氧化法烟气脱硫脱硝废水回收NaNO2工艺

doi:10.12034/j.issn.1009-606X.218244

过程工程学报 ›› 2019, Vol. 19 ›› Issue (3): 631-636.DOI: 10.12034/j.issn.1009-606X.218244

氧化法烟气脱硫脱硝废水回收NaNO₂工艺

陈艳¹，王晨晔^1*，王兴瑞¹，孟子衡^1,2，李会泉^1,2

1. 中国科学院绿色过程与工程重点实验室，湿法冶金清洁生产技术国家工程实验室，中国科学院过程工程研究所，北京 100190 2. 中国科学院大学化学工程学院，北京 100049

收稿日期:2018-07-18 修回日期:2018-09-30 出版日期:2019-06-22 发布日期:2019-06-20
通讯作者: 王晨晔 cywang@ipe.ac.cn
基金资助:
国家自然科学基金青年科学基金项目

Recovery technology of NaNO₂ from flue gas desulfurization and denitration wastewater by an oxidation process

Yan CHEN¹, Chenye WANG^1*, Xingrui WANG¹, Ziheng MENG^1,2, Huiquan LI^1,2

1. Key Laboratory of Green Process and Engineering of Chinese Academy of Sciences, National Engineering Lab for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 2. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-07-18 Revised:2018-09-30 Online:2019-06-22 Published:2019-06-20
Contact: WANG Chen-ye cywang@ipe.ac.cn

摘要/Abstract

摘要： 针对氧化法烟气脱硫脱硝废水中含大量亚硝酸盐造成水体污染及有价盐资源浪费问题，回收废水中的NaNO2，提出pH调控除杂?碳碱沉淀脱钙?结晶提纯分离工艺，分别考察了pH值、除钙剂投加方式、浓缩总盐浓度和结晶温度对废水中NaNO2结晶率和纯度的影响。结果表明，pH值和浓缩总盐浓度是影响脱硫脱硝废水中NaNO2结晶率及纯度的主要因素。在除杂pH=11、除钙剂湿投、浓缩总盐浓度70wt%、结晶温度50℃的条件下，NaNO2结晶率大于60%，产品质量达到GB/T 2367-2016标准。

关键词: 脱硫脱硝, 废水, 结晶, 亚硝酸钠

Abstract: The wastewater from the processes of desulfurization and denitration contained complex components, and the recovery of wastewater was limited by the co-existence of nitrates and nitrites. By now, this type of wastewater was mostly directly discharged after a simple treatment or was sent to the sewage treatment plant for further disposal, leading to series of environmental problems or causing instability of biochemical section in sewage treatment plants. Moreover, the cost of the recovery process will decrease via recovering the nitrogenous valuable salt. In this work, a low-cost process with high efficiency of desulfurization and denitration was developed. There were only nitrite ions as nitrogen-containing anions in the wastewater of desulfurization and denitration. Using steel slag slurry combined with ozone oxidation, this process achieved high desulfurization and denitration rate with accessory ingredient of Na2S2O3. There were cations such as Na+, Mg2+, Ca2+, Mn2+, Fe2+, etc. and anions such as NO2?, S2O32?, SO42?, etc. existing in the as-generated wastewater. The water pollution and marketable salt resources waste from wet flue gas desulfurization and denitration via a gas phase oxidation?wet absorption process was mainly solved in this work. A technology of pH adjustment?decalcification via adding sodium carbonate-evaporating crystallization to recovery NaNO2 from wastewater was proposed. The effects of pH, addition methods of sodium carbonate, concentrated total salt concentration, and crystallization temperature on the crystallization rate and purity of NaNO2 were discussed. The results indicated that the crystallization rate and the purity of NaNO2 from desulfurization and denitration wastewater were mainly affected by pH and total concentrated salt concentration. Under the optimal conditions, in which pH was 11, addition method of sodium carbonate was concentrated solution, total concentrated salt concentration was 70wt%, and crystallization temperature was 50℃, the crystallization rate of NaNO2 was greater than 60%. The products of NaNO2 met the quality requirement of national standard (GB/T 2367-2016).

Key words: desulfurization and denitration, wastewater, crystal, sodium nitrite

陈艳王晨晔王兴瑞孟子衡李会泉. 氧化法烟气脱硫脱硝废水回收NaNO₂工艺[J]. 过程工程学报, 2019, 19(3): 631-636.

Yan CHEN Chenye WANG Xingrui WANG Ziheng MENG Huiquan LI. Recovery technology of NaNO₂ from flue gas desulfurization and denitration wastewater by an oxidation process[J]. Chin. J. Process Eng., 2019, 19(3): 631-636.

参考文献

[1]曾凡刚, 王玮, 吴燕红, 等.化石燃料燃烧产物对大气环境质量的影响及研究现状[J].中央民族大学学报, 2001, 10(2):113-120
Zeng F G, Wang W, Wu Y H, et al.The Influence of Fossil Fuel Combustion Products on Atmospheric Environment Quality and Its Research Status[J].Journal of Central University for Nationalities, 2001, 10(2):113-120
[2]熊天龙, 李艳松, 刘琪琪, 等.焦化行业烟气低温SCR脱硝中试研究[J]. 四川化工, 2016, 1: 52-55.[J].四川化工, , :-
Xiong T L, Li Y S, Liu Q Q, et al.Pilot Study on SCR Denitrification of Flue Gas in Coking Industry at Low Temperature[J]. Sichuan Chemical Industry, 2016, 1: 52-55.
[3]Ren S, Yang J, Zhang T S, et al.Role of Cerium in Improving NO Reduction with NH3 over Mn-Ce/ASC Catalyst in Low-temperature Flue Gas[J]. Chemical Engineering Research & Design, 2018, 133: 1-10.
[4]Ma Q, Wang Z H, Lin F W, et al.Characteristics of O3 Oxidation for Simultaneous Desulfurization and Denitration with Limestone–Gypsum Wet Scrubbing-Application in a Carbon Black Drying Kiln Furnace[J]. Energy and Fuels, 2016, 30: 2302-2308.
[5]Hao R L, Yang S, Zhao L, et al.Follow-up Research of Ultraviolet Catalyzing Vaporized H2O2 for Simultaneous Removal of SO2 and NO: Absorption of NO2 and NO by Na-based WFGD by Product (Na2SO3)[J]. Fuel Processing Technology, 2017, 160: 64-69.
[6]Meng Z H, Wang C Y, Chen Y, et al.Simultaneous Removal of SO2 and NOx from Coal-fired Flue Gas using Steel slag Slurry[J].Energy and Fuels, 2018, 32(2):2028-2036
[7]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: 18-21.
Zhang X.Experimental and Mechanism Investigation on Multi-pollutant Absorption by Ozone with Calcium based Scrubbing and By-product Treatment[D]. Hangzhou: Zhejiang University, 2012: 18-21.
[8]张相, 朱燕群, 王智化, 等.臭氧氧化多种污染物协同脱及副产物提纯的试验研究[J].工程热物理学报, 2012, 33(7):1259-1262
Zhang X, Zhu Y Q, Wang Z H, et al.Experimental Study on Synergistic Desorption of Various Pollutants by Ozone Oxidation and Purification of By-products[J].Journal of Engineering Thermal Physics, 2012, 33(7):1259-1262
[9]Ma Q, Wang Z H, Lin F W, et al.Characteristics of O3 Oxidation for Simultaneous Desulfurization and Denitration with Limestone-gypsum Wet Scrubbing: Application in A Carbon Black Drying Kiln Furnace[J]. Energy and Fuels, 2016, 30: 2302-2308.
[10]张瑞.臭氧预氧化采用钙法烟气同步脱硫脱硝的研究[D]. 上海: 华东理工大学. 2014: 31-32.
Zhang R.Study on Simultaneous Desulfurization and Denitrification of Flue Gas by Calcium Method in Ozone Preoxidation[M]. Shanghai: East China University of Science and Technology. 2014: 31-32.
[11]Fang P, Cen C P, Tang Z X, et al.Simultaneous Removal of SO2 and NOx by Wet Scrubbing using Urea Solution[J].Chemical Engineering Journal, 2011, 168(1):52-59
[12]Zhou Y, Li C T, Fan C Z, et al.Wet Remove of Sulfur Dioxide and Nitrogen Oxides from Simulated Flue Gas by Ca(ClO)2 Solution[J].Environmental Progress & Sustainable Energy, 2015, 34(6):1586-1595
[13]杨业, 徐超群, 朱艳群, 等.臭氧氧化结合硫代硫酸钠溶液喷淋同时脱硫脱销[J].化工学报, 2016, 67(5):2041-2047
Yang Y, Xu C Q, Zhu Y Q, et al.Simultaneous Removal of SO2 and NOx by Combination of Ozone Oxidation and Na2S2O3 Solution Spray[J].Journal of Chemical Industry, 2016, 67(5):2041-2047
[14]Kordylewski W, Halat A, Luszkiewicz D.Influence of Oxidizing Reactor on Flue Gas Denitrification by Ozonation and Possibility of by-product Peparation[J].Chemical and Process Engineering-inzynieria Chemiczna I Procesowa, 2017, 38(1):177-191
[15]Barman S, Philip L.Integrated System for the Treatment of Oxides of Nitrogen from Flue Gases[J].Environmental Science& technology, 2006, 40(3):1035-1041
[16]Zhongbiao Wu, Haiqiang Wang, Yue Liu, et al.Study of A Photocatalytic Oxidation and Wet Absorption Combined Process for Removal of Nitrogen Oxides[J]. Chemical Engineering Journal, 2008, 144: 221–226.
[17]张国伟, 江奇志, 李强, 等.浅谈脱硫脱硝高浊度废水处理工艺[J]. 山东化工, 2016, (24): 147-149.
Zhang G W, Jiang W Q, Li Q, et al.Desulfurization and Denitrification of High Turbidity Wastewater Treatment Technology[J]. Shandong Chemical Industry, 2016, (24): 147-149.
[18]王晓伟.化学吸收-生物法烟气同步脱硫脱硝吸收液中SO42-和NO3-的生物转化[D]. 大连: 大连理工大学. 2016: 8-11.
Wang X W.Bioconversion of Sulfate and Nitrate in Scrubbing Liquor of Chemical Absorption-Biological Treatment Intergrated Flue Gas Simultaneous Desulfurization and Denitration Process[D]. Dalian: Dalian University of Technology. 2016: 8-11.
[19]王丽秋, 王小方, 李会泉, 等.焦炉烟气湿法钢渣联合脱硫脱硝工艺及机理研究[J].燕山大学学报, 2016, 40(4):348-354
Wang L Q, Wang X F, Li H Q, et al.Investigation on Technology and Mechanism of The Combine Desulfurization and Denitration of Steel Slag with Coke Oven Flue Gas Wet Process[J].Journal of Yanshan University, 2016, 40(4):348-354
[20]李会泉, 王兴瑞, 孟子衡, 等.一种臭氧氧化联合钢渣吸收的烟气脱硫脱硝工艺: CN106474893A [P]. 2017年3月8日.
Li H Q, Wang X R, Meng Z H, et al.The Process of Flue Gas Desulfurization and Denitrification by Ozone Oxidation Combined with Steel Slag Absorption: CN106474893A [P]. 2017-03-08.
[21]李会泉, 孟子衡, 王兴瑞.一种工业烟气臭氧分步氧化吸收同时脱硫脱硝的装置及方法: CN106955571A [P]. 2017年7月18日.
Li H Q, Meng Z H, Wang X R.A Device and Method for Simultaneous Desulfurization and Denitrification of Industrial Flue Gas Ozone by Step Oxidation and Absorption: CN106955571A [P]. 2017-07-18.
[22]王晨晔, 陈艳, 李会泉, 等.一种对钢渣作为吸收剂联合脱硫脱硝工艺产生的废液回收处理的方法: CN106830428A [P]. 2017年6月13日.
Wang C Y, Chen Y, Li H Q, et al.A Method for Recovery and Treatment of Waste Liquid from Desulfurization and Denitrification Process with Steel Slag as Absorbent : CN106830428A [P]. 2017-06-13.
[23]颜亚盟, 张仂.硫酸钙在盐水中的溶解度及溶度积实验研究[J].天津科技, 2014, 41(10):13-17
Yan Y M, Zhang L.Experimental study on the solubility and solubility of calcium sulfate in brine[J].Tianjin Science & Technology, 2014, 41(10):13-17

氧化法烟气脱硫脱硝废水回收NaNO₂工艺

Recovery technology of NaNO₂ from flue gas desulfurization and denitration wastewater by an oxidation process

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