Research progress of NO x reduction by carbonaceous substances for denitration in cement kiln

doi:10.16085/j.issn.1000-6613.2022-1894

Abstract

Abstract:

With the popularization of “ultra-low emission” standard in cement industry, the NO _x emission limit is gradually reduced to 100mg/m³ or even 50mg/m³. The carbonaceous denitration in cement kiln is carried out by controlling pulverized coal combustion to produce coke and CO as the NO _x reducing agent. It has the advantages of no additional denitration agents, no ammonia emission, good compatibility with the cement production processes and low cost of technical revamp and operation, providing the auxiliary processes for the cement industry to achieve the “ultra-low emission” standard. In this paper, the main implementations of carbonaceous substance denitration were introduced, including the low nitrogen oxide burning in rotary kiln, the staged combustion in decomposition furnace and the addition of reduction zone. Then, the characteristics and mechanism of NO _x reduction by coke and CO were discussed. The reduction effects of coke are related to its specific surface area and reactive sites. The CO reduction can occur without catalysis, but the efficiency could be ignored when CO concentration is less than 1%. Coke, CaO and coal ash act as catalysts to reduce the lower temperature window limit of NO reduction by CO from 900℃ to 600—800℃. Finally, the influence of CO on SNCR and its mechanism were summarized. It is considered that carbonaceous denitrification and amino denitrification could be coupling and work together. Further research on carbonaceous denitration in cement kilns could focus on the following aspects: evaluating the denitration characteristics under more comprehensive and systematic conditions, clarifying the denitration mechanism by combining experimental and theoretical investigation, and developing the combined technology of carbonaceous denitrification and amino denitrification.

Key words: cement kiln, denitration, coke, carbon monoxide, catalysis, calcium oxide, fly ash

摘要：

随着水泥行业“超低排放”的推进，NO _x 排放要求逐步向100mg/m³甚至50mg/m³看齐。水泥窑碳基脱硝通过控制煤粉燃烧产生焦炭和CO还原NO _x，具有无须添加脱硝剂、避免氨逃逸、与生产流程结合良好、改造和运行成本低的优势，可作为水泥行业实现“超低排放”的辅助工艺。本文首先介绍了碳基脱硝的主要实施方式，包括回转窑低氮燃烧、分解炉分级燃烧和增设还原区等。然后讨论了焦炭和CO还原NO _x 的特性和机制。焦炭还原效果与其比表面积和活性位点有关。CO还原反应可在无催化条件下发生，但CO体积分数小于1%时效果可以忽略。焦炭、CaO和煤灰等可作为催化剂，将CO还原NO的温度窗口下限从900℃降低至600~800℃。最后综述了CO对选择性非催化法（SNCR）的影响及其机制，认为碳基脱硝与氨基脱硝具有耦合协同潜质。水泥窑碳基脱硝的进一步研究可以关注以下方面：在更为全面和系统的工况下评价脱硝特性，试验和理论结合明确脱硝机制，开发碳基与氨基协同脱硝技术等。

关键词: 水泥窑, 脱硝, 焦炭, 一氧化碳, 催化, 氧化钙, 飞灰

CLC Number:

TQ172

LI Dongze, ZHANG Xiang, TIAN Jian, HU Pan, YAO Jie, ZHU Lin, BU Changsheng, WANG Xinye. Research progress of NO _x reduction by carbonaceous substances for denitration in cement kiln[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4882-4893.

李东泽, 张祥, 田键, 胡攀, 姚杰, 朱林, 卜昌盛, 王昕晔. 基于水泥窑脱硝的碳基还原NO _x 研究进展[J]. 化工进展, 2023, 42(9): 4882-4893.

Figures/Tables 9

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实施范围	氮氧化物（以NO₂计）	氨^①	现有企业执行时间	新建企业执行时间	标准号	备注
全国	400	10	2015年07月01日起	2014年03月01日起	GB 4915—2013^[13]
重点地区	320	8	依地区制定^②	依地区制定^②	GB 4915—2013^[13]
安徽省	100	8	2020年10月01日起	2020年03月14日起	DB 34/3576—2020^[14]
江苏省	100	8	2022年07月01日起		DB 32/4149—2021^[15]	阶段Ⅰ
江苏省	50	8	2024年01月01日起	2022年07月01日起	DB 32/4149—2021^[15]	阶段Ⅱ
河南省	100	8	2021年01月01日起	2020年06月01日起	DB 41/1953—2020^[16]
河南省	50	8	分阶段分环节^③	分阶段分环节^③	征求意见稿^[17]	超低排放标准
河北省	100	8	2021年10月01日起	2020年03月04日起	DB 13/2167—2020^[18]	超低排放标准
宁夏回族自治区	100	8	2022年底前实现	2022年底前实现	电子通告^[19]	超低排放标准
浙江省	100		2020年12月15日起^④	2020年12月15日起^④	改造实施方案^[20]	超低排放标准
浙江省	50		2025年6月底前	2025年6月前	改造实施方案^[20]	超低排放标准
山西省	50	5	分阶段分地区^⑤	分阶段分地区^⑤	改造实施方案^[21]	超低排放标准

实施范围	氮氧化物（以NO₂计）	氨^①	现有企业执行时间	新建企业执行时间	标准号	备注
全国	400	10	2015年07月01日起	2014年03月01日起	GB 4915—2013^[13]
重点地区	320	8	依地区制定^②	依地区制定^②	GB 4915—2013^[13]
安徽省	100	8	2020年10月01日起	2020年03月14日起	DB 34/3576—2020^[14]
江苏省	100	8	2022年07月01日起		DB 32/4149—2021^[15]	阶段Ⅰ
江苏省	50	8	2024年01月01日起	2022年07月01日起	DB 32/4149—2021^[15]	阶段Ⅱ
河南省	100	8	2021年01月01日起	2020年06月01日起	DB 41/1953—2020^[16]
河南省	50	8	分阶段分环节^③	分阶段分环节^③	征求意见稿^[17]	超低排放标准
河北省	100	8	2021年10月01日起	2020年03月04日起	DB 13/2167—2020^[18]	超低排放标准
宁夏回族自治区	100	8	2022年底前实现	2022年底前实现	电子通告^[19]	超低排放标准
浙江省	100		2020年12月15日起^④	2020年12月15日起^④	改造实施方案^[20]	超低排放标准
浙江省	50		2025年6月底前	2025年6月前	改造实施方案^[20]	超低排放标准
山西省	50	5	分阶段分地区^⑤	分阶段分地区^⑤	改造实施方案^[21]	超低排放标准

反应温度/℃	NO体积分数/%	CO体积分数/%	H₂O体积分数/%	CO₂体积分数/%	停留时间	NO还原率/%	参考文献
950	0.03	0.5	0	0	13~16ms	0	李竞岌等^[48]
975	0.05	0.2	0	0	<55s	0	付梦龙等^[49]
900	0.1	4	2	15	<3s	55	杨建蒙等^[50]
900	0.1	4	2	25	1.42s	29	孙立超^[24]
900	0.1	1	2	15	1.42s	0	李森等^[51]
900	0.1	4	2	15	1.42s	29	李森等^[51]
900	0.1	5	2	15	1.42s	38	李森等^[51]

反应温度/℃	NO体积分数/%	CO体积分数/%	H₂O体积分数/%	CO₂体积分数/%	停留时间	NO还原率/%	参考文献
950	0.03	0.5	0	0	13~16ms	0	李竞岌等^[48]
975	0.05	0.2	0	0	<55s	0	付梦龙等^[49]
900	0.1	4	2	15	<3s	55	杨建蒙等^[50]
900	0.1	4	2	25	1.42s	29	孙立超^[24]
900	0.1	1	2	15	1.42s	0	李森等^[51]
900	0.1	4	2	15	1.42s	29	李森等^[51]
900	0.1	5	2	15	1.42s	38	李森等^[51]

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