湿法烟气脱硝Fe Ⅱ EDTA-NO液的NO真空解吸

doi:10.16085/j.issn.1000-6613.2022-0076

摘要/Abstract

摘要：

Fe^ⅡEDTA络合湿法脱硝是一种非常具有前景的烟气脱硝工艺，其中Fe^ⅡEDTA-NO液的NO解吸对Fe^ⅡEDTA的循环利用具有重要意义。本文首次将真空解吸技术应用于Fe^ⅡEDTA/抗坏血酸（VC）混合脱硝系统。在实验室规模的反应器中，深入研究了真空度和温度等操作因素对NO解吸性能的影响。实验结果表明，Fe^ⅡEDTA-NO液的NO可以通过直接加热或真空进行解吸，真空度的大幅度上升可以显著提高解吸性能，且高温有利于NO的解吸。此外，与直接加热再生相比，真空解吸可提高解吸速率并降低总能耗。动力学结果表明，Fe^ⅡEDTA-NO的解吸过程为一级动力学，同时，Fe^ⅡEDTA-NO解吸的活化能、活化熵、活化焓分别为2.83kJ/mol、196.90J/(K·mol)、159.76kJ/mol。最后，解吸吸收循环实验过程表明，脱硝富液Fe^ⅡEDTA-NO在NO真空解吸后仍能捕获NO，而且在循环实验中，经过11个循环后，NO的平均去除率降至90%以下。

关键词: 一氧化氮, 蒸发, 解吸, 烟道气

Abstract:

Complex wet denitrification by Fe^ⅡEDTA is a promising process to remove nitric oxide (NO) from flue gas, in which the desorption of NO from Fe^ⅡEDTA-NO solution is of great importance for the reuse of Fe^ⅡEDTA solution. In this paper, vacuum desorption technology was first employed for denitrification system of mixed Fe^ⅡEDTA and ascorbic acid (VC). The effect of operating factors including vacuum degree and temperature on NO desorption performance was thoroughly investigated in a lab-scale reactor. The experimental results showed NO could be desorbed from Fe^ⅡEDTA-NO rich solution by direct heating or vacuum, and the increase of vacuum degree and temperature could significantly improve the desorption performance. In addition, compared with direct heating regeneration, vacuum desorption could improve desorption rate and lower the total energy consumption. The kinetics study showed that the desorption process presented first-order kinetics regarding Fe^ⅡEDTA-NO. Meanwhile, the activation energy, activation entropy, and activation enthalpy of Fe^ⅡEDTA-NO desorption were calculated to be 2.83kJ/mol, 196.90J/(K·mol), and 159.76kJ/mol, respectively. Finally, the absorption-desorption recycling experiments showed that Fe^ⅡEDTA-NO rich solution, after vacuum desorption of NO, could continue to capture NO, while the average NO removal eﬃciency would decrease below 90% after 11 cycles.

Key words: nitric oxide, evaporation, desorption, flue gas

中图分类号:

X701

钟丽蓉, 何飞强, 董贝贝, 刘紫薇, 丁健桦. 湿法烟气脱硝Fe ^Ⅱ EDTA-NO液的NO真空解吸[J]. 化工进展, 2022, 41(11): 6176-6184.

ZHONG Lirong, HE Feiqiang, DONG Beibei, LIU Ziwei, DING Jianhua. Vacuum desorption of NO from Fe ^Ⅱ EDTA-NO solution generated in wet flue gas denitrification[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 6176-6184.

图/表 9

图1 FeⅡEDTA-NO液的NO解吸实验装置1—带磁搅拌的恒温槽；2—磁搅拌器；3—三口烧瓶；4—温度计；5—真空表；6—针阀；7—冷凝管；8—收集瓶；9—真空度控制；10—气体吸收瓶；11—真空泵

图2 NO吸收-解吸循环实验1—空气压缩机；2—针阀；3—转子流量计；4—无气缸；5—玻璃三通；6—储气罐；7—带磁力搅拌的恒温槽；8—磁力搅拌器；9—温度计；10—流量计；11—冷凝管；12—真空表；13—真空度控制；14—气体吸收瓶；15—真空泵

表1 NO吸收-解吸循环实验条件

实验条件	NO吸收	NO解吸
吸收液体积/mL	500 （0.01mol/L Fe^ⅡEDTA+2% VC）	500
温度/℃	25	70
真空度/kPa	常压	79~81
气体流速/L·min^-1	0.4
NO浓度/mL·m^-3	500
时间/min	40	60

图3 25~100℃常压解吸下FeⅡEDTA-NO浓度的变化

图4 真空度对解吸的影响

图5 ln[FeⅡEDTA-NO2-]随时间变化线性拟合图

图6 温度对解吸的影响

图7 不同温度下的动力学

图8 NO吸收-解吸循环实验

参考文献 32

1	LI Jue, WANG Li, HAN Chunqiu, et al. Industrial TiO₂ based nacreous pigments as functional building materials: photocatalytic removal of NO[J]. Chinese Journal of Chemical Engineering, 2020, 28(10): 2587-2591.
2	HE Feiqiang, ZHU Xinyu, CHEN Xianchun, et al. Performance, optimization, and mechanism of nitric oxide removal by thiourea dioxide/Fe^ⅡEDTA reaction systems[J]. Chinese Journal of Chemical Engineering, 2020, 28(11): 2918-2927.
3	郝润龙, 钱真, 符乐, 等. 微波诱导催化脱硝研究进展[J]. 化工进展, 2021, 40(5): 2747-2752.
	HAO Runlong, QIAN Zhen, FU Le, et al. Research progress of microwave-induced catalytic denitrification[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2747-2752.
4	陈赛, 贾明生, 郭明高, 等. SNCR脱硝技术在液态排渣煤粉工业锅炉中的应用[J]. 化工进展, 2020, 39(10): 4290-4296.
	CHEN Sai, JIA Mingsheng, GUO Minggao, et al. Application of SNCR to reduction of NO _x in an industrial scale slag-tap pulverized coal boiler[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4290-4296.
5	何飞强, 邓先和, 陈民. 乙二胺四乙酸铁络合物湿法络合脱硝液的再生研究进展[J]. 化工进展, 2018, 37(2): 737-743.
	HE Feiqiang, DENG Xianhe, CHEN Min. Research progress on Fe(Ⅱ)EDTA regeneration accompanied wet denitrification[J]. Chemical Industry and Engineering Progress, 2018, 37(2): 737-743.
6	SADA E, KUMAZAWA H, TAKADA Y. Chemical reactions accompanying absorption of nitric oxide into aqueous mixed solutions of iron(Ⅱ)-EDTA and sodium sulfite[J]. Industrial & Engineering Chemistry Fundamentals, 1984, 23(1): 60-64.
7	WANG Shijie, ZHANG Qi, ZHANG Gu, et al. Effects of sintering flue gas properties on simultaneous removal of SO₂ and NO by ammonia-Fe(‍Ⅱ)EDTA absorption[J]. Journal of the Energy Institute, 2017, 90(4): 522-527.
8	ZHU Haisong, MAO Yanpeng, YANG Xiaojuan, et al. Simultaneous absorption of NO and SO₂ into Fe^Ⅱ‍-EDTA solution coupled with the Fe^Ⅱ‍-EDTA regeneration catalyzed by activated carbon[J]. Separation and Purification Technology, 2010, 74(1): 1-6.
9	YAN Bei, YANG Jiehong, GUO Meng, et al. Study on NO enhanced absorption using Fe^ⅡEDTA in (NH₄)₂SO₃ solution[J]. Journal of Industrial and Engineering Chemistry, 2014, 20(4): 2528-2534.
10	ZHOU Zuoming, JING Guohua, ZHENG Xiangjiao. Reduction of Fe(‍Ⅲ)EDTA by Klebsiella sp. strain FD-3 in NO _x scrubber solutions[J]. Bioresource Technology, 2013, 132: 210-216.
11	HE Feiqiang, DENG Xianhe, CHEN Min. Mechanism and kinetics of Fe(‍Ⅱ)EDTA-NO reduction by iron powder under anaerobic condition[J]. Fuel, 2016, 186: 605-612.
12	HE Feiqiang, DENG Xianhe, CHEN Min. Evaluation of Fe(‍Ⅱ)EDTA-NO reduction by zinc powder in wet flue gas denitrification technology with Fe(Ⅱ)EDTA[J]. Fuel, 2017, 199: 523-531.
13	HE Feiqiang, QIAN Yong, XU Jianping. Performance, mechanism, and kinetics of Fe(‍Ⅲ)EDTA reduction by thiourea dioxide[J]. Energy & Fuels, 2019, 33: 3331-3338.
14	HE Feiqiang, ZHU Xinyu, CHEN Xianchun, et al. Simultaneous removal of NO and SO₂ from flue gas by Fe^ⅡEDTA/sodium dithionite solutions[J]. Journal of Chemical Technology & Biotechnology, 2020, 95: 1392-1399.
15	HE Feiqiang, DENG Xianhe, CHEN Min. Nitric oxide removal by combined urea and Fe^ⅡEDTA reaction systems[J]. Chemosphere, 2017, 168: 623-629.
16	HE Feiqiang, ZHU Xinyu, CHEN Xianchun, et al. Performance, mechanism, and kinetics of NO removal by combined ascorbic acid and Fe^ⅡEDTA reaction systems[J]. Fuel, 2021, 284: 119070.
17	ZHU Xinyu, HE Feiqiang, XIA Meng, et al. Evaluation of Fe(‍Ⅲ)EDTA reduction with ascorbic acid in a wet denitrification system[J]. RSC Advances, 2019, 9(42): 24386-24393.
18	ZHANG Liqiang, JIANG Haitao, MA Chunyuan, et al. Microwave regeneration characteristics of activated carbon for flue gas desulfurization[J]. Journal of Fuel Chemistry and Technology, 2012, 40(11): 1366-1371.
19	CHEN Min, DENG Xianhe, HE Feiqiang. Study on the regeneration of basic aluminum sulfate SO₂-rich solution by vacuum desorption[J]. Energy & Fuels, 2016, 30(10): 8469-8478.
20	XU H, ZHANG S T, LU X B, et al. Effect of ultrasound on SO₂ desorption from sodium alkali desulphurization regeneration solution[J]. Chemical Engineering & Technology, 2010, 33(2): 231-236.
21	XUE Juanqin, LI Jingxian, LU Xi, et al. Absorption of sulfur dioxide using membrane and enhancement of desorption with ultrasound[J]. Transactions of Nonferrous Metals Society of China, 2010, 20(5): 930-934.
22	PI Xinxin, SUN Fei, GAO Jihui, et al. Microwave irradiation induced high-efficiency regeneration for desulfurized activated coke: a comparative study with conventional thermal regeneration[J]. Energy & Fuels, 2017, 31(9): 9693-9702.
23	VADILLO J M, HOSPITAL-BENITO D, MOYA C, et al. Modelling and simulation of hollow fiber membrane vacuum regeneration for CO₂ desorption processes using ionic liquids[J]. Separation and Purification Technology, 2021, 277: 119465.
24	CHEN Guifang, SUN Xiaofei, FENG Yunqi, et al. Desorption of CO₂, SO₂, and NH₃ in the vacuum evaporation of desulfurization wastewater[J]. Environmental Science and Pollution Research, 2021, 28(6): 6664-6674.
25	ZHANG Shihan, LI Wei, WU Chengzhi, et al. Reduction of Fe(‍Ⅱ)EDTA-NO by a newly isolated Pseudomonas sp. strain DN-2 in NO _x scrubber solution[J]. Applied Microbiology and Biotechnology, 2007, 76(5): 1181-1187.
26	TERAMOTO M, KITADA S, OHNISHI N, et al. Separation and concentration of CO₂ by capillary-type facilitated transport membrane module with permeation of carrier solution[J]. Journal of Membrane Science, 2004, 234(1/2): 83-94.
27	FAVRE E. Carbon dioxide recovery from post-combustion processes: can gas permeation membranes compete with absorption? [J]. Journal of Membrane Science, 2007, 294(1/2): 50-59.
28	YAN Shuiping, FANG Mengxiang, LUO Zhongyang, et al. Regeneration of CO₂ from CO₂-rich alkanolamines solution by using reduced thickness and vacuum technology: regeneration feasibility and characteristic of thin-layer solvent[J]. Chemical Engineering and Processing: Process Intensification, 2009, 48(1): 515-523.
29	WEXLER A. Vapor pressure formulation for water in range 0 to 100℃. A revision[J]. Journal of Research of the National Bureau of Standards Section A, Physics and Chemistry, 1976, 80A(5/6): 775-785.
30	LUTHER III G W, POPP J I. Kinetics of the abiotic reduction of polymeric manganese dioxide by nitrite: an anaerobic nitrification reaction[J]. Aquatic Geochemistry, 2002, 8: 15-36.
31	WANG Xiaojun, ZHANG Yu, DONG Xiyang, et al. Fe(‍Ⅱ)EDTA-NO reduction by sulfide in the anaerobic aqueous phase: stoichiometry and kinetics[J]. Energy & Fuels, 2013, 27(10): 6024-6030.
32	ZHONG Lirong, HE Feiqiang, LIU Ziwei, et al. Adsorption of uranium (‍Ⅵ) ions from aqueous solution by acrylic and diaminomaleonitrile modiﬁed cellulose[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 641: 128565.

[1]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[2]	王云刚, 焦健, 邓世丰, 赵钦新, 邵怀爽. 冷凝换热与协同脱硫性能实验分析[J]. 化工进展, 2023, 42(8): 4230-4237.
[3]	李吉焱, 景艳菊, 邢郭宇, 刘美辰, 龙永, 朱照琪. 耐盐型太阳能驱动界面光热材料及蒸发器的研究进展[J]. 化工进展, 2023, 42(7): 3611-3622.
[4]	杨家添, 唐金铭, 梁恣荣, 黎胤宏, 胡华宇, 陈渊. 新型淀粉基高吸水树脂抑尘剂的制备及其应用[J]. 化工进展, 2023, 42(6): 3187-3196.
[5]	赵尧, 周志辉, 吴红丹, 胡传智, 张国春, 吴睿鹏. Silicalite-1分子筛膜渗透蒸发条件的响应面分析与优化[J]. 化工进展, 2023, 42(5): 2586-2594.
[6]	何川, 吴国勋, 李昂, 张发捷, 卞子君, 卢承政, 王丽朋, 赵民. 垃圾焚烧脱硝催化剂钙镁失活与活性恢复特性[J]. 化工进展, 2023, 42(5): 2413-2420.
[7]	谢迎春, 马洪亭, 徐畅, 马硕, 陈默, 刘军, 孙国强. 竖管渗流降膜蒸发式冷凝器传热特性分析[J]. 化工进展, 2023, 42(3): 1187-1194.
[8]	周皞, 张恒, 温妮妮, 王旭瑞, 徐璐, 李玮, 苏亚欣. Cu-SAPO-44分子筛的制备及其C₃H₆-SCR脱硝性能[J]. 化工进展, 2023, 42(3): 1373-1382.
[9]	尚玉, 肖满, 崔秋芳, 涂特, 晏水平. CO₂捕集工艺中热再生气余热的PVDF/BN-OH平板复合膜回收特性[J]. 化工进展, 2023, 42(3): 1618-1628.
[10]	张赫, 李小可, 熊颖, 文劲. 基于水凝胶界面光蒸发的压裂返排液脱盐降污处理[J]. 化工进展, 2023, 42(2): 1073-1079.
[11]	王胜楠, 郑旭. 空气取水用活性炭纤维复合吸附剂的研究[J]. 化工进展, 2023, 42(10): 5567-5573.
[12]	毛停停, 李双福, 黄李茗铭, 周川玲, 韩凯. 面向水处理与有机溶剂回收的太阳能界面蒸发系统与材料[J]. 化工进展, 2023, 42(1): 178-193.
[13]	李超, 苗家兵, 王丽萍, 崔永杰, 李依帆. 蒸发母液中锂的提取[J]. 化工进展, 2022, 41(S1): 637-642.
[14]	郑宿正, 李南茜, 董德平. 平板陶瓷毛细芯环路热管的实验与仿真[J]. 化工进展, 2022, 41(7): 3510-3518.
[15]	毛纪金, 张东辉, 孙利利, 雷钦晖, 屈健. 两种烧结通道的沸腾传热和阻力特性对比[J]. 化工进展, 2022, 41(7): 3483-3492.