiO_x mixed oxide with CTAB-assisted synthesis[J]. Chemical Communications, 2015, 51(16): 3470-3473.
37	Wu S, Zhang L, Wang X, et al. Synthesis, characterization and catalytic performance of FeMnTiO_x mixed oxides catalyst prepared by a CTAB-assisted process for mid-low temperature NH₃-SCR[J]. Applied Catalysis A: General, 2015, 505: 235-242.
38	Qi G, Yang R T. Performance and kinetics study for low-temperature SCR of NO with NH₃ over MnO_x–CeO₂ catalyst[J]. Journal of Catalysis, 2003, 217(2): 434-441.
39	Xu L, Li X S, Crocker M, et al. A study of the mechanism of low-temperature SCR of NO with NH₃ on MnO_x/CeO₂[J]. Journal of Molecular Catalysis A: Chemical, 2013, 378: 82-90.
40	Andreoli S, Deorsola F A, Pirone R. MnO_x/CeO₂ catalysts synthesized by solution combustion synthesis for the low-temperature NH₃-SCR[J]. Catalysis Today, 2015, 253: 199-206.
41	Shen B, Wang F, Liu T. Homogeneous MnO_x–CeO₂ pellets prepared by a one-step hydrolysis process for low-temperature NH₃-SCR[J]. Powder Technology, 2014, 253: 152-157.
42	Yao X, Ma K, Zou W, et al. Influence of preparation methods on the physicochemical properties and catalytic performance of MnO_x-CeO₂ catalysts for NH₃-SCR at low temperature[J]. Chinese Journal of Catalysis, 2017, 38(1): 146-159.
43	Liu C, Gao G, Shi J W, et al. MnO_x-CeO₂ shell-in-shell microspheres for NH₃-SCR de-NO_x at low temperature[J]. Catalysis Communications, 2016, 86: 36-40.
44	Li S, Huang B, Yu C. A CeO₂-MnO_x core-shell catalyst for low-temperature NH₃-SCR of NO[J]. Catalysis Communications, 2017, 98: 47-51.
45	Ma Z, Sheng L, Wang X, et al. Oxide catalysts with ultra-strong resistance to SO₂ deactivation for removing nitric oxide at low temperature[J]. Advanced Materials, 2019, 31(42): 1903719.
46	Weiman L, Haidi L, Yunfa C. Mesoporous MnO_x-CeO₂ composites for NH₃-SCR: the effect of preparation methods and a third dopant[J]. RSC Advances, 2019, 9(21): 11912-11921.
47	Wei Y, Sun Y, Su W, et al. MnO₂ doped CeO₂ with tailored 3-D channels exhibits excellent performance for NH₃-SCR of NO[J]. RSC Advances, 2015, 5(33): 26231-26235.
48	Gan L, Li K, Yang W, et al. Core-shell-like structured α-MnO₂@CeO₂ catalyst for selective catalytic reduction of NO: promoted activity and SO₂ tolerance[J]. Chemical Engineering Journal, 2019, 391: 123473.
49	Zhang L, Zhang D, Zhang J, et al. Design of meso-TiO₂@MnO_x-CeO_x/CNTs with a core–shell structure as DeNO_x catalysts: promotion of activity, stability and SO₂-tolerance[J]. Nanoscale, 2013, 5(20): 9821-9829.
50	Ran X, Li M, Wang K, et al. Spatially confined tuning the interfacial synergistic catalysis in mesochannels toward selective catalytic reduction[J]. ACS Applied Materials & Interfaces, 2019, 11(21): 19242-19251.
51	Li L, Sun B, Sun J, et al. Novel MnO_x-CeO₂ nanosphere catalyst for low-temperature NH₃-SCR[J]. Catalysis Communications, 2017, 100: 98-102.
52	Ma K, Zou W, Zhang L, et al. Construction of hybrid multi-shell hollow structured CeO₂-MnO_x materials for selective catalytic reduction of NO with NH₃[J]. RSC advances, 2017, 7(10): 5989-5999.
53	Xiong Y, Tang C, Yao X, et al. Effect of metal ions doping (M= Ti⁴⁺, Sn⁴⁺) on the catalytic performance of MnO_x/CeO₂ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. Applied Catalysis A: General, 2015, 495: 206-216.
54	Zhang L, Shi L, Huang L, et al. Rational design of high-performance deNO_x catalysts based on Mn_xCo_3–_xO₄ nanocages derived from metal-organic frameworks[J]. ACS Catalysis, 2014, 4(6): 1753-1763.
55	Meng D, Zhan W, Guo Y, et al. A highly effective catalyst of Sm-MnO_x for the NH₃-SCR of NO_x at low temperature: promotional role of Sm and its catalytic performance[J]. ACS Catalysis, 2015, 5(10): 5973-5983.
56	Xu Q, Fang Z, Chen Y, et al. Titania–samarium–manganese composite oxide for the low-temperature selective catalytic reduction of NO with NH₃[J]. Environmental Science & Technology, 2020, 54(4): 2530-2538.
57	Wang Z, Guo R, Shi X, et al. The superior performance of CoMnO_x catalyst with ball-flowerlike structure for low-temperature selective catalytic reduction of NO_x by NH₃[J]. Chemical Engineering Journal, 2020, 381: 122753.
58	Liu Y, Guo R, Duan C, et al. A highly effective urchin-like MnCrO_x catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Fuel, 2020, 271: 117667.
59	Gao G, Shi J W, Fan Z, et al. MnM₂O₄ microspheres (M= Co, Cu, Ni) for selective catalytic reduction of NO with NH₃: comparative study on catalytic activity and reaction mechanism via in-situ diffuse reflectance infrared Fourier transform spectroscopy[J]. Chemical Engineering Journal, 2017, 325: 91-100.
60	Yan L, Liu Y, Zha K, et al. Scale–activity relationship of MnO_x-FeO_y nanocage catalysts derived from Prussian blue analogues for low-temperature NO reduction: experimental and DFT studies[J]. ACS Applied Materials & Interfaces, 2017, 9(3): 2581-2593.
61	Wan Y, Zhao W, Tang Y, et al. Ni-Mn bi-metal oxide catalysts for the low temperature SCR removal of NO with NH₃[J]. Applied Catalysis B: Environmental, 2014, 148: 114-122.
62	Zuo J, Chen Z, Wang F, et al. Low-temperature selective catalytic reduction of NO_x with NH₃ over novel Mn-Zr mixed oxide catalysts[J]. Industrial & Engineering Chemistry Research, 2014, 53(7): 2647-2655.
63	Chang H, Li J, Chen X, et al. Effect of Sn on MnO_x-CeO₂ catalyst for SCR of NO_x by ammonia: enhancement of activity and remarkable resistance to SO₂[J]. Catalysis Communications, 2012, 27: 54-57.
64	Inomata Y, Hata S, Mino M, et al. Bulk vanadium oxide versus conventional V₂O₅/TiO₂: NH₃-SCR catalysts working at a low temperature below 150℃[J]. ACS Catalysis, 2019, 9(10): 9327-9331.
65	Smirniotis P G, Peña D A, Uphade B S. Low-temperature selective catalytic reduction (SCR) of NO with NH₃ by using Mn, Cr, and Cu oxides supported on Hombikat TiO₂[J]. Angewandte Chemie International Edition, 2001, 40(13): 2479-2482.
66	Li S, Wang X, Tan S, et al. CrO₃ supported on sargassum-based activated carbon as low temperature catalysts for the selective catalytic reduction of NO with NH₃[J]. Fuel, 2017, 191: 511-517.
67	Zhang Y, Zhang H, Zhou L, et al. DRIFT study on Cr₂O₃-SO42-/TiO₂ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. Chemical Research in Chinese Universities, 2014, 30(2): 279-283.
68	Yu S, Xu S, Sun B, et al. Synthesis of CrO_x/C catalysts for low temperature NH₃-SCR with enhanced regeneration ability in the presence of SO₂[J]. RSC Advances, 2018, 8(7): 3858-3868.
69	Zeng Z, Lu P, Li C, et al. Removal of NO by carbonaceous materials at room temperature: a review[J]. Catalysis Science & Technology, 2012, 2(11): 2188-2199.
70	付亚利, 张永发, 李国强,等. 非沥青基煤质氧化活性炭的脱硝特性[J]. 环境工程学报, 2016, 7(10): 3727-3732.
	Fu Y L, Zhang Y F, Li G Q, et al. Denitrification characteristics of non-pitch coal-based oxidized activated carbon[J]. Chinese Journal of Environmental Engineering, 2016, 7(10): 3727-3732.
71	Guo Q, Jing W, Hou Y, et al. On the nature of oxygen groups for NH₃-SCR of NO over carbon at low temperatures[J]. Chemical Engineering Journal, 2015, 270: 41-49.
72	Adapa S, Gaur V, Verma N. Catalytic oxidation of NO by activated carbon fiber (ACF)[J]. Chemical Engineering Journal, 2006, 116(1): 25-37.
73	Yu S, Jiang N, Zou W, et al. A general and inherent strategy to improve the water tolerance of low temperature NH₃-SCR catalysts via trace SiO₂ deposition[J]. Catalysis Communications, 2016, 84: 75-79.
74	Wang H, Huang B, Yu C, et al. Research progress, challenges and perspectives on the sulfur and water resistance of catalysts for low temperature selective catalytic reduction of NO_x by NH₃[J]. Applied Catalysis A: General, 2019, 588: 117207.
75	Gao C, Shi J W, Fan Z, et al. Sulfur and water resistance of Mn-based catalysts for low-temperature selective catalytic reduction of NO_x: a review[J]. Catalysts, 2018, 8(1): 11.
76	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: 582-588.
77	Liu H, Fan Z, Sun C, et al. Improved activity and significant SO₂ tolerance of samarium modified CeO₂-TiO₂ catalyst for NO selective catalytic reduction with NH₃[J]. Applied Catalysis B: Environmental, 2019, 244: 671-683.
78	Sun C, Liu H, Chen W, et al. Insights into the Sm/Zr co-doping effects on N₂ selectivity and SO₂ resistance of a MnO_x-TiO₂ catalyst for the NH₃-SCR reaction[J]. Chemical Engineering Journal, 2018, 347: 27-40.
79	Wang X, Lan Z, Liu Y, et al. Facile fabrication of hollow tubular mixed oxides for selective catalytic reduction of NO_x at low temperature: a combined experimental and theoretical study[J]. Chemical Communications, 2017, 53(5): 967-970.
80	Li H, Zhang D, Maitarad P, et al. In situ synthesis of 3D flower-like NiMnFe mixed oxides as monolith catalysts for selective catalytic reduction of NO with NH₃[J]. Chemical Communications, 2012, 48(86): 10645-10647.
81	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, 2020, 260: 118168.
82	Chen Y, Li C, Chen J, et al. Self-prevention of well-defined-facet Fe₂O₃/MoO₃ against deposition of ammonium bisulfate in low-temperature NH₃-SCR[J]. Environmental Science & Technology, 2018, 52(20): 11796-11802.
83	Ma Z, Sheng L, Wang X, et al. Oxide catalysts with ultrastrong resistance to SO₂ deactivation for removing nitric oxide at low temperature [J]. Advanced Materials, 2020, 32(6): 1907806.
84	Yu J, Guo F, Wang Y, et al. Sulfur poisoning resistant mesoporous Mn-base catalyst for low-temperature SCR of NO with NH₃ [J]. Applied Catalysis B: Environmental, 2010, 95(1/2): 160-168
85	Guo K, Fan G, Gu D, et al. Pore size expansion accelerates ammonium bisulfate decomposition for improved sulfur resistance in low-temperature NH₃-SCR[J]. ACS Applied Materials & Interfaces, 2019, 11(5): 4900-4907.
86	Ma K, Guo K, Li L, et al. Cavity size dependent SO₂ resistance for NH₃-SCR of hollow structured CeO₂-TiO₂ catalysts[J]. Catalysis Communications, 2019, 128: 105719.
87	Fan Z, Shi J W, Niu C, et al. The insight into the role of Al₂O₃ in promoting the SO₂ tolerance of MnO_x for low-temperature selective catalytic reduction of NO_x with NH₃[J]. Chemical Engineering Journal, 2020, 398: 125572.
88	Huang Z, Gu X, Wen W, et al. A “smart” hollandite deNO_x catalyst: self-protection against alkali poisoning[J]. Angewandte Chemie International Edition, 2013, 52(2): 660-664.
89	Li C, Huang Z, Liu X, et al. Rational design of alkali-resistant catalysts for selective NO reduction with NH₃[J]. Chemical Communications, 2019, 55(66): 9853-9856.
90	Liu X, Gao J, Chen Y, et al. Rational design of alkali-resistant NO reduction catalysts using a stable hexagonal V-doped MoO₃ support for alkali trapping[J]. ChemCatChem, 2018, 10(18): 3999-4003.
91	Zheng L, Zhou M, Huang Z, et al. Self-protection mechanism of hexagonal WO₃-based deNO_x catalysts against alkali poisoning[J]. Environmental Science & Technology, 2016, 50(21): 11951-11956.
92	Hao Z, Shen Z, Li Y, et al. The role of alkali metal in α-MnO₂ catalyzed ammonia-selective catalysis[J]. Angewandte Chemie International Edition, 2019, 58(19): 6351-6356.
93	Ciardelli C, Nova I, Tronconi E, et al. A “Nitrate Route” for the low temperature “Fast SCR” reaction over a V₂O₅-WO₃/TiO₂ commercial catalyst[J]. Chemical Communications, 2004, (23): 2718-2719.
94	Chen Z, Si Z, Cao L, et al. Decomposition behavior of ammonium nitrate on ceria catalysts and its role in the NH₃-SCR reaction[J]. Catalysis Science & Technology, 2017, 7(12): 2531-2541.
95	van der Grift C J G, Woldhuis A F, Maaskant O L. The shell DENOX system for low temperature NO_x removal[J]. Catalysis Today, 1996, 27(1/2): 23-27.
96	张霄玲, 鲍佳宁, 余剑, 等. 工业MnO_x颗粒催化剂的制备及其低温脱硝应用研究[J]. 化工学报, 2020, 71(11): 5169-5177.
	Zhang X L, Bao J N, Yu J, et al. The preparation and industrial application of MnO_x particle catalyst for low temperature denitration[J]. CIESC Journal, 2020,71(11): 5169-5177.
97	曾红, 刘平乐, 张喻升,等. 表面涂覆型低温脱硝催化剂的开发与中试应用[J]. 过程工程学报, 2017, 17(6): 1208-1216.
	Zeng H, Liu P L, Zhang Y S, et al. Development and pilot test of surface-coating SCR de-nitration catalyst at low temperature[J]. The Chinese Journal of Process Engineering, 2017, 17(6): 1208-1216.
98	皇甫林, 李长明, 王超, 等. 硅系黏结剂对涂覆型蜂窝体催化剂性能的影响[J]. 过程工程学报, 2020, 20(4): 484-492.
	Huangfu L, Li C M, Wang C, et al. Effect of silicon-based binder on the performance of coated honeycomb catalyst[J]. The Chinese Journal of Process Engineering, 2020, 20(4): 484-492.
99	赵勇刚, 董林, 李奇隽, 等. 低温脱硝催化剂在火电厂锅炉启动期间的中试应用[J]. 工业催化, 2018, 26(4): 64-71.
	Zhao Y G, Dong L, Li Q J, et al. Pilot-scale application of low temperature deNO_x catalyst for start-up of boiler in thermal power plant[J]. Industrial Catalysis, 2018, 26(4): 64-71.
100	王成志, 曹鹏, 颜鑫, 等. 中试规模下蜂窝式Mn-Ce/Al₂O₃脱硝催化剂的低温性能[J]. 环境工程学报, 2018, 12(4):75-84.
	Wang C Z, Cao P, Yan X, et al. Low temperature performance of honeycomb Mn-Ce/Al₂O₃ de-nitration catalyst in pilot-scale[J]. Chinese Journal of Environmental Engineering, 2018, 12(4):75-84.
101	唐志雄, 曾环木, 陈雄波, 等. 燃煤烟气低温SCR脱硝中试研究[J]. 环境工程学报, 2014, 8(3): 1120-1124.
	Tang Z X, Zeng H M, Chen X B, et al. Pilot-scale study of selective catalytic reduction of NO_x at low temperature[J]. Chinese Journal of Environmental Engineering, 2014, 8(3): 1120-1124.
102	Wang C, Yu F, Zhu M, et al. Microspherical MnO₂-CeO₂-Al₂O₃ mixed oxide for monolithic honeycomb catalyst and application in selective catalytic reduction of NO_x with NH₃ at 50-150℃[J]. Chemical Engineering Journal, 2018, 34: 182-192.
103	科技部网站新闻稿. 国家863计划 “固定源烟气处理稀土催化材料的应用与开发” 课题在新疆石河子通过验收[EB/OL]. .
	News release from website of Ministry of Science and Technology. The National 863 Program “Application and development of rare earth catalytic materials for flue gas treatment from stationary sources” was accepted in Shihezi, Xinjiang [EB/OL]. .

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