Absorption of NO<sub>2</sub> by magnesium sulfite and ions distribution in liquid phase

doi:10.3785/j.issn.1008-973X.2020.10.015

Journal of ZheJiang University (Engineering Science)

2020, Vol. 54

Issue (10): 1978-1985 DOI: 10.3785/j.issn.1008-973X.2020.10.015

Absorption of NO₂ by magnesium sulfite and ions distribution in liquid phase

Meng-di ZHANG1(

),Meng-yue YING1,Yue LIU1,*(

),Zhong-biao WU1,2

1. College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058, China
2. Zhejiang Provincial Engineering Research Center of Industrial Boiler and Furnace Flue Gas Pollution Control, Hangzhou 310058, China

Download:

HTML

PDF(1657KB) HTML
Export: BibTeX | EndNote (RIS)

Abstract

Magnesium sulfite was employed as simulated magnesia wet flue gas desulfurization (WFGD) slurry for NO₂ absorption. The NO₂ absorption efficiency and the distributions of aqueous ions in the absorption solution under different operating conditions were analyzed. The experimental results show that the presence of oxygen greatly influences on NO₂ absorption. The absorption of NO₂ mainly occur via a series of chain reactions with SO₃^2?, finally generating SO₄^2? and NO₂^?. Oxygen can competitively consume SO₃^2?, resulting in a great decrease in NO₂ absorption efficiency. The addition of catechol can retard the consumption of SO₃^2? by O₂ so that NO₂ absorption efficiency can maintain, and this effect is enhanced with an increase of content. The pH value affects the absorption reaction through the existing form of S (IV). The denitrification efficiency reduces under acidic conditions, and increased NO₃^? content can be observed owing to the disproportionation of NO₂^?. The accumulation of nitrite ions can slightly inhibit the absorption of NO₂, while other anions such as NO₃^?, SO₄^2? and Cl^? have no significant effects. Some metal cations like Mn²⁺ and Co²⁺ can accelerate the oxidation rate of SO₃^2?, which affect the absorption of NO₂ to some extent.

Key words： magnesium sulfite nitrogen dioxide aqueous absorption ions distribution chain reaction

Received: 02 September 2019 Published: 28 October 2020

CLC:

X 701

Corresponding Authors: Yue LIU E-mail: zhangmd@zju.edu.cn;yueliu@zju.edu.cn

	Service
	E-mail this article
	Add to my bookshelf
	Add to citation manager
	E-mail Alert
	RSS
	Articles by authors
	Meng-di ZHANG
	Meng-yue YING
	Yue LIU
	Zhong-biao WU

Cite this article:

Meng-di ZHANG,Meng-yue YING,Yue LIU,Zhong-biao WU. Absorption of NO₂ by magnesium sulfite and ions distribution in liquid phase. Journal of ZheJiang University (Engineering Science), 2020, 54(10): 1978-1985.

URL:

http://www.zjujournals.com/eng/10.3785/j.issn.1008-973X.2020.10.015 OR http://www.zjujournals.com/eng/Y2020/V54/I10/1978

亚硫酸镁对NO₂的液相吸收及产物离子分布

以亚硫酸镁模拟氧化镁湿法脱硫浆液对NO₂进行吸收，考察不同操作条件下的NO₂吸收效率及吸收液中主要离子的分布情况. 结果表明，O₂对吸收过程的影响很大，NO₂主要通过与SO₃^2?之间发生的链式反应在液相中产生SO₄^2?和NO₂^?，O₂会与NO₂发生竞争作用，极大地消耗了SO₃^2?，导致脱硝效率迅速下降. 抗氧化剂邻苯二酚的添加可以抑制SO₃^2?的氧化，且添加的浓度越高，抑制效果越好. 溶液的pH值主要通过影响S（IV）的存在形态来影响吸收反应，当pH值较低时，吸收反应的速率降低，且在酸性条件下，NO₂^?易发生歧化反应转化为NO₃^?. NO₂^?的累积将会在一定程度上降低NO₂的吸收，其他阴离子NO₃^?、SO₄^2?及Cl^?对NO₂的吸收无明显影响. 金属阳离子例如Mn²⁺及Co²⁺会加速SO₃^2?的氧化，在一定程度上影响NO₂的吸收.

关键词： 亚硫酸镁, 二氧化氮, 液相吸收, 离子分布, 链式反应

Fig.1 Schematic diagram of experimental setup for NO₂ absorption

Fig.2 Effect of O₂ on NO₂ absorption efficiency and pH

Fig.3 Effect of O₂ on ions distribution

Fig.4 Effect of initial pH on NO₂ absorption efficiency and pH value variation

Fig.5 Effect of initial pH on ions distribution

Fig.6 Effect of pH on NO₂ absorption rate

Fig.7 Effect of catechol concentration on NO₂ absorption efficiency and pH

Fig.8 Effect of catechol concentration on ions distribution

Fig.9 Effect of different anions on NO₂ absorption efficiency and pH

Fig.10 Effect of NO₂^– on ions distribution

Fig.11 Effect of metal cations on NO₂ absorption efficiency and pH

Fig.12 Effect of metal cations on ions distribution


[1]	PIERRET M C, VIVILLE D, DAMBRINE E, et al Twenty-five year record of chemicals in open field precipitation and throughfall from a medium-altitude forest catchment (Strengbach - NE France): an obvious response to atmospheric pollution trends[J]. Atmospheric Environment, 2019, 202: 296- 314 doi: 10.1016/j.atmosenv.2018.12.026

[2]	HE H, WANG Y S, MA Q X, et al Mineral dust and NOx promote the conversion of SO2 to sulfate in heavy pollution days [J]. Scientific Reports, 2014, 4: 4172

[3]	WANG X Q, LIU Y, WU Z B Highly active NbOPO4 supported Cu-Ce catalyst for NH3-SCR reaction with superior sulfur resistance [J]. Chemical Engineering Journal, 2019, 382: 122941

[4]	MENG Z H, WANG C Y, WANG X R, et al Simultaneous removal of SO2 and NOx from flue gas using (NH4)2S2O3/steel slag slurry combined with ozone oxidation [J]. Fuel, 2019, 255: 115760 doi: 10.1016/j.fuel.2019.115760

[5]	LI G, WANG B D, XU W Q, et al Simultaneous removal of SO2 and NOx from flue gas by wet scrubbing using a urea solution [J]. Environmental Technology, 2019, 40 (20): 2620- 2632 doi: 10.1080/09593330.2018.1454513

[6]	JIA Y, DU D Q, ZHANG X X, et al Simultaneous removal of SO2 and NOX with ammonia absorbent in a packed column [J]. Korean Journal of Chemical Engineering, 2013, 30 (9): 1735- 1740 doi: 10.1007/s11814-013-0091-y

[7]	SKALSKA K, MILLER J S, LEDAKOWICZ S Trends in NOx abatement: a review [J]. Science of the Total Environment, 2010, 408 (19): 3976- 3989 doi: 10.1016/j.scitotenv.2010.06.001

[8]	[J]. 2014, 274: 376- 383

[9]	LI F B, LI X Z, AO C H, et al Photocatalytic conversion of NO using TiO2–NH3 catalysts in ambient air environment [J]. Applied Catalysis B: Environmental, 2004, 54 (4): 275- 283 doi: 10.1016/j.apcatb.2004.09.006

[10]	TANG N, LIU Y, WANG H Q, et al Mechanism study of NO catalytic oxidation over MnOx/TiO2 catalysts [J]. The Journal of Physical Chemistry C, 2011, 115 (16): 8214- 8220 doi: 10.1021/jp200920z

[11]	WU C Y, CHOU M S Reduction of nitrogen dioxide from etching vent gases by scrubbing with caustic sodium sulfide solution[J]. Journal of Chemical Technology and Biotechnology, 2014, 89 (12): 1850- 1858 doi: 10.1002/jctb.4266

[12]	SUN Y, HONG X W, ZHU T L, et al The chemical behaviors of nitrogen dioxide absorption in sulfite solution[J]. Applied Sciences, 2017, 7 (4): 377 doi: 10.3390/app7040377

[13]	KORALEGEDARA N H, PINTO P X, DIONSIOU D D, et al Recent advances in flue gas desulfurization gypsum processes and applications: a review[J]. Journal of Environmental Management, 2019, 251: 109572 doi: 10.1016/j.jenvman.2019.109572

[14]	TANG N, LIU Y, WANG H Q, et al Enhanced absorption process of NO2 in CaSO3 slurry by the addition of MgSO4[J]. Chemical Engineering Journal, 2010, 160 (1): 145- 149 doi: 10.1016/j.cej.2010.03.022

[15]	WANG Z H, ZHANG X, ZHOU Z J, et al Effect of additive agents on the simultaneous absorption of NO2 and SO2 in the calcium sulfite slurry [J]. Energy and Fuels, 2012, 26 (9): 5583- 5589 doi: 10.1021/ef3007504

[16]	SUN Y, MENG Y, GUO X Y, et al Study of nitrogen oxide absorption in the calcium sulfite slurry[J]. Journal of Material Cycles and Waste Management, 2016, 18 (4): 618- 624 doi: 10.1007/s10163-016-0526-8

[17]	唐念. Mn/TiO2催化氧化NO联合CaSO3浆液吸收的烟气脱硝新工艺研究[D]. 杭州: 浙江大学, 2011: 72-75. TANG Nian. New combined process for flue gas denitrification: NO catalytic oxidation over Mn/TiO2 catalysts and absorption with CaSO3 slurry [D]. Hangzhou: Zhejiang University, 2011: 72-75.

[18]	PASIUK B W, BRONIKOWSKI T, ULEJCZYK M Mechanism and kinetics of autoxidation of calcium sulfite slurries[J]. Environmental Science and Technology, 1992, 26 (10): 1976- 1981 doi: 10.1021/es00034a015

[19]	WU B B, TIAN H Z, HAO Y, et al Effects of wet flue gas desulfurization and wet electrostatic precipitators on emission characteristics of particulate matter and its ionic compositions from four 300 MW level ultralow coal-fired power plants[J]. Environmental Science and Technology, 2018, 52 (23): 14015- 14026 doi: 10.1021/acs.est.8b03656

[20]	CRONKRIGHT W A, LEDDY W J Improving mass transfer characteristics of limestone slurries by use of magnesium sulfate[J]. Environmental Science and Technology, 1976, 10 (6): 569- 572 doi: 10.1021/es60117a003

[21]	俎玉筠工业废水中亚硝酸盐的处理[J]. 工业水处理, 1990, 10 (4): 32- 33 ZU Yu-yun Treatment of nitrite in industrial wastewater[J]. Industrial Water Treatment, 1990, 10 (4): 32- 33

[22]	REZAEI H, JAFARI A, KAMAREHIE B, et al Health-risk assessment related to the fluoride, nitrate, and nitrite in the drinking water in the Sanandaj, Kurdistan County, Iran[J]. Human and Ecological Risk Assessment, 2019, 25 (5): 1242- 1250 doi: 10.1080/10807039.2018.1463510

[23]	LITTLEJIHN D, WANG Y Z, CHANG S G Oxidation of aqueous sulfite ion by nitrogen dioxide[J]. Environmental Science and Technology, 1993, 27 (10): 2162- 2167 doi: 10.1021/es00047a024

[24]	汪黎东. 烟气脱硫添加剂对正盐生成促进的实验研究[D]. 保定: 华北电力大学(保定), 2005: 36-37. WANG Li-dong. Experimental studies on accelerating effect of flue gas desulfurization additives for formation of sulfate [D]. Baoding: North China Electric Power University, 2005: 36-37.

[25]	张相. 臭氧结合钙基吸收多种污染物及副产物提纯的试验与机理研究[D]. 杭州: 浙江大学, 2012: 57-58. ZHANG Xiang. Experimental and mechanism investigation on multi-pollutant absorption by ozone with calcium based scrubbing and by-product treatment [D]. Hangzhou: Zhejiang University, 2012: 57-58.

[26]	郭东明. 脱硫工程技术与设备[M]. 北京: 化学工业出版社, 2012: 29-30.

[27]	HUIE R E, NETA P Rate constants for some oxidations of S(IV) by radicals in aqueous solutions[J]. Atmospheric Environment (1967), 1987, 21 (8): 1743- 1747 doi: 10.1016/0004-6981(87)90113-2

[28]	WANG L D, ZHAO Y Kinetics of sulfite oxidation in wet desulfurization with catalyst of organic acid[J]. Chemical Engineering Journal, 2008, 136 (2/3): 221- 226

[29]	CLIFTON C, ALTSTEIN N, HUIE R Rate constant for the reaction of nitrogen dioxide with sulfur(IV) over the pH range 5.3-13[J]. Environmental Science and Technology, 1988, 22 (5): 586- 589 doi: 10.1021/es00170a018

[30]	SHEN C H, ROCHELLE G T Nitrogen dioxide absorption and sulfite oxidation in aqueous sulfite[J]. Environmental Science and Technology, 1998, 32 (13): 1994- 2003 doi: 10.1021/es970466q

[31]	WU Q, SUN C L, WANG H Q, et al The role and mechanism of triethanolamine in simultaneous absorption of NOx and SO2 by magnesia slurry combined with ozone gas-phase oxidation [J]. Chemical Engineering Journal, 2018, 341: 157- 163 doi: 10.1016/j.cej.2018.01.150

[32]	汪黎东, 赵毅, 马永亮, 等苯酚抑制条件下亚硫酸盐氧化的本征反应动力学[J]. 化学学报, 2008, 66 (21): 2336- 2340 WANG Li-dong, ZHAO Yi, MA Yong-liang, et al Intrinsic kinetics of sulfite oxidation with inhibitor of phenol[J]. Acta Chimica Sinica, 2008, 66 (21): 2336- 2340 doi: 10.3321/j.issn:0567-7351.2008.21.004

[33]	魏刚, 熊蓉春, 张小冬某些物质对亚硫酸盐氧化的阻滞作用[J]. 水处理技术, 1999, 25 (5): 277- 280 WEI Gang, XIONG Rong-chun, ZHANG Xiao-dong Inhibition of some materials on sulfite oxidation[J]. Technology of Water Treatment, 1999, 25 (5): 277- 280 doi: 10.3969/j.issn.1000-3770.1999.05.007

[34]	王秉, 胡智文, 郑海玲, 等 β-环糊精-Cu(Ⅱ)配合物催化氧化邻苯二酚及其反应动力学[J]. 化工学报, 2009, 60 (6): 1459- 1465 WANG Bing, HU Zhi-wen, ZHENG Hai-ling, et al Oxidation of catechol catalyzed by β-cyclodextrin-Cu(II) complexes and its reaction kinetics[J]. Journal of Chemical Industry and Engineering(China), 2009, 60 (6): 1459- 1465 doi: 10.3321/j.issn:0438-1157.2009.06.019

[1]	XU Xi, XU Dian, YAN Pei, ZHU Wei-zhuo, ZHENG Cheng-hang, GAO Xiang, LUO Zhong-yang, NI Ming-jiang, CEN Ke-fa. Particle collection in wire-plate electrostatic precipitators at high temperature[J]. Journal of ZheJiang University (Engineering Science), 2017, 51(3): 487-493.

[2]	YU Jin pin, QIU Kun zan, SONG Hao, GAO Xiang, ZHOU Jin song. Catalytic oxidation experiment of element mercury over Cr/TiO2 catalyst[J]. Journal of ZheJiang University (Engineering Science), 2015, 49(11): 2186-2192.

[3]	LIN Fa-wei, ZHU Yan-qun, XU Chao-qun, MA Qiang, WANG Zhi-hua, ZHOU Jun-hu, CEN Ke-fa. Experimental study on residual ozone decomposition in process of multi-pollutants removal by ozone[J]. Journal of ZheJiang University (Engineering Science), 2015, 49(7): 1249-1254.

[4]	WAN Yi, HUANG Wei-wei, ZHENG Cheng-hang, GAO Xiang, CEN Ke-fa. Spray characteristics of wet electrostatic precipitator[J]. Journal of ZheJiang University (Engineering Science), 2015, 49(2): 336-343.

[5]	WANG Hui-ting, DING Hong-lei, YAO Guo-xin, ZHANG Yong-xin,. Experimental study on SO2 absorption rate enhanced by additive in limestone-gypsum WFGD process[J]. Journal of ZheJiang University (Engineering Science), 2014, 48(1): 50-55.

[6]	MAO Jian-hong,JIANG Xin-wei,ZHONG Yi,SONG Hao,WU Wei-hong,PAN Shu-ping,GAO Xiang. The effect of splitters layout at variable cross-section inclined flue on AIG inlet flow field[J]. Journal of ZheJiang University (Engineering Science), 2011, 45(8): 1453-1457.

[7]	MAO Jian-hong,SONG Hao,WU Wei-hong,ZHONG Yi,GAO Xiang,LUO Zhong-yang,CEN Ke-fa. Design and optimization of splitters in SCR system for coal fired boiler[J]. Journal of ZheJiang University (Engineering Science), 2011, 45(6): 1124-1129.

[8]	YANG Jian-tao, PAN Hua, CHEN Jie, SU Qing-fa, WANG Da-hui, SHI Yao. Two-stage system of non-thermal plasma and adsorption for decomposition of hydrogen sulfide[J]. Journal of ZheJiang University (Engineering Science), 2010, 44(12): 2411-2415.

Viewed

Full text

Abstract

Cited

Shared

Discussed