CIESC Journal ›› 2018, Vol. 69 ›› Issue (7): 3234-3241.doi: 10.11949/j.issn.0438-1157.20171687

Previous Articles     Next Articles

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. 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:2018-04-13
  • Supported by:

    supported by the Chongqing Special Key Technology of Industrial Generic Innovation Project (STC2016zdcy-ztzx 20001).

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

CLC Number: 

  • X51

[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.

[1] SUN Tong, LU Ping, CAI Jie, WU Jiang. Effects of Na/K additives on NO reduction and its promotion mechanism in SNCR process [J]. CIESC Journal, 2017, 68(3): 1178-1184.
[2] WU Xiaolei1,LIU Bo1,REN Zheng2,WANG Yuanhua1,XU Xiangrong3,LI Xucan3. CFD study on combustion properties and NOx emission of reboiling furnace for xylene tower [J]. Chemical Industry and Engineering Progree, 2014, 33(09): 2298-2303.
[3] REN Ruipeng 1,CHEN Hu1,CHEN Jian2,Lü Yongkang1. Study on catalytic oxidations catalysts in removal of NO from flue gas [J]. Chemical Industry and Engineering Progree, 2014, 33(06): 1453-1458.
[4] HUANG Zhenyu,YIN Ke,ZHOU Zhijun,WANG Zhihua,YANG Weijuan,ZHOU Junhu. Experimental investigation on evaporation characteristics of urea-aqueous-solution droplet [J]. Chemical Industry and Engineering Progree, 2014, 33(04): 817-823.
[5] LI Qiong, WU Yuxin, YANG Hairui, LÜ Junfu. Simulation and optimization of SNCR process [J]. CIESC Journal, 2013, (5): 1789-1796.
[6] LI Li1,HUANG Huacun2,WEI Tengyou1,SUN Jianhua1,TONG Zhangfa1. Influence of cerium additive on selective catalytic reduction of NOx with MnOx/ACFN catalyst [J]. Chemical Industry and Engineering Progree, 2013, 32(11): 2655-2660.
[7] GU Weirong,ZHOU Mingji,MA Wei. Technology status and analysis on coal-fired flue gas denitrification [J]. Chemical Industry and Engineering Progree, 2012, 31(09): 2084-2092.
[8] SUN Mojie,JIANG Jiaxu,YU Dayu. Research process in flue gas denitration by denitrifying bacteria [J]. Chemical Industry and Engineering Progree, 2012, 31(06): 1179-1183.
[9] JIANG Jianqing1,PAN Hua2,SUN Guojin1,SHAO Zhenhua1,SHI Yao1. Research advances in selective catalytic reduction of NOx over transition metal-based zeolite catalysts [J]. Chemical Industry and Engineering Progree, 2012, 31(01 ): 98-106.
[10] FAN Xueyou,JIA Yong,ZHONG Qin. Experimental study on ammonia absorption for simultaneous desulfurization and denitrification [J]. Chemical Industry and Engineering Progree, 2012, 31(01 ): 213-216.
[11] BAI Yuan,LI Zhonghua,XUE Jianming,WANG Xiaoming. Experimental study on affecting factors for the performance of denitrification using H2O2 solution in coal-fired flue gas [J]. Chemical Industry and Engineering Progree, 2012, 31(01 ): 208-212.
[12] BAI Yuan,XUE Jianming,LI Zhonghua,WANG Xiaoming. Progress in photocatalytic oxidation of nitrogen oxides from flue gas [J]. , 2010, 29(3): 569-.
[13] LI Yu, LIU Youzhi, ZHANG Luyao, SU Qiang, JIN Guoliang. Absorption of NOx into Nitric Acid Solution in Rotating Packed Bed [J]. , 2010, 18(2): 244-248.
[14] YE Weijun,WEI Zaishan,ZHENG Qizhan. Removal of nitrogen oxides of low concentrations in biofilter packed with activated carbon [J]. , 2008, 27(8): 1265-.
[15] CHU Wenhai,GAO Naiyun,ZHAO Shigu. Advance in analytical techniques of disinfection by-products NDMA in drinking water [J]. , 2008, 27(10): 1512-.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!