氨基湿法脱硫脱硝吸收液电解制备过硫酸铵

doi:10.11949/j.issn.0438-1157.20170796

摘要/Abstract

摘要：

燃煤烟气污染物资源循环利用是烟气污染治理的发展方向，为探究直接电解氨基湿法脱硫脱硝吸收液制备过硫酸铵进行资源化回收的可行性，在板框式隔膜流动电解槽中考察了硫酸铵浓度、硫氰酸铵浓度、硫酸浓度、温度、电流密度、流速、电解时间以及吸收液中杂质成分等工艺参数对电解制备过硫酸铵的影响特性。结果表明，吸收液中的尿素和氨水对电流效率有抑制作用，而SO₃^2-和NO₃^-对电流效率几乎没有影响，模拟吸收液的电流效率仅为69.88%，远低于单一电解硫酸铵溶液86.98%的电流效率。对吸收液采取去除尿素、亚硫酸根氧化和吸收液pH调节（pH=2.2）预处理后，其电流效率达到85.12%。氨基湿法脱硫脱硝吸收液电解工艺不仅可高效制备过硫酸铵，阴极还可副产氢气，电解结晶后余液进一步与氨基湿法脱硫脱硝循环吸收液耦合，还可较大提升烟气脱硝效率，是一种新型的绿色高效的烟气净化技术路线，具有极大的发展前景。

关键词: 资源化, 过硫酸铵, 脱硫脱硝, 电解, 氢气

Abstract:

The resource recycling of flue gas pollution is the developing direction of exhaust pollutant treatment. In order to explore the feasibility of the direct electrolysis process for resource recycling of the absorption solution from the ammonia-based wet desulfurization and denitrification, the effect of electrolyte compositions and concentrations, temperature, current densities, flow rate, electrolytic time and impurities of absorption on current efficiency of persulfate production were investigated in a two-compartment electrolytic cell under batch recirculation. The experimental results indicated that urea and ammonia has inhibitory effect on current efficiency, while ammonium sulfite and nitrite existing in anode chamber showed no significant influence on current efficiency. The current efficiency of simulated absorbent solution decreased to 69.88%, which was much lower than 86.98% by the pure ammonium sulfate electrolysis process under the optimal condition. Therefore, necessary pretreatments for the absorption solution, which contained the removal of heavy metal ions and urea, the oxidation of sulfite and the adjustment of pH, must be adopted before entering the electrolysis system. Using the pretreated absorption solution, the current efficiency could reach to 85.12%. The electrolytic reactor could effectively produce persulfate in anodic chamber and hydrogen by-product in cathodic chamber at the same time. Furthermore, the remainder solution after crystallization could be coupled with circulation absorption solution, and thus improving the denitrification efficiency. Therefore, it is a novel environmentally effective technology for flue gas cleaning with great prospects for development.

Key words: resource recycling, ammonium persulfate, desulfurization and denitrification, electrolysis, hydrogen

中图分类号:

X773

冯浩, 熊源泉, 吴波. 氨基湿法脱硫脱硝吸收液电解制备过硫酸铵[J]. 化工学报, 2017, 68(12): 4691-4701.

FENG Hao, XIONG Yuanquan, WU Bo. Electrochemical production of ammonium persulfate using absorption solution from ammonia-based wet desulfurization and denitrification[J]. CIESC Journal, 2017, 68(12): 4691-4701.

参考文献 30

[1]	汤志刚, 贺志敏, EBRAHIM, 等. 焦炉烟道气双氨法一体化脱硫脱硝:从实验室到工业实验[J]. 化工学报, 2017, 68(2):496-508. TANG Z G, HE Z M, EBRAHIM, et al. Desulfurization and denitration integrative process for coke oven flue gas using dual ammonia solution:from laboratory to industrial test[J]. CIESC Journal, 2017, 68(2):496-508.
[2]	黄荣廷, 潘丹萍, 盛溢, 等. 氨法烟气脱硫过程中气溶胶颗粒生成特性[J]. 化工学报, 2015, 66(11):4366-4372. HUANG R T, PAN D P, SHENG Y, et al. Properties of aerosol formation during wet ammonia-based desulfurization process[J]. CIESC Journal, 2015, 66(11):4366-4372.
[3]	WU B, XIONG Y Q, RU J B, et al. Removal of NO from flue gas using heat-activated ammonium persulfate aqueous solution in a bubbling reactor[J]. RSC Advances, 2016, 6(5):33919-33930.
[4]	王颖, 熊源泉, 张晋萍. 脱硫脱硝吸收液中硫酸铵电化学制备过硫酸铵的实验研究[J]. 东南大学学报(自然科学版), 2015, 45(4):738-744. WANG Y, XIONG Y Q, ZHANG J P. Experimental study on electrosynthesis of ammonium persulfate using ammonium sulfate solutions from wet simultaneous desulfurization and denitrification[J]. Journal of Southeast University (Natural Science Edition), 2015, 45(4):738-744.
[5]	范学友, 贾勇, 钟秦. 氧化法、氨法脱硫、脱硝副产物硫酸铵、硝酸铵结晶研究[J]. 无机盐工业, 2012, 44(5):25-27. FAN X Y, JIA Y, ZHONG Q. Study on crystallization of ammonium sulfate and ammonium nitrate by-produced from desulfurization and denitrification with oxidation and ammonia methods[J]. Inorganic Chemicals Industry, 2012, 44(5):25-27.
[6]	YANG C L, HU Y, CAO L M, et al. Performance optimization of an electromembrane reactor for recycling and resource recovery of desulfurization residuals[J]. AIChE Journal, 2014, 60(7):2613-2624.
[7]	ZHU J, HⅡ K K, HELLGARDT K, et al. Toward a green generation of oxidant on demand:practical electrosynthesis of ammonium persulfate[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(4):2027-2036.
[8]	DAVIS J R, BAYGENTS J C, FARRELL J. Understanding persulfate production at boron doped diamond film anodes[J]. Electrochimica Acta, 2014, 150:68-74.
[9]	BALAJI S, MUTHURAMAN G, MOON I S. Influence of cathode on the electro-generation of peroxydisulfuricacid oxidant and its application for effective removal of SO2 by room temperature electro-scrubbing process[J]. Journal of Hazardous Materials, 2015, 299:437-443.
[10]	DAVIS J R, BAYGENTS J C, FARRELL J. Effect of current density and sulfuric acid concentration on persulfuric acid generation by boron-doped diamond film anodes[J]. Journal of Applied Electrochemistry, 2014, 44(7):841-848.
[11]	LUO H J, LI C L, SUN X, et al. Cathodic indirect oxidation of organic pollutant paired to anodic persulfate production[J]. Journal of Electroanalytical Chemistry, 2017, 792:110-116.
[12]	赵建宏, 孙培永, 王留成, 等. 电解法生产过硫酸铵的研究[J]. 郑州大学学报(工学报), 2006, 27(1):109-112. ZHAO J H, SUN P Y, WANG L C, et al. Study on the process for electrosynthesis of ammonium persulfate[J]. Journal of Zhengzhou University(Engineering Science), 2006, 27(1):109-112.
[13]	南湖, 王宇新.SPEEK复合膜在电解制备过硫酸铵中的应用[J]. 化学工业与工程, 2013, 30(1):53-58. NAN H, WANG Y X. Application of SPEEK composite membranes in electrosynthesis of ammonium persulfate[J]. Chemical Industry and Engineering, 2013, 30(1):53-58.
[14]	MICHAUD P, MAHE E, HAENNI W, et al.Preparation of peroxodisulfuric acid using boron-doped diamond thin film electrodes[J]. Electrochemical and Solid State Letters, 2000, 3:77-79.
[15]	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(1):213-216. FAN X Y, JIA Y, ZHONG Q. Experimental study on ammonia absorption for simultaneous desulfurization and denitrification[J]. Chemical Industry and Engineering Progress, 2012, 31(1):213-216.
[16]	LIANG C J, HUANG C F.A rapid spectrophotometric determination of persulfate anion in ISCO[J]. Chemosphere, 2008, 73(1):1540-1543.
[17]	SERRANO K, MICHAUD P, COMNINELLIS C, et al. Electrochemical preparation of peroxoidsulfuric acid using boron doped diamond thin film electrodes[J]. Electrochimica Acta, 2002, 48:431-436.
[18]	BALEJ J, MILADA T A, SPAL'KOVA H. The influence of reaction conditions on the course of electrolytic preparation of ammonium peroxodisulphate:the influence of the relative degree of saturation of starting solution and of the temperature[J]. Collection of Czechoslovak Chemical Communication, 1981, 46(11):2795-2808.
[19]	FELIX H, SUSANNE D, RALF Z. Continuous electrooxdiation of sulfuric acid on boron-doped diamond electrodes[J]. Electrochimica Acta, 2014, 147:589-595.
[20]	YANG C L, HU Y, LI M, et al. Circulating regeneration and resource recovery of flue gas desulfurization residuals using a membrane electroreactor:from lab concept to commercial scale[J]. Environmental Science& Technology, 2012, 46(20):11273-11279.
[21]	张广宏, 陈延林. 电解法制备过硫酸铵研究综述[J]. 广州化工, 2012, 19(40):19-21. ZHANG G H, CHEN Y L. Study on electrolytic method for preparing ammonium persufate[J]. Guangzhou Chemical Industry, 2012, 19(40):19-21.
[22]	刘恩辉. 脱硫吸收液膜电解再生前水质净化方法研究[D]. 天津:天津大学, 2008:8-10. LIU E H. Study on the purifying methods of water quality of desulfurization absorption liquid before membrane electrolysis regeneration[D]. Tianjin:Tianjin University, 2008:8-10.
[23]	田立伟. 膜电解再生钠碱脱硫工业性试验研究[D].天津:天津大学, 2006:50-51. TIAN L W. Industrialized study on a recycling natrium-alkali via ion-exchange membrane electrolysis FGD technology[D]. Tianjin:Tianjin University, 2006:50-51.
[24]	ADEWUYI Y G, KHAN M A, SAKYI N Y. Kinetics and modeling of the removal of nitric oxide by aqueous sodium persulfate simultaneously activated by temperature and Fe2+[J]. Industrial & Engineering Chemistry Research, 2014, 53(2):828-839.
[25]	武春锦, 吕武华, 梅毅, 等. 湿法烟气脱硫技术及运行经济性分析[J]. 化工进展, 2015, 34(12):4368-4374. WU C J, LÜ W H, MEI Y, et al. Application and running economic analysis of wet flue gas desulfurization technology[J]. Chemical Industry and Engineering Progress, 2015, 34(12):4368-4374.
[26]	DING J, ZHONG Q, ZHANG S, et al. Simultaneous removal of NOx and SO2 from coal-fired flue gas by catalytic oxidation-removal process with H2O2[J]. Chemical Engineering Journal, 2014, 243:176-182.
[27]	杜振, 钱俆悦, 何胜, 等. 燃煤电厂烟气SCR脱硝成本分析与优化[J]. 中国电力, 2013, 46(10):124-128. DU Z, QIAN X Y, HE S, et al. Analysis and optimization for operating costs of gas SCR DeNOx in coal-fired power plants[J]. Electric Power, 2013, 46(10):124-128.
[28]	王艳, 程轲, 易鹏. 超低排放背景下燃煤电厂烟气控制技术费效评估[J]. 环境污染与防治, 2017, 39(3):331-335. WANG Y, CHENG K, YI P. Cost-benefit evaluation of smoke control technologies for coal-fired power plants in the context of ultra-low emission[J]. Chinese Journal of Environmental Engineering, 2017, 39(3):331-335.
[29]	ZHANG J, ZHANG Y X, YANG H et al. Cost-effectiveness optimization for SO2 emissions control from coal-fired power plants on a national scale:a case study in China[J]. Journal of Cleaner Production, 2017, 165(1):1005-1012.
[30]	史占飞, 熊源泉, 印建朴. 脱硫脱硝经济性分析[J]. 资源与环境, 2010, 2(2):48-49. SHI Z F, XIONG Y Q, YIN J P. Economic analysis on desulfurization and denitrification[J]. Energy Research & Utilization, 2010, 2(2):48-49.