Fe~(2+)/过氧化物体系氧化活性及其处理生活污水效果比较
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摘要
为了加快对分散性生活污水的有效治理,利用过氧化钙、过氧化镁及过氧化锌与Fe2+形成不同类芬顿体系,通过亚甲基蓝溶液在被氧化过程中的色度变化,考察了体系的氧化能力,在此基础上比较了体系对于生活污水中COD的去除效果。结果表明,在Fe2+/过氧化物为1∶2的最佳摩尔比下,pH越低,Fe2+/过氧化物的氧化能力越强;同时,过氧化物氧化亚甲基蓝过程可用一级反应动力学模型来拟合,比较过氧化钙、过氧化镁和过氧化锌,Fe2+/CaO2体系的氧化反应速率最大,其速率常数k可达2.55 min-1。用修正的Gompertz模型拟合表明,3种过氧化物在生活污水中释氧速率也是Fe2+/CaO2体系最快。摩尔比为1∶2的Fe2+/过氧化物体系在污水初始pH为3时,CaO2对污水COD的去除效果最好,COD的去除率达到74.9%;随着溶液pH的提高,MgO2、ZnO2对COD的作用受pH影响比CaO2更明显;Fe2+/过氧化物体系在自然酸度条件下对COD的去除表现为Fe2+的絮凝作用为主,当初始酸度调节至pH=5时,这一体系对COD的氧化作用明显加强。通过对Fe2+/过氧化物类芬顿体系作用与性能之比较,明确了Fe2+/CaO2更适合用于生活污水中COD的去除。
Peroxides, such as calcium peroxide, magnesium peroxide, and zinc peroxide, have been used as chemical reagents of the Fenton-like system. In this study, the oxidation ability of these compounds with Fe~(2+)was investigated by monitoring the color change of methylene blue in solutions, with a focus on the removal efficiency of the chemical oxygen demand(COD)in domestic sewage. Under the optimum molar ratio of Fe~(2+)to peroxides, 1∶2, the highest oxidation ability was reached and simulated with the first order kinetic equation.Comparing Fe~(2+)/MgO2, Fe~(2+)/ZnO2, and Fe~(2+)/CaO2, the reaction rate of the Fe~(2+)/CaO2-methylene blue system was the highest, with a constant rate of 2.55 min-1. Moreover, the fitting of the modified Gompertz model showed that the rate of oxygen release of Fe~(2+)/CaO2 among the three kinds of peroxides was also the highest. As a consequence, COD removal in domestic sewage by using Fe~(2+)/peroxides with a molar ratio of 1∶2 showed a maximum removal efficiency for COD, especially for wastewater at pH 3, where the removal rate of COD approached 74.9%.With increasing pH(>3.0), the removal of COD by MgO2 or ZnO2 was mainly affected by the pH of the domestic sewage. For the natural acidity, the removal of COD by Fe~(2+)/peroxide systems was mainly caused by the flocculation of Fe~(2+), and the oxidation ability of the system would be much stronger when the initial pH was adjusted to 5.0.
Peroxides, such as calcium peroxide, magnesium peroxide, and zinc peroxide, have been used as chemical reagents of the Fenton-like system. In this study, the oxidation ability of these compounds with Fe~(2+)was investigated by monitoring the color change of methylene blue in solutions, with a focus on the removal efficiency of the chemical oxygen demand(COD)in domestic sewage. Under the optimum molar ratio of Fe~(2+)to peroxides, 1∶2, the highest oxidation ability was reached and simulated with the first order kinetic equation.Comparing Fe~(2+)/MgO2, Fe~(2+)/ZnO2, and Fe~(2+)/CaO2, the reaction rate of the Fe~(2+)/CaO2-methylene blue system was the highest, with a constant rate of 2.55 min-1. Moreover, the fitting of the modified Gompertz model showed that the rate of oxygen release of Fe~(2+)/CaO2 among the three kinds of peroxides was also the highest. As a consequence, COD removal in domestic sewage by using Fe~(2+)/peroxides with a molar ratio of 1∶2 showed a maximum removal efficiency for COD, especially for wastewater at pH 3, where the removal rate of COD approached 74.9%.With increasing pH(>3.0), the removal of COD by MgO2 or ZnO2 was mainly affected by the pH of the domestic sewage. For the natural acidity, the removal of COD by Fe~(2+)/peroxide systems was mainly caused by the flocculation of Fe~(2+), and the oxidation ability of the system would be much stronger when the initial pH was adjusted to 5.0.
引文
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[14]徐苏云,何品晶,唐琼瑶,等. Fenton法处理类长填龄渗滤液的氧化和絮凝作用[J].环境科学研究, 2008, 21(4):20-24.XU Su-yun, HE Pin-jing, TANG Qiong-yao, et al. Roles of oxidation and coagulation during Fenton treatment of mature leachate[J]. Research of Environmental Sciences, 2008, 21(4):20-24.
[15] Zang C, Zhang X, Hu S, et al. The role of exposed facets in the Fenton-like reactivity of CeO2 nanocrystal to the OrangeⅡ[J]. Applied Catalysis B:Environmental, 2017, 216:106-113.
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[21]赵娜娜,于淼,汪群慧,等.乙醇预发酵对餐厨垃圾甲烷发酵动力学特性及底物的影响[J].环境工程, 2017, 35(1):108-122.ZHAO Na-na, YU Miao, WANG Qun-hui, et al. Effects of ethanol pre-fermentation on the kinetics and substrate of methane fermentation of food waste[J]. Environmental Engineering, 2017, 35(1):108-122.
[22] Yu W, Yang J, Shi Y, et al. Roles of iron species and pH optimization on sewage sludge conditioning with Fenton′s reagent and lime[J]. Water Research, 2016, 95:124-133.
[23] Kang Y W, Hwang K Y. Effects of reaction could conditions on the oxidation efficiency in the Fenton process[J]. Water Research, 2000, 34:2786-2790.
[24] Wang H, Zhao Y, Li T, et al. Properties of calcium peroxide for release of hydrogen peroxide and oxygen:A kinetics study[J]. Chemical Engineering Journal, 2016, 303:450-457.
[25] Lu W H, Xiang X Q, Yang L, et al. The temporal-spatial distribution and changes of dissolved oxygen in the Changjiang Estuary and its adjacent waters for the last 50 a[J]. Acta Oceanologica Sinica, 2017, 36(5):90-98.
[26]张盛汉,谭德俊,陈泉源.硫酸亚铁/过硫酸钾体系深度处理印染废水[J].东华大学学报(自然科学版), 2013, 39(6):814-817.ZHANG Sheng-han, TAN De-jun, CHEN Quan-yuan. Application of ferrous sulphate/potassium peroxydisulfate in dyeing wastewater tertiary treatment[J]. Journal of Donghua University(Natural Science Edition), 2013, 39(6):814-817.
[27] Esch T R, Bredow T. Bulk and surface properties of magnesium peroxide MgO2[J]. Applied Surface Science, 2016, 389:1202-1207.
[28] Ginos A, Manios T, Mantzavinos D. Treatment of olive mill effluents by coagulation-flocculation-hydrogen peroxide oxidation and effect on phytotoxicity[J]. Journal of Hazardous Materials, 2006, 133(1):135-142.
[29]黄雪.过氧化物对生活污水的处理及其效果研究[D].武汉:华中农业大学, 2016.HUANG Xue. The study of effects on treating sewage with peroxides[D]. Wuhan:Huazhong Agricultural University, 2016
[30] Chen Z, Zhang W J, Wang D S, et al. Enhancement of waste activated sludge dewaterability using calcium peroxide pre-oxidation and chemical re-flocculation[J]. Water Research, 2016, 103:170-181.
[31] Gulkaya I, Surucu G A, Dilek F B. Importance of H2O2/Fe2+ratio in Fenton′s treatment of a carpet dyeing wastewater[J]. Journal of Hazardous Materials, 2006, 136(3):763-769.
[32] Maurer D L, Koziel J A, Bruning K, et al. Farm-scale testing of soybean peroxidase and calcium peroxide for surficial swine manure treatment and mitigation of odorous VOCs, ammonia and hydrogen sulfide emissions[J]. Atmospheric Environment, 2017, 166:467-478.
[2] Tang J, Shi T Z, Wu X W, et al. The occurrence and distribution of antibiotics in Lake Chaohu, China:Seasonal variation, potential source and risk assessment[J]. Chemosphere, 2015, 122:154-161.
[3] Hayley A, Deborah K, Melinda J. Quantification of human-associated fecal indicators reveal sewage from urban watersheds as a source of pollution to Lake Michigan[J]. Water Research, 2016, 100:556-567.
[4] Shannon M A, Bohn P W, Elimelech M, et al. Science and technology for water purification in the coming decades[J]. Nature, 2008, 452:301-310.
[5]王妙,张华俊,陈海峰,等.沸石联合过氧化钙对黑臭河道底泥营养盐释放的作用研究[J].广东化工, 2017, 44(342):36-37.WANG Miao, ZHANG Hua-jun, CHEN Hai-feng, et al. The control of zeolite combined with calcium peroxide on nutrients release from sediment in malodorous rivers[J]. Guangdong Chemical Industry, 2017, 44(342):36-37.
[6]王熙,孙飞云,董文艺.用过氧化钙控制城市河道底泥嗅味物质及氮磷释放试验研究[J].水利水电技术, 2012, 43(8):66-69.WANG Xi, SUN Fei-yun, DONG Wen-yi. The experimental study on the control of the odor substances, nitrogen and phosphorus release in sediment of urban river channel with calcium peroxide[J]. Water Resources and Hydropower Engineering, 2012, 43(8):66-69.
[7] Nyk?nen A, Kontio H, Klutas O, et al. Increasing lake water and sediment oxygen levels using slow release peroxide[J]. Science of the Total Environment, 2012, 429:317-324.
[8] Wang H F, Zhao Y S, Li T Y, et al. Properties of calcium peroxide for release of hydrogen peroxide and oxygen:A kinetics study[J]. Chemical Engineering Journal, 2016, 303:450-457.
[9] Zhang X, Gu X G, Lu S G, et al. Application of calcium peroxide activated with Fe(Ⅱ)-EDDS complex in trichloroethylene degradation[J].Chemosphere, 2016, 160:1-6.
[10] Xue Y F, Gu X G, Lu S G, et al. The destruction of benzene by calcium peroxide activated with Fe(Ⅱ)in water[J]. Chemical Engineering Journal, 2016, 302:187-193.
[11] Qian Y J, Zhang J, Zhang Y L, et al. Degradation of 2, 4-dichlorophenol by nanoscale calcium peroxide:Implication for groundwater remediation[J]. Separation and Purification Technology, 2016, 166:222-229.
[12] Goi A, Viisimaa M, Trapido M, et al. Polychlorinated biphenyls-containing electrical insulating oil contaminated soil treatment with calcium and magnesium peroxides[J]. Chemosphere, 2011, 82:1196-1201.
[13]翟永清,于士文,姚子华,等. CaO2/H+/FeSO4体系处理染料废水的研究[J].工业水处理, 2003(10):24-26.ZHAI Yong-qing, YU Shi-wen, YAO Zi-hua, et al. Study on the treatment of dye wastewater by CaO2/H+/FeSO4 system[J]. Industrial Water Treatment, 2003(10):24-26.
[14]徐苏云,何品晶,唐琼瑶,等. Fenton法处理类长填龄渗滤液的氧化和絮凝作用[J].环境科学研究, 2008, 21(4):20-24.XU Su-yun, HE Pin-jing, TANG Qiong-yao, et al. Roles of oxidation and coagulation during Fenton treatment of mature leachate[J]. Research of Environmental Sciences, 2008, 21(4):20-24.
[15] Zang C, Zhang X, Hu S, et al. The role of exposed facets in the Fenton-like reactivity of CeO2 nanocrystal to the OrangeⅡ[J]. Applied Catalysis B:Environmental, 2017, 216:106-113.
[16] Arienzo M. Degradation of 2, 4, 6-trinitrotoluene in water and soil slurry utilizing a calcium peroxide compound[J]. Chemosphere, 2000,40(4):331-337.
[17] Zhang X, Gu X G, Lu S G, et al. Degradation of trichloroethylene in aqueous solution by calcium peroxide activated with ferrous ion[J].Journal of Hazardous Materials, 2015, 284:253-260.
[18] Northup A, Cassidy D. Calcium peroxide(CaO2)for use in modified Fenton chemistry[J]. Journal of Hazardous Materials, 2008, 152(3):1164-1170.
[19]刘娇,孟范平,王震宇.亚甲基蓝光度法研究基于CaO2的Fenton反应条件[J].化工学报, 2011, 62(9):2521-2525.LIU Jiao, MENG Fan-ping, WANG Zhen-yu. Study on condition of CaO2-based Fenton reaction by methylene blue spectrophotometric method[J]. CIESC Journal, 2011, 62(9):2521-2525.
[20]国家环境保护总局.水和废水监测分析方法(第四版)[M].北京:中国环境科学出版社, 2002.State Environmental Protection Administration. Method for monitoring and analyzing water and wastewater[M]. 4th Edition. Beijing:China Environmental Science Press, 2002.
[21]赵娜娜,于淼,汪群慧,等.乙醇预发酵对餐厨垃圾甲烷发酵动力学特性及底物的影响[J].环境工程, 2017, 35(1):108-122.ZHAO Na-na, YU Miao, WANG Qun-hui, et al. Effects of ethanol pre-fermentation on the kinetics and substrate of methane fermentation of food waste[J]. Environmental Engineering, 2017, 35(1):108-122.
[22] Yu W, Yang J, Shi Y, et al. Roles of iron species and pH optimization on sewage sludge conditioning with Fenton′s reagent and lime[J]. Water Research, 2016, 95:124-133.
[23] Kang Y W, Hwang K Y. Effects of reaction could conditions on the oxidation efficiency in the Fenton process[J]. Water Research, 2000, 34:2786-2790.
[24] Wang H, Zhao Y, Li T, et al. Properties of calcium peroxide for release of hydrogen peroxide and oxygen:A kinetics study[J]. Chemical Engineering Journal, 2016, 303:450-457.
[25] Lu W H, Xiang X Q, Yang L, et al. The temporal-spatial distribution and changes of dissolved oxygen in the Changjiang Estuary and its adjacent waters for the last 50 a[J]. Acta Oceanologica Sinica, 2017, 36(5):90-98.
[26]张盛汉,谭德俊,陈泉源.硫酸亚铁/过硫酸钾体系深度处理印染废水[J].东华大学学报(自然科学版), 2013, 39(6):814-817.ZHANG Sheng-han, TAN De-jun, CHEN Quan-yuan. Application of ferrous sulphate/potassium peroxydisulfate in dyeing wastewater tertiary treatment[J]. Journal of Donghua University(Natural Science Edition), 2013, 39(6):814-817.
[27] Esch T R, Bredow T. Bulk and surface properties of magnesium peroxide MgO2[J]. Applied Surface Science, 2016, 389:1202-1207.
[28] Ginos A, Manios T, Mantzavinos D. Treatment of olive mill effluents by coagulation-flocculation-hydrogen peroxide oxidation and effect on phytotoxicity[J]. Journal of Hazardous Materials, 2006, 133(1):135-142.
[29]黄雪.过氧化物对生活污水的处理及其效果研究[D].武汉:华中农业大学, 2016.HUANG Xue. The study of effects on treating sewage with peroxides[D]. Wuhan:Huazhong Agricultural University, 2016
[30] Chen Z, Zhang W J, Wang D S, et al. Enhancement of waste activated sludge dewaterability using calcium peroxide pre-oxidation and chemical re-flocculation[J]. Water Research, 2016, 103:170-181.
[31] Gulkaya I, Surucu G A, Dilek F B. Importance of H2O2/Fe2+ratio in Fenton′s treatment of a carpet dyeing wastewater[J]. Journal of Hazardous Materials, 2006, 136(3):763-769.
[32] Maurer D L, Koziel J A, Bruning K, et al. Farm-scale testing of soybean peroxidase and calcium peroxide for surficial swine manure treatment and mitigation of odorous VOCs, ammonia and hydrogen sulfide emissions[J]. Atmospheric Environment, 2017, 166:467-478.