次氯酸盐氧化剂同时脱硫脱硝一体化

doi:10.16085/j.issn.1000-6613.2023-1447

摘要/Abstract

摘要：

为了实现冶炼烟气的有效脱硫脱硝，采用两种次氯酸盐——NaClO和Ca(ClO)₂在串联式鼓泡反应器中对模拟冶炼烟气进行了同时去除NO和SO₂的对比性实验。考察了两种氧化剂的浓度、反应器个数、反应温度以及溶液的pH等参数对同时去除NO和SO₂效率的影响。结果表明，当使用次氯酸盐氧化剂时，SO₂均稳定在较好的去除范围内，NO的去除效率随着氧化剂浓度的升高和反应器个数的增加而提高，随着反应温度的升高和溶液pH的增大而减小。两种氧化剂的对比实验表明，相较于NaClO来说，Ca(ClO)₂具有更好的脱硫脱硝效率。在最佳反应条件下，即Ca(ClO)₂浓度为25mmol/L、反应器个数为3、反应温度为25℃、溶液pH为6时，有最佳的同时脱硫脱硝效率，分别为95.4%和88%。此外，还提出了次氯酸盐吸收剂同时脱硫脱硝的反应机理，NO与次氯酸盐氧化剂进行接触反应生成NO₂^-和NO₃^-，SO₂则与之反应生成SO₄^2-，在与Ca(ClO)₂反应时会生成部分CaSO₄沉淀，NO和SO₂在此过程中得以去除。

关键词: 次氯酸钠, 次氯酸钙, 脱硫脱硝, 冶炼烟气, 鼓泡反应器

Abstract:

Comparative experiments on the simultaneous removal of NO and SO₂ from simulated smelting flue gas were carried out using two hypochlorite salts of NaClO and Ca(ClO)₂, respectively, in a tandem bubbling reactor. The effects of operation parameters such as the oxidizing agent concentration, the number of reactors, the reaction temperature, and the pH of the solution on the removal efficiency were investigated. The results showed that, when the hypochlorite oxidant was used, the removal of SO₂ was always good and the removal efficiency of NO increased with the increase of the oxidant concentration and reactor number. With the increase of reaction temperature and solution pH, the removal of NO by hypochlorite oxidant gradually weakened. Comparison results showed that Ca(ClO)₂ has better desulfurization and denitrification efficiency than NaClO. Under the optimal reaction conditions, the best simultaneous desulfurization and denitrification efficiencies of 95.4% and 88%, respectively, were obtained with a Ca(ClO)₂ concentration of 25mmol/L, three reactors in series, reaction temperature of 25℃, and pH=6. In addition, the reaction mechanism of simultaneous desulfurization and denitrification by hypochlorite absorber was also proposed, in which NO was converted into NO₂^- and NO₃^- by contact reaction with hypochlorite oxidizer, and SO₂ was oxidized into SO₄^2-, and CaSO₄ precipitation would be generated in the case of Ca(ClO)₂, so that NO and SO₂ could be removed in the process.

Key words: sodium hypochlorite, calcium hypochlorite, desulfurization and denitrification, smelting flue gas, bubble column reactor

中图分类号:

李一, 梁李斯, 张立兴, 乔江鱼, 崔忠宜, 陈进, 徐强, 赵晨. 次氯酸盐氧化剂同时脱硫脱硝一体化[J]. 化工进展, 2024, 43(9): 5282-5289.

LI Yi, LIANG Lisi, ZHANG Lixing, QIAO Jiangyu, CUI Zhongyi, CHEN Jin, XU Qiang, ZHAO Chen. Simultaneous desulfurization and denitrification with hypochlorite oxidant[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5282-5289.

图/表 6

图1 实验装置1、2、3—N2、NO、SO2气瓶；4—质量流量控制器； 5—混合罐； 6—阀门； 7—鼓泡反应器； 8—水浴加热锅； 9—溶液； 10—烟气分析仪

图2 溶液浓度对脱硫脱硝效率的影响

图3 反应器数量对脱硫脱硝效率的影响

图4 反应温度对脱硫脱硝效率的影响

图5 pH对去除效率的影响

图6 反应后溶液离子色谱图

参考文献 28

1	孙军红. 废气治理及新技术探讨[J]. 皮革制作与环保科技, 2022(3):99-101.
	SUN Junhong. Discussion on waste gas treatment and new technology[J]. Leather Manufacture and Environmental Technology, 2022(3): 99-101.
2	王兴楠. 工业废气治理的方法及对策思考[J]. 中国高新科技, 2022(3): 109-110.
	WANG Xingnan. Methods and countermeasures of industrial waste gas treatment[J]. China High - Tech, 2022(3): 109-110.
3	WANG Qianwen, WANG Leilei, WU Hao, et al. Promoting fine particle removal in double-tower cascade wet flue gas desulfurization system by flue gas temperature reduction[J]. Powder Technology, 2020,373:581-589.
4	CHEN Xiaoyu, SUN Pengxiang, CUI Lin, et al. Limestone-based dual-loop wet flue gas desulfurization under oxygen-enriched combustion[J]. Fuel, 2022, 322: 124161.
5	Guo BIN, TAO Luan. Non-thermal plasma for simultaneous NO _x and SO₂ removal from coal-combustion flue gas[J]. Bulgaeian Chemical Communications, 2016, 48: 166-171.
6	WANG Jiangen, YI Honghong, TANG Xiaolong, et al. Simultaneous removal of SO₂ and NO _x by catalytic adsorption using γ-Al₂O₃ under the irradiation of non-thermal plasma: Competitiveness, kinetic, and equilibrium[J]. Chemical Engineering Journal, 2020, 384: 123334.
7	WANG Liang, LIU Manyi, REN Shan, et al. Recent advance for NO _x removal with carbonaceous material for low-temperature NH₃-SCR reaction[J]. Catalysis Today, 2023, 418: 114053.
8	YOON Hyung Jun, PARK Hyun-Woo, PARK Dong-Wha. Simultaneous oxidation and absorption of NO _x and SO₂ in an integrated O₃ oxidation/wet atomizing system[J]. Energy & Fuels, 2016, 30(4): 3289-3297.
9	ZHAO Junxiong, WEI Qifeng, BI Dongkui, et al. A brand new two-phase wet oxidation absorption system for the simultaneous removal of SO₂ and NO _x from simulated marine exhaust gas[J]. Chemosphere, 2022, 307: 135830.
10	CHIN Terence, Ivan TAM, YIN Chunyang. Wet scrubbing process with oxidation and reduction in series for removal of SO₂ and NO from marine diesel engine exhaust[J]. Chemical Engineering Journal, 2023, 464: 142299.
11	李峰. 氧化吸收法脱硝在瓦斯电站中的应用[J]. 山西化工, 2016, 36(3): 54-58, 63.
	LI Feng. Application of oxidation and absorption method in gas power plant[J]. Shanxi Chemical Industry, 2016, 36(3): 54-58, 63.
12	HAO Runlong, WANG Xiaohui, ZHAO Xu, et al. A novel integrated method of vapor oxidation with dual absorption for simultaneous removal of SO₂ and NO: Feasibility and prospect[J]. Chemical Engineering Journal, 2018, 333: 583-593.
13	HAO Runlong, MAO Yumin, MAO Xingzhou, et al. Cooperative removal of SO₂ and NO by using a method of UV-heat/H₂O₂ oxidation combined with NH₄OH-(NH₄)₂SO₃ dual-area absorption[J]. Chemical Engineering Journal, 2019, 365: 282-290.
14	WANG Jie, ZHONG Wenqi. Simultaneous desulfurization and denitrification of sintering flue gas via composite absorbent[J]. Chinese Journal of Chemical Engineering, 2016, 24(8): 1104-1111.
15	FANG Ping, CEN Chaoping, WANG Xinming, et al. Simultaneous removal of SO₂, NO and Hg⁰ by wet scrubbing using urea + KMnO₄ solution[J]. Fuel Processing Technology, 2013, 106: 645-653.
16	ZHAO Yi, HAO Runlong, YUAN Bo, et al. Simultaneous removal of SO₂, NO and Hg⁰ through an integrative process utilizing a cost-effective complex oxidant[J]. Journal of Hazardous Materials, 2016, 301: 74-83.
17	XI Hongyuan, ZHOU Song, ZHANG Zhao. Novel method using Na₂S₂O₈ as an oxidant to simultaneously absorb SO₂ and NO from marine diesel engine exhaust gases[J]. Energy & Fuels, 2020, 34(2): 1984-1991.
18	KANG Myung Soo, SHIN Jaeuk, YU Tae U, et al. Simultaneous removal of gaseous NO _x and SO₂ by gas-phase oxidation with ozone and wet scrubbing with sodium hydroxide[J]. Chemical Engineering Journal, 2020, 381: 122601.
19	FLAGIELLO D, ERTO A, LANCIA A, et al. Advanced flue-gas cleaning by wet oxidative scrubbing (WOS) using NaClO₂ aqueous solutions[J]. Chemical Engineering Journal, 2022, 447: 137585.
20	LU Peng, YAN Xianhui, YE Lyumeng, et al. Performance and mechanism of CO₂ absorption during the simultaneous removal of SO₂ and NO _x by wet scrubbing process[J]. Journal of Environmental Sciences, 2024, 135: 534-545.
21	钱真, 姚琬颖, 刘国辉, 等. 氯系氧化剂在烟气脱硫脱硝脱汞中的研究进展[J]. 化工环保, 2021, 41(6): 688-693.
	QIAN Zhen, YAO Wanying, LIU Guohui, et al. Research progresses of chlorine-based oxidants for desulfurization, denitration and demercuration of flue gas[J]. Environmental Protection of Chemical Industry, 2021, 41(6): 688-693.
22	肖灵, 程斌, 莫建松, 等. 次氯酸钠湿法烟气脱硝及同时脱硫脱硝技术研究[J]. 环境科学学报, 2011, 31(6): 1175-1180.
	XIAO Ling, CHENG Bin, MO Jiansong, et al. Removal of NO and SO₂ from flue gas by wet scrubbing using aqueous NaClO solution[J]. Acta Scientiae Circumstantiae, 2011, 31(6): 1175-1180.
23	MONDAL Monoj Kumar, CHELLUBOYANA Vaishnava Raghunath. New experimental results of combined SO₂ and NO removal from simulated gas stream by NaClO as low-cost absorbent[J]. Chemical Engineering Journal, 2013, 217: 48-53.
24	刘海龙, 王晋刚, 张少峰. 次氯酸钙溶液脱硫脱硝一体化过程热力学分析[J]. 环境科学与技术, 2012, 35(6): 55-57, 63.
	LIU Hailong, WANG Jingang, ZHANG Shaofeng. Thermodynamics analysis of integrated process for simultaneous desulfurization and denitrification with calcium hypochlorite solution[J]. Environmental Science & Technology, 2012, 35(6): 55-57, 63.
25	马倩, 张少峰, 王晋刚, 等. 次氯酸钙湿法烟气脱硝工艺试验研究[J]. 河北工业大学学报, 2014, 43(5): 67-71.
	MA Qian, ZHANG Shaofeng, WANG Jingang, et al. Experimental research on flue gas denitrification with CaClO₂ solution[J]. Journal of Hebei University of Technology, 2014, 43(5): 67-71.
26	ZHAO Yi, GUO Tianxiang, CHEN Zhouyan, et al. Simultaneous removal of SO₂ and NO using M/NaClO₂ complex absorbent[J]. Chemical Engineering Journal, 2010, 160(1): 42-47.
27	WEI Jinchao, LUO Yunbai, YU Ping, et al. Removal of NO from flue gas by wet scrubbing with NaClO₂/(NH₂)₂CO solutions[J]. Journal of Industrial and Engineering Chemistry, 2009, 15(1): 16-22.
28	HAN Zhitao, YANG Shaolong, PAN Xinxiang, et al. New experimental results of NO removal from simulated flue gas by wet scrubbing using NaClO solution[J]. Energy & Fuels, 2017, 31(3): 3047-3054.

[1]	武西宁, 张宁, 秦佳敏, 徐龙, 魏朝阳, 马晓迅. 低冷量下强化CO₂吸收的甲醇基纳米流体性能[J]. 化工进展, 2024, 43(5): 2811-2822.
[2]	闫博引, 韩春宇, 夏晶晶, 王松雪, 武桂芝, 夏文香, 李金成. UV/H₂O₂和UV/NaClO工艺降解吉非罗齐的比较[J]. 化工进展, 2023, 42(11): 6102-6112.
[3]	郑鹏, 李蔚玲, 郭亚飞, 孙健, 王瑞林, 赵传文. 鼓泡床中电石渣加速碳酸化分析与响应面优化[J]. 化工进展, 2022, 41(3): 1528-1538.
[4]	任高林, 张学伟, 魏强, 王永亮, 雷晨辉, 徐一慧, 马文鑫. 10种石灰石浆液箱搅拌机的选型与计算[J]. 化工进展, 2021, 40(S1): 50-60.
[5]	魏楠, 吴晅, 薄宇轩, 刘鹏, 马骏. 气泡在颗粒床层表面的生成脱离行为[J]. 化工进展, 2021, 40(2): 678-687.
[6]	窦金孝,赵永奇,段晓谞,柴红宁,余江龙. 络合亚铁乙二醇-四丁基溴化铵低共熔溶剂协同吸收SO₂和NO[J]. 化工进展, 2020, 39(2): 453-460.
[7]	刘露, 骆嘉钦, 阚青, 马晓迅. 乙醇胺对介质阻挡耦合电晕放电同时脱除NO、SO₂的影响[J]. 化工进展, 2020, 39(11): 4685-4692.
[8]	阚青,杨岚,刘露,马晓迅. 添加剂CH₃COONH₄对介质阻挡-电晕放电耦合法脱除NO、SO₂的影响[J]. 化工进展, 2019, 38(10): 4786-4796.
[9]	许源, 陶汉中, 张栋玮. 内插扭带对鼓泡反应器脱硫脱硝效果的影响[J]. 化工进展, 2019, 38(06): 2992-3001.
[10]	李成伟, 张安超, 宋军, 张立享, 张丹, 刘志超. Ag/BiOI光催化剂湿法脱除烟气中气态单质汞性能及机理[J]. 化工进展, 2018, 37(04): 1442-1450.
[11]	武传朋, 张晨昕, 郭大为, 毛安国. 还原法脱除烟气中SO_x和/或NO_x的研究进展[J]. 化工进展, 2017, 36(S1): 457-463.
[12]	刘汝锋，刘婷灵，尚小琴，钟建明，何柳红，邓炳财，李淑妍. 高铁酸钾的制备工艺研究与表征[J]. 化工进展, 2013, 32(08): 1902-1904.
[13]	范学友，贾勇，钟秦. 氨吸收法同时脱硫脱硝的实验研究[J]. 化工进展, 2012, 31(01 ): 213-216.
[14]	石晓鹏，梅华，沈健. Ni2O3催化剂的制备及其催化NaClO分解产生活性氧的性能 [J]. 化工进展, 2009, 28(6): 962-.
[15]	陈炳和，赵辉爽. 2,4-二甲基苯甲酸的制备反应机理探讨及合成工艺改进 [J]. 化工进展, 2008, 27(10): 1650-.