甲胺作还原剂的选择性非催化还原脱硝特性的实验研究

doi:10.11949/j.issn.0438-1157.20171687

化工学报 ›› 2018, Vol. 69 ›› Issue (7): 3234-3241.DOI: 10.11949/j.issn.0438-1157.20171687

甲胺作还原剂的选择性非催化还原脱硝特性的实验研究

蒲舸¹, 杜建太¹, 张章², 张定海², 吴棒¹, 黄蓓蓓¹, 朱团辉¹

1 重庆大学低品位能源利用技术及系统教育部重点实验室, 重庆 400044;
2 东方电气集团东方锅炉股份有限公司, 四川成都 611731

收稿日期:2017-12-27 修回日期:2018-03-13 出版日期:2018-07-05 发布日期:2018-07-05
通讯作者: 蒲舸
基金资助:
重庆市重点产业共性关键技术创新专项（STC2016zdcyztzx20001）。

Experimental study of selective non-catalytic reduction process with methylamine as reducing agent

PU Ge¹, DU Jiantai¹, ZHANG Zhang², ZHANG Dinghai², WU Bang¹, HUANG Beibei¹, ZHU Tuanhui¹

1 Key Laboratory of Low-grade Energy Utilization Technologies and Systems, Chongqing University, Chongqing 400044, China;
2 Dongfang Boiler Group Co. Ltd., Dongfang Electric Group, Chengdu 611731, Sichuan, China

Received:2017-12-27 Revised:2018-03-13 Online:2018-07-05 Published:2018-07-05
Supported by:
supported by the Chongqing Special Key Technology of Industrial Generic Innovation Project (STC2016zdcy-ztzx 20001).

摘要/Abstract

摘要：

为改善工业窑炉以及锅炉低负荷运行工况下的脱硝特性，本文对甲胺作还原剂的选择性非催化还原（SNCR）脱硝特性进行了实验研究，探讨了各控制因素对脱硝特性的影响以及分析了反应机理。实验结果表明：脱硝效率随反应温度呈双峰特性，拐点温度为750℃，最佳温度窗口为450～600℃；脱硝效率随氨氮比（NSR）增大而升高，反应产生的副产物NO₂和N₂O浓度随之增大；氧含量对SNCR脱硝特性具有双重特性，高浓度和低浓度氧气均对脱硝反应不利；物料浓度随NO初始浓度增加而增大，脱硝效率和副产物也提高； SO₂浓度越高，脱硝效率下降越多；水汽含量增大，脱硝效率也随之增大。本文的实验结论有助于SNCR脱硝工艺应用于工业窑炉以及优化锅炉低负荷运行时的脱硝特性。

关键词: 甲胺, 脱硝, 选择性非催化还原, 氮氧化物, 控制因素

Abstract:

Selective non-catalytic reduction (SNCR) denitration efficiency is lower than the minimum designed requirement when the boiler is operating under low load. To improve the characteristics of such working conditions, the feature of selective non-catalytic reduction denitration with methylamine as reductants is studied and the reaction mechanism is analyzed in the tube furnace reaction system. The effect of oxygen content, NSR, initial concentration of NO, SO₂ and water content on the denitrification properties of methylamine SNCR is discussed. The results show that:the relationship between denitration efficiency and temperature is bimodal, the inflection point temperature is 750℃, and the best temperature window for practical industrial application is 450-600℃. The NO reduction efficiency was increased with the increase of NSR, and the concentration of NO₂ and N₂O was also augmented. The maximum NO removal efficiency was 85.0%. The oxygen content has dual characteristics to SNCR denitrification reaction, the efficiency of NO reduction is the greatest under the condition of 3% oxygen content. The increase of the initial concentration of NO makes the material concentration of the simulated flue gas increase, the NO reduction efficiency and the by-product increase. The higher concentration of SO₂, the greater the reduction of NO reduction efficiency. The increase of water content was beneficial to the denitrification reaction. The experimental conclusion of methylamine SNCR denitrification in this paper is helpful to the application of selective non-catalytic reduction process with methylamine as reducing agent to industrial furnace and to optimize the denitrification characteristics of the boiler at low load operation.

Key words: methylamine, NO reduction, SNCR, nitrogen oxide, control factors

中图分类号:

蒲舸, 杜建太, 张章, 张定海, 吴棒, 黄蓓蓓, 朱团辉. 甲胺作还原剂的选择性非催化还原脱硝特性的实验研究[J]. 化工学报, 2018, 69(7): 3234-3241.

PU Ge, DU Jiantai, ZHANG Zhang, ZHANG Dinghai, WU Bang, HUANG Beibei, ZHU Tuanhui. Experimental study of selective non-catalytic reduction process with methylamine as reducing agent[J]. CIESC Journal, 2018, 69(7): 3234-3241.

参考文献 30

[1]	周昊, 张志中, 鲍强, 等. 添加剂对NOxOUT脱硝及N2O、CO生成的影响特性[J]. 化工学报, 2014, 65(6):2232-2240. ZHOU H, ZHANG Z Z, BAO Q, et al. Influence of additives on NO xOUT denitration and formation of N2O and CO[J]. CIESC Journal, 2014, 65(6):2232-2240.
[2]	第一次全国污染源普查资料编纂委员会. 污染源普查技术报告[M]. 北京:中国环境科学出版社, 2011:125. The Information Compilation Committee of the First National Pollution Census. Pollution Source Census Technical Report[M]. Beijing:China Environmental Science Press, 2011:125.
[3]	卢志民. SNCR反应机理及混合特性研究[D]. 杭州:浙江大学, 2006. LU Z M. Study on reaction mechanism and mixing characteristics of SNCR technique[D]. Hangzhou:Zhejiang University, 2006.
[4]	段传和. 选择性非催化还原法(SNCR)烟气脱硝[M]. 北京:中国电力出版社, 2012:6-12. DUAN C H. Selective Non-Catalytic Reduction (SNCR) of NOx in Flue Gas[M]. Beijing:China Electric Power Press, 2012:6-12.
[5]	沈文锋, 向柏祥, 张海, 等. 煤粉炉SNCR对SO3生成影响的数值模拟[J]. 化工学报, 2017, 68(8):3225-3231. SHEN W F, XIANG B X, ZHANG H, et al. Numerical simulation on formation of SO3 during SNCR process in pulverized coal-fired boiler[J]. CIESC Journal, 2017, 68(8):3225-3231.
[6]	赵玉. 长三角地区钢铁行业烟气污染控制技术评价研究[D]. 杭州:浙江大学, 2017. ZHAO Y. Study on the evaluation of air pollution control technologies for steel industries in Yangtze River Delta[D]. Hangzhou:Zhejiang University, 2017.
[7]	李穹, 吴玉新, 杨海瑞, 等. SNCR脱硝特性的模拟及优化[J]. 化工学报, 2013, 64(5):1789-1796. LI Q, WU Y X, YANG H R, et al. Simulation and optimization of SNCR process[J]. CIESC Journal, 2013, 64(5):1789-1796.
[8]	YAO T, DUAN Y, YANG Z, et al. Experimental characterization of enhanced SNCR process with carbonaceous gas additives[J]. Chemosphere, 2017, 177:149-156.
[9]	顾颜. 煤粉炉SNCR脱硝过程的数值模拟研究[D]. 北京:华北电力大学, 2015. GU Y. Numerical simulation of SNCR process about pulverized coal fired boiler[D]. Beijing:North China Electric Power University, 2015.
[10]	KAMBARA S, HAYAKAWA Y, MASUI M, et al. Removal of nitric oxide by activated ammonia generated by vacuum ultraviolet radiation[J]. Fuel, 2012, 94(1):274-279.
[11]	王鲁元, 程星星, 张兴宇, 等. CeO2纳米棒负载Co催化CO脱除NOx的机理[J]. 化工学报, 2016, 67(s1):260-269. WANG L Y, CHENG X X, ZHANG X Y, et al. Mechanism of nitric oxides reduction by carbon monoxide over cobalt oxides supported by CeO2 nanorod[J]. CIESC Journal, 2016, 67(s1):260-269.
[12]	CHEN H, CHEN D Z, FAN S, et al. SNCR De-NOx within a moderate temperature range using urea-spiked hydrazine hydrate as reductant[J]. Chemosphere, 2016, 161:208-218.
[13]	陈慧, 陈德珍, 王娜. 中温条件下烟气De-NOx技术的研究现状与发展[J]. 中国电机工程学报, 2013, 20:17-27. CHEN H, CHEN D Z, WANG N. The state-of-art and development of moderate-temperature-based flue gas De-NOx technology[J]. Proceedings of the CSEE, 2013, 20:17-27.
[14]	CULLIS C F, WILLSHER J P. The thermal oxidation of methylamine[J]. Proc. R. Soc. London, 1951, 209(1097):218-238.
[15]	EMELÉUS H J, JOLLEY L J. Kinetics of the thermal decomposition of methylamine[J]. J. Am. Chem. Soc., 1935, 2:929-935.
[16]	YOSHIHARA Y, TANAKA T. Reduction of oxides of nitrogen in diesel exhaust with addition of methylamine[J]. Trans. Japan Soc. Mech. Eng., Series B, 1995, 61(582):766-771.
[17]	NAKANISHI Y, YOSHIHARA Y, NISHIWAKI K, et al. Reduction of nitric oxide in diesel exhaust with the addition of methylamine[J]. J. Eng. Gas Turb. Power, 1999, 121(3):563-568.
[18]	DUO W, DAM-JOHANSEN K, ØSTERGAARD K. Widening the temperature range of the thermal De-NOx process. An experimental investigation[J]. Symposium on Combustion, 1991, 23(1):297-303.
[19]	杨杰. 车用柴油机NOx净化过程(SCR、SNCR)的数值模拟[D]. 济南:山东建筑大学, 2010. YANG J. Numerical simulation of exhaust after treatment system(ureaSCR and SNCR) of diesel[D]. Jinan:Shandong Jianzhu University, 2010.
[20]	田海影. 柴油机尾气NOx的净化技术研究[D]. 济南:山东建筑大学, 2011. TIAN H Y. Research on the technology of removing NOx from diesel engine[D]. Jinan:Shandong Jianzhu University, 2011.
[21]	DORKO E A, PCHELKIN N R, WERT J C, et al. Initial shock tube studies of monomethylamine[J]. J. Phys. Chem., 2002, 83(2):297-302.
[22]	KANTAK M V, MANRIQUE K S D, AGLAVE R H, et al. Methylamine oxidation in a flow reactor:mechanism and modeling[J]. Combust. Flame, 1997, 108(3):235-265.
[23]	HJULER K, GLARBORG P, DAMJOHANSEN K. Mutually promoted thermal oxidation of nitric oxide and organic compounds[J]. Ind. Eng. Chem. Res., 1995, 34(5):5802-5806.
[24]	QIN Y. Chemical kinetics analysis of alternative reagents for the SNCR process[D]. Bethlehem:Lehigh University, 2014.
[25]	HWANG S M, HIGASHIHARA T, GARDINER W C, et al. Shock tube and modeling study of monomethylamine oxidation[J]. J. Phys. Chem. A, 1990, 7(7):2883-2889.
[26]	孙桐, 卢平, 蔡杰, 等. Na/K添加剂对SNCR脱硝及NO还原机制的影响[J]. 化工学报, 2017, 68(3):1178-1184. SUN T, LU P, CAI J, et al. Effects of Na/K additives on NO reduction and its promotion mechanism in SNCR process[J]. CIESC Journal, 2017, 68(3):1178-1184.
[27]	KANG Z, YUAN Q, ZHAO L, et al. Study of the performance, simplification and characteristics of SNCR De-NOx in large-scale cyclone separator[J]. Appl. Therm. Eng., 2017, 123:635-645.
[28]	FU S L, QIANG S, QIANG Y. Mechanism study on the adsorption and reactions of NH3, NO, and O2, on the CaO surface in the SNCR DeNO x process[J]. Chem. Eng. J., 2016, 285:137-143.
[29]	KLIPPENSTEIN S J, HARDING L B, GLARBORG P, et al. The role of NNH in NO formation and control[J]. Combust. Flame, 2011, 158(4):774-789.
[30]	FAN W, ZHU T, SUN Y, et al. Effects of gas compositions on NOx reduction by selective non-catalytic reduction with ammonia in a simulated cement precalciner atmosphere[J]. Chemosphere, 2014, 113:182-187.

甲胺作还原剂的选择性非催化还原脱硝特性的实验研究

Experimental study of selective non-catalytic reduction process with methylamine as reducing agent

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[2]	张媛媛, 曲江源, 苏欣欣, 杨静, 张锴. 循环流化床燃煤机组SNCR脱硝过程气液传质和反应特性[J]. 化工学报, 2023, 74(6): 2404-2415.
[3]	刘坤, 尹远, 耿文强, 夏昊天. 不同操作参数下介质阻挡放电的固氮性能研究及机理分析[J]. 化工学报, 2022, 73(9): 4045-4053.
[4]	王佳怡, 范垂钢, 李松庚. 碳氧官能团对煤焦低温还原NO的影响[J]. 化工学报, 2022, 73(5): 2140-2148.
[5]	张逸伟, 唐海荣, 何勇, 朱燕群, 王智化. 臭氧低温氧化烟气脱硝过程中的氮平衡试验研究[J]. 化工学报, 2022, 73(4): 1732-1742.
[6]	韩维辰, 王佳铭, 贺曼罗, 贺高红, 焉晓明, 阮雪华. 潜伏型环氧固化剂甲基异丁基酮二亚胺的合成及工艺优化[J]. 化工学报, 2021, 72(7): 3832-3838.
[7]	杨林, 孟小谜, 姚露, 赖雨果, 蒋文举. 天然矿物共混活性焦联合低温脱硫脱硝[J]. 化工学报, 2021, 72(4): 2241-2248.
[8]	游洋, 刘应书, 杨雄, 吴晓永, 赵春雨, 王正, 侯环宇, 李子宜. 面向烟气NO_x净化与回收的新型吸附工艺[J]. 化工学报, 2021, 72(4): 2132-2138.
[9]	卿梦霞, 张鑫, 刘亮, 张巍, 王乐乐, 苏胜, 孔凡海, 向军. 燃煤烟气脱硝副产物硫酸氢铵/硫酸铵沉积与分解特性研究[J]. 化工学报, 2021, 72(2): 1132-1141.
[10]	张顾平, 王贝贝, 周舟, 陈冬赟, 路建美. 半导体材料在光催化低浓度氮氧化物的研究进展[J]. 化工学报, 2021, 72(1): 259-275.
[11]	周鑫, 邱鸣慧, 罗平. 陶瓷膜接触器化学吸收氮氧化物的传质过程与阻力分析[J]. 化工学报, 2020, 71(8): 3652-3660.
[12]	王晨,陈泽翔,王建强,沈美庆,王军. 基于NH₃-SCR反应铜基小孔分子筛催化剂Na中毒对比研究[J]. 化工学报, 2020, 71(12): 5551-5560.
[13]	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.
[14]	张霄玲,鲍佳宁,李运甲,皇甫林,李文松,高士秋,许光文,李长明,余剑. 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.
[15]	陈潇雪, 宋敏, 孟凡跃, 卫月星. Fe _x MnCe₁-AC低温SCR催化剂SO₂中毒机理研究[J]. 化工学报, 2019, 70(8): 3000-3010.