化学破乳-Fenton氧化处理乳化液废水
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摘要
采用化学破乳-Fenton试剂处理乳化液废水,考察了相关因素对处理效果的影响特点和规律。实验结果表明,酸化作用中,静电作用对破乳有着关键性影响,降低乳化液废水p H值,有利于乳化液废水的油水分离;混凝剂投加量和废水p H值直接决定着破乳效果,油滴分散体系脱稳的适宜p H值既能使油滴间静电斥力较小,又能使大分子量的、大比表面积的多核络合离子通过电中和、吸附架桥、卷扫的作用来强化油水分散体系脱稳。Fenton氧化中,对于特定的Fe2+浓度,随着n(H2O2)/n(Fe2+)增加,COD去除程度增加,但增加的幅度越来越小,同时COD去除率达到稳定所需要的时间相应增加,适宜的摩尔比为20;废水Fenton体系H2O2开始阶段急速降低然后趋于平缓,体系Fe2+反应开始很短时间内急剧降低并趋于某一稳定值,H2O2浓度、Fe2+浓度随时间变化遵循一级反应动力学模型。
The chemical demulsification-Fenton oxidation was used for the treatment of emulsion wastewater. The characteristics and laws of related factors on treatment effect were investigated. The results showed that electrostatic effect had a critical impact on demulsification,and low p H was advantageous to the oilwater separation of emulsion wastewater in acidification. The dosing amount of coagulant and the p H value of wastewater had a critical impact on demulsification. The appropriate p H value condition of unstability of oil droplets dispersed system should be as follows: smaller electrostatic repulsion between oil droplets,the existence of multi-core complexing ions having large molecular weight and specific surface. The multi-core complexing ions could strengthen the unstability of oil-water dispersions by charge neutralization,adsorption bridging and furl mechanism. In the Fenton oxidation system,the COD removal rate increased with the increase of H2O2/ Fe2 +ratio for a certain Fe2 +dosage,but the increase rate tended to be reduced. Meanwhile,the required time of COD removal rate reaching stability increased correspondingly,and the suitable molar ratio of the H2O2/ Fe2 +was 20. In the wastewater Fenton system,H2O2 concentration decreased drastically and then began to flatten,and Fe2 +concentration fell sharply in a very short time and tended to be a stable value. The change of H2O2,Fe2 +concentration with time conformed to the first order reaction kinetics model.
The chemical demulsification-Fenton oxidation was used for the treatment of emulsion wastewater. The characteristics and laws of related factors on treatment effect were investigated. The results showed that electrostatic effect had a critical impact on demulsification,and low p H was advantageous to the oilwater separation of emulsion wastewater in acidification. The dosing amount of coagulant and the p H value of wastewater had a critical impact on demulsification. The appropriate p H value condition of unstability of oil droplets dispersed system should be as follows: smaller electrostatic repulsion between oil droplets,the existence of multi-core complexing ions having large molecular weight and specific surface. The multi-core complexing ions could strengthen the unstability of oil-water dispersions by charge neutralization,adsorption bridging and furl mechanism. In the Fenton oxidation system,the COD removal rate increased with the increase of H2O2/ Fe2 +ratio for a certain Fe2 +dosage,but the increase rate tended to be reduced. Meanwhile,the required time of COD removal rate reaching stability increased correspondingly,and the suitable molar ratio of the H2O2/ Fe2 +was 20. In the wastewater Fenton system,H2O2 concentration decreased drastically and then began to flatten,and Fe2 +concentration fell sharply in a very short time and tended to be a stable value. The change of H2O2,Fe2 +concentration with time conformed to the first order reaction kinetics model.
引文
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[10]姚群峰,徐顺清,周宜开,等.邻菲罗啉分光光度法测定铁的价态.中国卫生检验杂志,2000,10(1):3-5Yao Qunfeng,Xu Shunqing,Zhou Yikai,et al.Spectrophotometric determination of Iron Valency states with 1,10-phenanthroline.Chinese Journal of Health Laboratory Technology,2000,10(1):3-5(in Chinese)
[11]张乃东,郑威,彭永臻.褪色光度法测定芬顿体系中产生的羟自由基.分析化学,2003,31(5):552-554Zhang Naidong,Zheng Wei,Peng Yongzhen.Determination of hydroxyl radical in Fenton system by decoloring spectrophotometry.Chinese Journal of Analytical Chemistry,2003,31(5):552-554(in Chinese)
[12]徐晓军.化学絮凝剂作用原理.北京:科学出版社,2005
[13]Neyens E.,Baeyens J.A review of classic Fenton’s peroxidation as an advanced oxidation technique.Journal of Hazardous Materials,2003,98(1-3):33-50
[14]杨林.Fenton氧化处理染料废水过程的特征研究.重庆:重庆大学硕士学位论文,2012Yang Lin.The characteristics study on degradation of dye wastewater process by Fenton oxidation.Chongqing:Master Dissertation of Chongqing University,2012(in Chinese)
[15]李再兴,左剑恶,剧盼盼,等.Fenton氧化法深度处理抗生素废水二级出水.环境工程学报,2013,7(1):132-136Li Zaixing,Zuo Jian’e,Ju Panpan,et al.Advanced treatment of secondary effluent of antibiotic wastewater using Fenton oxidation method.Chinese Journal of Environmental Engineering,2013,7(1):132-136(in Chinese)
[2]Ríos G.,Pazos C.,Coca J.Destabilization of cutting oil emulsions using inorganic salts as coagulants.Colloids and Surfaces A:Physicochemical and Engineering Aspects,1998,138(2-3):383-389
[3]Bensadok K.,Belkacem M.,Nezzal G.Treatment of cutting oil/water emulsion by coupling coagulation and dis-solved air floatation.Desalination,2007,206(1-3):440-448
[4]Chakrabarty B.,Ghoshal A.K.,Purkait M.K.Crossflow ultrafiltration of stable oil-in-water emulsion using polysulfone membranes.Chemical Engineering Journal,2010,165(2):447-456
[5]Yuan Songhu,Tong Man,Wu Gaoming,Destabilization of emulsions by natural minerals.Journal of Hazardous Materials,2011,192(3):1882-1885
[6]刘新宇,刘宇红.含油乳化废水的破乳方法.内蒙古石油化工,2007,(8):401-402Liu Yuxin,Liu Yuhong.Demulsification of emulsified oil wastewater.Inner Mongolia Petrochemical Industry,2007,(8):401-402(in Chinese)
[7]刘国强,王铎,王立国,等.膜技术处理含油废水的研究.膜科学与技术,2007,27(1):68-72Liu Guoqiang,Wang Duo,Wang Liguo,et al.Membrane technologies applied to oily wastewater treatment.Membrane Science and Technology,2007,27(1):68-72(in Chinese)
[8]刘宏.化学破乳特性与高分子聚合物破乳.工业水处理,2000:20(9):22-24Liu Hong.Researches on the influence factors of chemical demulsification and demulsification of high polymer.Industrial Water Treatment,2000:20(9):22-24(in Chinese)
[9]姜成春,庞素艳,马军,等.钛盐光度法测定Fenton氧化中的过氧化氢.中国给水排水,2006,22(4):88-91Jiang Chengchun,Pang Suyan,Ma Jun,et al.Spectrophotometric determination of hydrogen peroxide in Fenton reaction with titanium oxalate.China Water&Wastewater,2006,22(4):88-91(in Chinese)
[10]姚群峰,徐顺清,周宜开,等.邻菲罗啉分光光度法测定铁的价态.中国卫生检验杂志,2000,10(1):3-5Yao Qunfeng,Xu Shunqing,Zhou Yikai,et al.Spectrophotometric determination of Iron Valency states with 1,10-phenanthroline.Chinese Journal of Health Laboratory Technology,2000,10(1):3-5(in Chinese)
[11]张乃东,郑威,彭永臻.褪色光度法测定芬顿体系中产生的羟自由基.分析化学,2003,31(5):552-554Zhang Naidong,Zheng Wei,Peng Yongzhen.Determination of hydroxyl radical in Fenton system by decoloring spectrophotometry.Chinese Journal of Analytical Chemistry,2003,31(5):552-554(in Chinese)
[12]徐晓军.化学絮凝剂作用原理.北京:科学出版社,2005
[13]Neyens E.,Baeyens J.A review of classic Fenton’s peroxidation as an advanced oxidation technique.Journal of Hazardous Materials,2003,98(1-3):33-50
[14]杨林.Fenton氧化处理染料废水过程的特征研究.重庆:重庆大学硕士学位论文,2012Yang Lin.The characteristics study on degradation of dye wastewater process by Fenton oxidation.Chongqing:Master Dissertation of Chongqing University,2012(in Chinese)
[15]李再兴,左剑恶,剧盼盼,等.Fenton氧化法深度处理抗生素废水二级出水.环境工程学报,2013,7(1):132-136Li Zaixing,Zuo Jian’e,Ju Panpan,et al.Advanced treatment of secondary effluent of antibiotic wastewater using Fenton oxidation method.Chinese Journal of Environmental Engineering,2013,7(1):132-136(in Chinese)