造纸废水Fenton深度处理工艺的升级改造
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摘要
针对Fenton氧化法深度处理造纸废水生化出水COD不达标的问题,本文提出Fenton氧化-活性炭吸附、Fenton活性炭复配、锰粉催化Fenton三种可行的升级改造工艺对其进行深度处理,并利用紫外可见和红外分析技术对造纸废水生化出水处理前后的水质变化进行了研究.实验结果表明:在最佳工艺运行条件下,三种升级改造工艺使出水COD浓度分别降至40 mg/L、33 mg/L、24 mg/L;紫外可见和红外光谱分析得出改造工艺对废水中的芳香族化合物、酚类、醇类等难降解污染物均有较好的去除效果;在满足排放标准(GB3544-2008)所规定的COD限值情况下,改造后的锰粉催化Fenton的药剂费用是0.947元/m~3,比传统Fenton法节约0.097元/m~3.因此,锰粉催化Fenton技术是比较经济高效的深度处理技术,能达到改造目的.
Advanced treatment of papermaking wastewater by Fenton process can not meet currently imposed regulations.In this study,the effluent from aeration tank was treated using various modified Fenton processes.The combination of Fenton oxidation and activated carbon adsorption Fenton reagent with activated carbon powder,Fenton oxidation catalyzed by manganese dioxide were brought forward and investigated respectively for the advanced treatment of papermaking wastewater.The results showed that after the treatment of the combination of upgrading Fenton processes,the effluent COD were reduced to 40 mg/L,33 mg/L,24 mg/L,respectively with the optimal conditions.The UV-Vis and IR spectroscopy results revealed the changes of organic matter before and after modified Fenton process.It was found that the main organic matter in wastewater such as phenols,alcohols and other non-degradable pollutants was able to be removed efficiently after treatment.The analysis of the cost of the three modified Fenton process showed that Fenton oxidation catalyzed by manganese dioxide is 0.947 yuan/m~3,which is 0.097 yuan/m~3 less than the traditional Fenton process.Therefore,Fenton oxidation catalyzed by manganese dioxide is a more cost-effective advanced treatment technology.
Advanced treatment of papermaking wastewater by Fenton process can not meet currently imposed regulations.In this study,the effluent from aeration tank was treated using various modified Fenton processes.The combination of Fenton oxidation and activated carbon adsorption Fenton reagent with activated carbon powder,Fenton oxidation catalyzed by manganese dioxide were brought forward and investigated respectively for the advanced treatment of papermaking wastewater.The results showed that after the treatment of the combination of upgrading Fenton processes,the effluent COD were reduced to 40 mg/L,33 mg/L,24 mg/L,respectively with the optimal conditions.The UV-Vis and IR spectroscopy results revealed the changes of organic matter before and after modified Fenton process.It was found that the main organic matter in wastewater such as phenols,alcohols and other non-degradable pollutants was able to be removed efficiently after treatment.The analysis of the cost of the three modified Fenton process showed that Fenton oxidation catalyzed by manganese dioxide is 0.947 yuan/m~3,which is 0.097 yuan/m~3 less than the traditional Fenton process.Therefore,Fenton oxidation catalyzed by manganese dioxide is a more cost-effective advanced treatment technology.
引文
[1] 陈得重.制浆造纸废水处理的发展现状及趋势[J].云南化工,2018,45(3):177-178.
[2] 田晓宇.Fenton-NaclO 法联用深度处理造纸废水实验研究[D].大连:大连海事大学,2015.
[3] 张安龙,张佳晔,罗清,等.酶促Fenton法处理造纸废水的研究[J].陕西科技大学学报,2018,36(2):15-20.
[4] Abou Elela S I,Ali M E M,Ibrahim H S.Combined treatment of retting flax wastewater using Fenton oxidation and granular activated carbon[J].Arabian Journal of Chemistry,2016,9(1):511-517.
[5] 张家明,王丽萍,邹红,等.Fenton试剂和活性炭复配对印染废水的深度处理研究[J].安徽大学学报(自然科学版),2018,42(4):87-92.
[6] 陈立群,张永刚.MnO2催化Fenton试剂降解苯酚废水[J].环境工程学报,2012,6(11):4 047-4 052.
[7] 周敬红,章志萍,王双飞.造纸废水生化处理出水UV/TiO2深度处理研究[J].广西大学学报(自然科学版),2011,36(2):353-357.
[8] 郗文君.生物促生剂强化造纸废水降解效能的研究[D].西安:陕西科技大学,2016.
[9] 王艳,马梦娟,宋朝霞,等.芝麻秆制备的活性炭对废水中铜离子的吸附[J].河南工程学院学报(自然科学版),2018,30(1):41-44.
[10] Brink A,Sheridan C M,Harding K G.The Fenton oxidation of biologically treated paper and pulp mill effluents:A performance and kinetic study[J].Process Safety and Environment Protection,2017,11(2):206-215.
[11] 杨晶.复合非均相催化剂的制备及深度处理印染废水的研究[D].广州:华南理工大学,2018.
[12] Carrasco Díaz M R,Castillejos Lopez E,Cerpa Naranjo E,et al.On the textural and crystalline properties of Fe-carbon xerogels.Application as Fenton-like catalysts in the oxidation of paracetamol by H2O2[J].Microporous and Mesoporous Materials,2017,237(1):282-293.
[13] Wang G,Zhao D Y,Kou F Y,et al.Removal of norfloxacin by surface Fenton system (MnFe2O4/H2O2) Kinetics,mechanism and degradation pathway[J].Chemical Engineering Journal,2018,351(1):747-755.
[14] Zhang X B,Dong G X,Hao Z C,et al,Fe-Mn/MCM-41 preparation,characterization,and catalytic activity for methyl orange in the process of heterogeneous Fenton reaction[J].Transactions of Tianjin University,2018,24(4):361-369.
[15] Zhang Z W,Lei L C,Xu S J.Heterogeneous UV/Fenton catalytic degradation of wastewater containing phenol with Fe-Cu-Mn-Y catalyst[J].Journal of Zhejiang University Science,2004,25(2):78-83.
[2] 田晓宇.Fenton-NaclO 法联用深度处理造纸废水实验研究[D].大连:大连海事大学,2015.
[3] 张安龙,张佳晔,罗清,等.酶促Fenton法处理造纸废水的研究[J].陕西科技大学学报,2018,36(2):15-20.
[4] Abou Elela S I,Ali M E M,Ibrahim H S.Combined treatment of retting flax wastewater using Fenton oxidation and granular activated carbon[J].Arabian Journal of Chemistry,2016,9(1):511-517.
[5] 张家明,王丽萍,邹红,等.Fenton试剂和活性炭复配对印染废水的深度处理研究[J].安徽大学学报(自然科学版),2018,42(4):87-92.
[6] 陈立群,张永刚.MnO2催化Fenton试剂降解苯酚废水[J].环境工程学报,2012,6(11):4 047-4 052.
[7] 周敬红,章志萍,王双飞.造纸废水生化处理出水UV/TiO2深度处理研究[J].广西大学学报(自然科学版),2011,36(2):353-357.
[8] 郗文君.生物促生剂强化造纸废水降解效能的研究[D].西安:陕西科技大学,2016.
[9] 王艳,马梦娟,宋朝霞,等.芝麻秆制备的活性炭对废水中铜离子的吸附[J].河南工程学院学报(自然科学版),2018,30(1):41-44.
[10] Brink A,Sheridan C M,Harding K G.The Fenton oxidation of biologically treated paper and pulp mill effluents:A performance and kinetic study[J].Process Safety and Environment Protection,2017,11(2):206-215.
[11] 杨晶.复合非均相催化剂的制备及深度处理印染废水的研究[D].广州:华南理工大学,2018.
[12] Carrasco Díaz M R,Castillejos Lopez E,Cerpa Naranjo E,et al.On the textural and crystalline properties of Fe-carbon xerogels.Application as Fenton-like catalysts in the oxidation of paracetamol by H2O2[J].Microporous and Mesoporous Materials,2017,237(1):282-293.
[13] Wang G,Zhao D Y,Kou F Y,et al.Removal of norfloxacin by surface Fenton system (MnFe2O4/H2O2) Kinetics,mechanism and degradation pathway[J].Chemical Engineering Journal,2018,351(1):747-755.
[14] Zhang X B,Dong G X,Hao Z C,et al,Fe-Mn/MCM-41 preparation,characterization,and catalytic activity for methyl orange in the process of heterogeneous Fenton reaction[J].Transactions of Tianjin University,2018,24(4):361-369.
[15] Zhang Z W,Lei L C,Xu S J.Heterogeneous UV/Fenton catalytic degradation of wastewater containing phenol with Fe-Cu-Mn-Y catalyst[J].Journal of Zhejiang University Science,2004,25(2):78-83.
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