焦粉吸附深度处理焦化废水研究
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摘要
为解决焦化废水经常规生化处理后污染指标不符合排放标准的问题,将焦化厂生产过程中自身产生的焦粉用于焦化厂废水处理工艺中生化出水的深度处理环节,考察了焦粉投加量、焦粉粒径、溶液pH值、吸附时间对焦化废水COD和色度去除率的影响,通过正交试验设计优化了工艺条件得到最优工艺方案,最后采用SEM-EDX对比分析了焦粉使用前后的形貌变化及表面元素分布。结果表明:焦粉投加量从40 g/L增至120 g/L时,COD和色度去除率显著提高;焦粉投加量大于120 g/L时,两者去除率增速减缓,投加量超过200 g/L后,两者去除率基本稳定。焦粉粒径超过5～6 mm后,COD和色度去除率基本稳定不变。焦化废水p H值调节至8附近时,两者去除率达到最大值。吸附时间从0. 5 h逐渐增加到2. 5 h时,COD和色度去除率显著提高;超过2. 5 h后,两者去除率基本稳定。通过L18(37)正交设计试验设计优化的最佳方案为焦粉投加量200 g/L,焦粉粒径5～6 mm,溶液p H值8,吸附时间3 h;在优化条件下的多次平行试验表明,COD平均去除率达到66. 8%,色度平均去除率达到71. 2%。SEM-EDX表征显示,吸附前,焦粉孔径大,表面有较大缝隙,吸附后孔径和缝隙明显减小,分析原因可能是有较多物质附着在焦粉表面及孔道内造成。吸附后焦粉表面碳、氧、硫、氮元素相对含量大幅增加,这说明焦粉对焦化废水中的有机物和部分含硫、含氮物质具有较好的吸附性能。
In order to solve the unqualified discharge standard of coking plant wastewater after conventional biochemical treatment,the coke powder produced by the coking plant was used in the advanced treatment of biochemical effluent in the wastewater treatment process of coking plant.The effects of coke powder dosage,solution p H value,particle size,and adsorption time on the removal rates of COD and chroma in coking wastewater were investigated.The optimal process plan was obtained by orthogonal experimental design,and the morphology and surface element distribution of coke powder before and after use were analyzed by SEM-EDX. The results show that the removal rates of COD and chroma increases significantly when the coke powder dosage increases from 40 g/L to 120 g/L.To further increase the coke powder dosage,the increase of the removal rates of both COD and chroma are slow down and then remained stable when the dosage of coke powder is more than 200 g/L.When the size of coke powder exceeds 5-6 mm,the removal rates of COD and chroma are stable,and the removal rates of both reach the maximum with solution p H value of 8. Besides,the removal rates of COD and chroma improve remarkably when the adsorption time prolonges from 0.5 h to 2.5 h and then will be stable as the adsorption time further increased.The optimum design of dosage of coke powder,the diameter of coke powder,the p H value and the adsorption time are 200 g/L,5 mm,8 and 3 h,respectively,based on the L18( 37) orthogonal design.The results of several parallel experiments in the optimized conditions show that the average removal rates of COD and chroma are 66.8%,and 71.2%,respectively.The SEM-EDX characterization results show that the pore size of coke powder is large,and there are large cracks on the surface before adsorption.While the pore size and cracks are obviously reduced due to the adhesion of abundant substances to the surface and pore channel of coke powder after adsorption.The relative contents of carbon,oxygen,sulfur,and nitrogen on the surface of coke powder increase greatly,indicating the good performance of coke powder on adsorption organic matter and part of sulfur and nitrogen-containing substances in coking wastewater.
In order to solve the unqualified discharge standard of coking plant wastewater after conventional biochemical treatment,the coke powder produced by the coking plant was used in the advanced treatment of biochemical effluent in the wastewater treatment process of coking plant.The effects of coke powder dosage,solution p H value,particle size,and adsorption time on the removal rates of COD and chroma in coking wastewater were investigated.The optimal process plan was obtained by orthogonal experimental design,and the morphology and surface element distribution of coke powder before and after use were analyzed by SEM-EDX. The results show that the removal rates of COD and chroma increases significantly when the coke powder dosage increases from 40 g/L to 120 g/L.To further increase the coke powder dosage,the increase of the removal rates of both COD and chroma are slow down and then remained stable when the dosage of coke powder is more than 200 g/L.When the size of coke powder exceeds 5-6 mm,the removal rates of COD and chroma are stable,and the removal rates of both reach the maximum with solution p H value of 8. Besides,the removal rates of COD and chroma improve remarkably when the adsorption time prolonges from 0.5 h to 2.5 h and then will be stable as the adsorption time further increased.The optimum design of dosage of coke powder,the diameter of coke powder,the p H value and the adsorption time are 200 g/L,5 mm,8 and 3 h,respectively,based on the L18( 37) orthogonal design.The results of several parallel experiments in the optimized conditions show that the average removal rates of COD and chroma are 66.8%,and 71.2%,respectively.The SEM-EDX characterization results show that the pore size of coke powder is large,and there are large cracks on the surface before adsorption.While the pore size and cracks are obviously reduced due to the adhesion of abundant substances to the surface and pore channel of coke powder after adsorption.The relative contents of carbon,oxygen,sulfur,and nitrogen on the surface of coke powder increase greatly,indicating the good performance of coke powder on adsorption organic matter and part of sulfur and nitrogen-containing substances in coking wastewater.
引文
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[14]刘红,张林霞,吴克明.吸附-氧化法处理焦化废水的研究[J].工业水处理,2003,23(5):35-37.LIU Hong,ZHANG Linxia,WU Keming. Study on the treatmentof coke plant wastewater by adsorption catalytic oxidation process[J].Industrial Water Treatment,2003,23(5):35-37.
[15]国家环境保护总局《水和废水监测分析方法》编委会.水和废水监测分析方法[M].4版.北京:中国环境科学出版社,2010:102-103.
[16]吴声彪,肖波,史晓燕,等.粉末活性炭法去除焦化废水中的COD[J].化工环保,2004,24(6):221-223.WU Shengbiao,XIAO Bo,SHI Xiaoyan,et al. Removal of CODfrom coking wastewater by powdered activated carbon[J]. Envi-ronmental Protection of Chemical Industry,2004,24(6):221-223.
[17]刘宪,李娅,沈毅,等.焦粉吸附法深度处理焦化生化废水的研究[J].工业安全与环保,2008,34(11):19-22.LIU Xian,LI Ya,SHEN Yi,et al. Study on coking wastewatertreatment by adsorption with dry extinguishing coke powder[J].Industrial Safety and Environmental Protection,2008,34(11):19-22.
[18]刘剑平,徐焱,李静,等.吸附法处理焦化尾水的实验研究[J].工业水处理,2013,33(11):53-55.LIU Jianping,XU Yan,LI Jing,et al.Experimental study on treat-ment of coking tail water by adsorption[J]. Industrial WaterTreatment,2013,33(11):53-55.
[2]蒋庆.黑猫焦化废水的水质分析及工艺优化[D].西安:西北大学,2016:21-53.
[3]刘尚超,薛改凤,张垒,等.焦化废水处理技术研究进展[J].工业水处理,2012,32(1):15-17.LIU Shangchao,XUE Gaifeng,ZHANG Lei,et al.Research progressin the treatment technology of wastewater from coke plants[J]. In-dustrial Water Treatment,2012,32(1):15-17.
[4]田永淑,侯润欣.焦化废水深度处理技术研究进展[J].河北联合大学学报,2013,35(3):113-116.TIAN Yongshu,HOU Runxin.Research progress on advanced treat-ment for coking wastewater[J].Journal of Hebei United University,2013,35(3):113-116.
[5]黄源凯,韦朝海,吴超飞,等.焦化废水污染指标的相关性分析[J].环境化学,2015,34(9):1661-1670.HUANG Yuankai,WEI Chaohai,WU Chaofei,et al.The correlationanalysis of pollution indexes in coking wastewater[J].Environmen-tal Chemistry,2015,34(9):1661-1670.
[6]潘碌亭,吴锦峰.焦化废水处理技术的研究现状与进展[J].环境科学与技术,2010,33(10):86-90.PAN Luting,WU Jinfeng.Progress on treatment technique of cokingwastewater[J]. Environmental Science&Technology,2010,33(10):86-90.
[7]刘聪,陈吕军,朱小彪,等.焦化废水A2/O处理过程中的组成和毒性变化规律[J].生态毒理学报,2014,9(2):291-298.LIU Cong,CHEN Lujun,ZHU Xiaobiao,et al. Compositional andToxic Variations of Coking Wastewater in an A2/O TreatmentProcess[J].Asian Journal of Ecotoxicology,2014,9(2):291-298.
[8]彭枫,潘霞.焦化废水生化出水深度处理试验研究[J].环境工程,2014,32(5):14-16.PENG Feng,PAN Xia. Experimental study on advanced treatmentof biologically treated coking wastewater[J]. Environmental Engi-neering,2014,32(5):14-16.
[9]刘纯玮,吴超,刘少芳,等.处理焦化废水活性炭的制备及性能表征的研究[J].中国煤炭,2016,42(9):75-79.LIU Chunwei,WU Chao,LIU Shaofang,et al.Research on prepara-tion and property characterization of activated carbons for cokingwastewater treatment[J].China Coal,2016,42(9):75-79.
[10] REN Yuan,LI Ting,WEI Chaohai. Competitive adsorption be-tween phenol,aniline and n-heptane in tailrace cokingwastewater[J].Water Air&Soil Pollution,2012,224(1):1-11.
[11]陈鹏,胡绍伟,王飞,等.焦粉吸附深度处理焦化废水实验[J].钢铁,2015,50(12):38-41.CHEN Peng,HU Shaowei,WANG Fei,et al. Experiment on theadvanced treatment of coking wastewater by coke powder adsorp-tion[J].Iron&Steel,2015,50(12):38-41.
[12]张洪恩,任云亮,李红超,等.焦粉吸附COD、挥发酚和氨氮的研究[J].燃料与化工,2016,47(4):57-59.ZHANG Hongen,REN Yunliang,LI Hongchao,et al.Research onadsorption of COD,volatile phenol and NH3-N in coking wastewater by CDQ coke breeze[J].Fuel&Chemical Processes,2016,47(4):57-59.
[13]魏锦扬.去除焦化反渗透浓水有机污染物试验研究[D].徐州:中国矿业大学,2017:30-46.
[14]刘红,张林霞,吴克明.吸附-氧化法处理焦化废水的研究[J].工业水处理,2003,23(5):35-37.LIU Hong,ZHANG Linxia,WU Keming. Study on the treatmentof coke plant wastewater by adsorption catalytic oxidation process[J].Industrial Water Treatment,2003,23(5):35-37.
[15]国家环境保护总局《水和废水监测分析方法》编委会.水和废水监测分析方法[M].4版.北京:中国环境科学出版社,2010:102-103.
[16]吴声彪,肖波,史晓燕,等.粉末活性炭法去除焦化废水中的COD[J].化工环保,2004,24(6):221-223.WU Shengbiao,XIAO Bo,SHI Xiaoyan,et al. Removal of CODfrom coking wastewater by powdered activated carbon[J]. Envi-ronmental Protection of Chemical Industry,2004,24(6):221-223.
[17]刘宪,李娅,沈毅,等.焦粉吸附法深度处理焦化生化废水的研究[J].工业安全与环保,2008,34(11):19-22.LIU Xian,LI Ya,SHEN Yi,et al. Study on coking wastewatertreatment by adsorption with dry extinguishing coke powder[J].Industrial Safety and Environmental Protection,2008,34(11):19-22.
[18]刘剑平,徐焱,李静,等.吸附法处理焦化尾水的实验研究[J].工业水处理,2013,33(11):53-55.LIU Jianping,XU Yan,LI Jing,et al.Experimental study on treat-ment of coking tail water by adsorption[J]. Industrial WaterTreatment,2013,33(11):53-55.