NO_x空气氧化与反应吸收工艺实验研究
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摘要
本文针对工业NOx废气的治理，讨论了现有的NOx治理技术现状，提出采用空气氧化NO的工艺方法和采用碱吸收反应治理工业NOx废气的技术路线，并进行了实验研究和分析。在实验中，以某化工厂排放NOx污染物的组成为模拟对象，用NO和N2混合配气，用空气作为O2的来源对NOx废气中的NO进行氧化，达到一定的氧化度后进入碱液吸收塔测定NOx的吸收率。同时研究分析了氧化时间和NOx氧化度的关系，提出了利用空气氧化碱吸收法脱除工业NOx废气的工艺技术，研究结果用于工业NOx废气的治理是可行的。
This paper aims at the purification of industrial NOx waste gases, and discussed the actuality of existing technology in this field. The technical experimental courses that air oxidation of NO and reactive absorption of NOx waste gases with alkaline solution was brought forward in this paper, which was researched and analyzed through experiment. In the experiment, the simulation object of NOx waste gases was on the base of NOx waste gases expelled from some chemical plant. The NOx waste gases used in this experiment is the mixture of pure NO and industrial N2. The NO was oxidized by O2 of the air. After the ratio of oxidation of NOx is obtained in some extent, the NOx waste gases were absorbed with alkaline solutions in the tower of absorption. The absorptivity of NOx was mensurated. In the same time, the relation of oxidation time and ratio of oxidation of NOx was studied and analyzed on the basis of the data got between absorptivity and oxidation time in this experiment. The technology that oxidation of NO by air and absorption of NOx waste gases by alkaline solutions were brought forward according to the conclusion of this experiment, which seems to be a feasible method to deal with the industrial NOx waste gases.
This paper aims at the purification of industrial NOx waste gases, and discussed the actuality of existing technology in this field. The technical experimental courses that air oxidation of NO and reactive absorption of NOx waste gases with alkaline solution was brought forward in this paper, which was researched and analyzed through experiment. In the experiment, the simulation object of NOx waste gases was on the base of NOx waste gases expelled from some chemical plant. The NOx waste gases used in this experiment is the mixture of pure NO and industrial N2. The NO was oxidized by O2 of the air. After the ratio of oxidation of NOx is obtained in some extent, the NOx waste gases were absorbed with alkaline solutions in the tower of absorption. The absorptivity of NOx was mensurated. In the same time, the relation of oxidation time and ratio of oxidation of NOx was studied and analyzed on the basis of the data got between absorptivity and oxidation time in this experiment. The technology that oxidation of NO by air and absorption of NOx waste gases by alkaline solutions were brought forward according to the conclusion of this experiment, which seems to be a feasible method to deal with the industrial NOx waste gases.
引文
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[2] 童志权, 工业废气净化与利用, 北京: 化学工业出版社, 2001, 297~314.
[3] 顾永祥 等, 氢氧化钠水溶液吸收氧化氮传质－反应过程, 高校化学工程学报, 1990, 4 (2): 157.
[4] 张玉和, 氮氧化物气体的治理, 化工环保, 1985, 5 (2): 121.
[5] 吴无恙 等, 喷射吸收治理NOx、SO2、HCl废气, 流体工程, 1988: 46.
[6] 荣桂安, 林志祥, 纯碱液喷射吸收高浓度NO和NO2混合气体的研究, 化学
反应工程与工艺, 1990, 6 (3): 74~82.
[7] 周轲, 利用废氨水预处理尾气中NOx的探讨, 中氮肥, 1990, 6: 79~81.
[8] 徐维正(摘译), 用尿素净化烟道气的新工艺, 化工科技动态, 1994, 4: 41~43.
[9] 马双忱 等, 液相催化氧化脱除烟气中SO2和NOx的机理讨论, 华北电力大
学学报, 2001, 28 (4):75~79.
[10] Lefers, J.B., The oxidation and absorption of nitrogen oxides in nitric acid in relation to the tail gas problem of nitric acid plant. Chem. Eng. Sci. 1980, 35: 145~153.
[11] Carta, G., and Pigford, R.L., Absorption of nitric oxide in nitric acid and water. Ind. Eng. Chem. Fundam. 1983, 22: 329~335.
[12] David, G. et al, The reaction of hydrogen peroxide with nitrogen dioxide and nitric oxide. J. Phy. Chem. 1972, 76: 1919~1924.
[13] Sada, E. et al, Absorption of NO in aqueous solutions of KMnO4. Chem. Eng. Sci. 1977, 32: 1171~1175.
[14] Uchida, S. et al, Absorption of nitrogen monoxide into aqueous KMnO4/NaOH and NaSO3/FeSO4 solutions. Ind. Eng. Chem. Process. Des. Dev. 1983, 22: 323~329.
[15] 罗立新, 模拟烟气中一氧化氮富氧氧化的实验研究, 广西电力技术, 1997,(1): 15~19.
[16] 严宣申, NO和O2的反应, 化学教育, 2002, (7): 84.
[17] 罗立新 等, 富氧条件下NO氧化的初步研究, 电力环境保护, 1996, 12 (3): 6~10.
[18] Hirokazu, T. et al, Gas-phase oxidation of nitric oxide. Biology and Chemistry. 1999, 3(3): 191~198.
[19] Sloc, M., Kinetics of the reaction of nitric oxide with molecular oxygen. Nature. 1966, 209: 706.
[20] Dinerman, C. E., and Ewing, G. E., Infrared spectrum, structure, and heat of formation of gaseous (NO)2. J. Chem. Phys. 1970, 53: 626~631.
[21] Ogg, R. A., The mechanism of nitrogen pentoxide decomposition. J. Chem. Phys. 1947, 15: 337~338.
[22] Brown, F. B., and Crist, R. H., Further studies on the oxidation of nitric oxide. J. Chem. Phys. 1941, 9: 840~846.
[23] Treacy, J. C., and Daniels, F., Kinetic study of the oxidation of nitric oxide with oxygen in the pressure range 1 to 20 mm. J. Am. Chem. Soc. 1955, 77: 2033~2036.
[24] Ashmore, P. G. et al, Reaction of nitric oxide and oxygen. Trans. Faraday Soc. 1962, 58: 685~691.
[25] Glasson, W. A., and Tuesday, C. S., The atmospheric thermal oxidation of
nitric oxide. J. Am. Chem. Soc. 1963, 85: 2901~2904.
[26] Morrion, M. E. et al, Rate and mechanism of gas-phase oxidation of parts-per-million concentrations of nitric oxide. Ind. Eng. Chem. Fundam. 1966, 5: 175~181.
[27] Greig, J. D., and Hall, P. G., Thermal oxidation of nitric oxide at low concentrations. Trans. Faraday. Soc. 1967, 63: 655~661.
[28] Atkinson, R. et al, Evaluated kinetic and photochemical data for atmospheric chemistry. J. Phy. Chem. Ref. Data. 1992, 21: 1125~1568.
[29] Joshi, J. B., Absorption of NOx gases. Chem. Eng. Commun. 1985, 33: 1~92.
[30] Lee, Y. N., and Schwartz, S. E., Reaction kinetics of nitrogen dioxide with liquid water at low partial pressure. J. Phys. Chem. 1981, (85): 840~848.
[31] Komiyama, H., and Inoue, H., Absorption of nitrogen oxides into water. Chem. Eng. Sci. 1980, 35: 154~161.
[32] Carta. G., Role of HNO2 in the absorption of nitrogen oxides in alkaline solutions. Ind. Eng. Chem. Fundam. 1984, 23(2): 260~264.
[33] Kameoka, V., and Pigford, R. L., Absorption of nitrogen dioxide into water, sulfuric acid, sodium hydroxide, and alkaline sodium sulfite aqueous solutions. Ind. Eng. Chem. Fundam. 1977, 16: 163~169.
[34] 王树楹, 现代填料塔技术指南, 北京: 中国石化出版社, 1998, 77~78.
[35] 燃化部第六设计院编, 气液传质设备设计, 咸阳: 燃化部第六设计院五室, 1973, 66~69.
[36] 时钧 等主编, 化学工程手册(上卷， 第1篇)，北京: 化学工业出版社, 1996, 139~140.
[37] 童志权 等, 液相连续催化氧化碱吸收氮氧化物的研究, 湘潭大学自然科学学报, 1992, 14 (4): 126~131.
[38] 国家环境保护局编, 空气和废气监测分析方法, 北京: 中国环境科学出版社, 1990, 383~385.
[39] 刘乃鸿，工业塔新型规整填料应用手册，天津: 天津大学出版社, 1993, 44~46.
[40] 中国标准出版社总编室编，GB16297－1996，中国国家标准汇编(221)，北京: 中国标准出版社, 1997.
[2] 童志权, 工业废气净化与利用, 北京: 化学工业出版社, 2001, 297~314.
[3] 顾永祥 等, 氢氧化钠水溶液吸收氧化氮传质－反应过程, 高校化学工程学报, 1990, 4 (2): 157.
[4] 张玉和, 氮氧化物气体的治理, 化工环保, 1985, 5 (2): 121.
[5] 吴无恙 等, 喷射吸收治理NOx、SO2、HCl废气, 流体工程, 1988: 46.
[6] 荣桂安, 林志祥, 纯碱液喷射吸收高浓度NO和NO2混合气体的研究, 化学
反应工程与工艺, 1990, 6 (3): 74~82.
[7] 周轲, 利用废氨水预处理尾气中NOx的探讨, 中氮肥, 1990, 6: 79~81.
[8] 徐维正(摘译), 用尿素净化烟道气的新工艺, 化工科技动态, 1994, 4: 41~43.
[9] 马双忱 等, 液相催化氧化脱除烟气中SO2和NOx的机理讨论, 华北电力大
学学报, 2001, 28 (4):75~79.
[10] Lefers, J.B., The oxidation and absorption of nitrogen oxides in nitric acid in relation to the tail gas problem of nitric acid plant. Chem. Eng. Sci. 1980, 35: 145~153.
[11] Carta, G., and Pigford, R.L., Absorption of nitric oxide in nitric acid and water. Ind. Eng. Chem. Fundam. 1983, 22: 329~335.
[12] David, G. et al, The reaction of hydrogen peroxide with nitrogen dioxide and nitric oxide. J. Phy. Chem. 1972, 76: 1919~1924.
[13] Sada, E. et al, Absorption of NO in aqueous solutions of KMnO4. Chem. Eng. Sci. 1977, 32: 1171~1175.
[14] Uchida, S. et al, Absorption of nitrogen monoxide into aqueous KMnO4/NaOH and NaSO3/FeSO4 solutions. Ind. Eng. Chem. Process. Des. Dev. 1983, 22: 323~329.
[15] 罗立新, 模拟烟气中一氧化氮富氧氧化的实验研究, 广西电力技术, 1997,(1): 15~19.
[16] 严宣申, NO和O2的反应, 化学教育, 2002, (7): 84.
[17] 罗立新 等, 富氧条件下NO氧化的初步研究, 电力环境保护, 1996, 12 (3): 6~10.
[18] Hirokazu, T. et al, Gas-phase oxidation of nitric oxide. Biology and Chemistry. 1999, 3(3): 191~198.
[19] Sloc, M., Kinetics of the reaction of nitric oxide with molecular oxygen. Nature. 1966, 209: 706.
[20] Dinerman, C. E., and Ewing, G. E., Infrared spectrum, structure, and heat of formation of gaseous (NO)2. J. Chem. Phys. 1970, 53: 626~631.
[21] Ogg, R. A., The mechanism of nitrogen pentoxide decomposition. J. Chem. Phys. 1947, 15: 337~338.
[22] Brown, F. B., and Crist, R. H., Further studies on the oxidation of nitric oxide. J. Chem. Phys. 1941, 9: 840~846.
[23] Treacy, J. C., and Daniels, F., Kinetic study of the oxidation of nitric oxide with oxygen in the pressure range 1 to 20 mm. J. Am. Chem. Soc. 1955, 77: 2033~2036.
[24] Ashmore, P. G. et al, Reaction of nitric oxide and oxygen. Trans. Faraday Soc. 1962, 58: 685~691.
[25] Glasson, W. A., and Tuesday, C. S., The atmospheric thermal oxidation of
nitric oxide. J. Am. Chem. Soc. 1963, 85: 2901~2904.
[26] Morrion, M. E. et al, Rate and mechanism of gas-phase oxidation of parts-per-million concentrations of nitric oxide. Ind. Eng. Chem. Fundam. 1966, 5: 175~181.
[27] Greig, J. D., and Hall, P. G., Thermal oxidation of nitric oxide at low concentrations. Trans. Faraday. Soc. 1967, 63: 655~661.
[28] Atkinson, R. et al, Evaluated kinetic and photochemical data for atmospheric chemistry. J. Phy. Chem. Ref. Data. 1992, 21: 1125~1568.
[29] Joshi, J. B., Absorption of NOx gases. Chem. Eng. Commun. 1985, 33: 1~92.
[30] Lee, Y. N., and Schwartz, S. E., Reaction kinetics of nitrogen dioxide with liquid water at low partial pressure. J. Phys. Chem. 1981, (85): 840~848.
[31] Komiyama, H., and Inoue, H., Absorption of nitrogen oxides into water. Chem. Eng. Sci. 1980, 35: 154~161.
[32] Carta. G., Role of HNO2 in the absorption of nitrogen oxides in alkaline solutions. Ind. Eng. Chem. Fundam. 1984, 23(2): 260~264.
[33] Kameoka, V., and Pigford, R. L., Absorption of nitrogen dioxide into water, sulfuric acid, sodium hydroxide, and alkaline sodium sulfite aqueous solutions. Ind. Eng. Chem. Fundam. 1977, 16: 163~169.
[34] 王树楹, 现代填料塔技术指南, 北京: 中国石化出版社, 1998, 77~78.
[35] 燃化部第六设计院编, 气液传质设备设计, 咸阳: 燃化部第六设计院五室, 1973, 66~69.
[36] 时钧 等主编, 化学工程手册(上卷， 第1篇)，北京: 化学工业出版社, 1996, 139~140.
[37] 童志权 等, 液相连续催化氧化碱吸收氮氧化物的研究, 湘潭大学自然科学学报, 1992, 14 (4): 126~131.
[38] 国家环境保护局编, 空气和废气监测分析方法, 北京: 中国环境科学出版社, 1990, 383~385.
[39] 刘乃鸿，工业塔新型规整填料应用手册，天津: 天津大学出版社, 1993, 44~46.
[40] 中国标准出版社总编室编，GB16297－1996，中国国家标准汇编(221)，北京: 中国标准出版社, 1997.