Recent progress on elimination of NOx from flue gas via SCR technology under ultra-low temperatures (< 150℃)

doi:10.11949/0438-1157.20200785

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 7

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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]. .
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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

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

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

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

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