机械化学法降解对溴氯苯的工况研究
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摘要
以对溴氯苯为研究物质,用机械化学法对其进行处理,重点考察了各球磨工艺参数对机械球磨过程降解效率与脱卤效率的影响.采用高效气相色谱仪(GC)与离子色谱仪(IC)分别对处理过程中底物浓度与卤素进行跟踪监测,考察转速、球磨时间、物料比以及球料比等工艺参数对底物降解率及脱卤率的影响,并经优化获得相对最佳球磨操作条件.结果表明:在一定转速范围内,球磨转速为600r/min时的处理效果最佳,脱氯率、脱溴率与降解率分别为78.15%,91.46%,99.9%.在球料比(质量比)、物料比(摩尔比)的实验组中,综合考虑能耗问题、物质有效利用与降解效率等因素,最优球料比、物料比确定为12.6∶1与102∶1.比较了几种脱卤试剂的脱卤效果,CaO作为脱卤试剂时,脱卤效率最高.
This paper carries out a study of mechanochemical technology to treat 4-bromochlorobenzene which is a typical halogenated aromatic organic substance.It focuses on the exploration of dehalogenation efficiency and degradation efficiency during mechanochemical milling process. High-efficiency gas chromatograph(GC)and ion chromatograph(IC)were employed to monitor concentrations of the substrate and inorganic halogen ions in the mechanochemical process,respectively.Then,it investigated the influence of rotational speed,grinding time,ratio of balls to materials,materials ratio on dehalogenation efficiency and degradation efficiency.The results of this study were as follows:in the condition of selected rotational speed range and gradient,dehalogenation efficiency and degradation efficiency at 600 r/min were obviously better than other rotational speeds,thedechlorination efficiency,debromination efficiency and degradation efficiency were 91.2%,93.8% and 99.9%.In the experimental groups of studying the influence of the ratio of balls to materials and materials ratio,results showed that dehalogenation efficiency increased with the increase of materials ratio and the ratio of balls to materials.The optimum ball material ratio and material ratio were determined to be 12.6∶1 and 102∶1.Through comparison of several dehalogenation agents,it was found that CaO acted as the most efficient dehalogenation agent for mechanochemical dehalogenation.
This paper carries out a study of mechanochemical technology to treat 4-bromochlorobenzene which is a typical halogenated aromatic organic substance.It focuses on the exploration of dehalogenation efficiency and degradation efficiency during mechanochemical milling process. High-efficiency gas chromatograph(GC)and ion chromatograph(IC)were employed to monitor concentrations of the substrate and inorganic halogen ions in the mechanochemical process,respectively.Then,it investigated the influence of rotational speed,grinding time,ratio of balls to materials,materials ratio on dehalogenation efficiency and degradation efficiency.The results of this study were as follows:in the condition of selected rotational speed range and gradient,dehalogenation efficiency and degradation efficiency at 600 r/min were obviously better than other rotational speeds,thedechlorination efficiency,debromination efficiency and degradation efficiency were 91.2%,93.8% and 99.9%.In the experimental groups of studying the influence of the ratio of balls to materials and materials ratio,results showed that dehalogenation efficiency increased with the increase of materials ratio and the ratio of balls to materials.The optimum ball material ratio and material ratio were determined to be 12.6∶1 and 102∶1.Through comparison of several dehalogenation agents,it was found that CaO acted as the most efficient dehalogenation agent for mechanochemical dehalogenation.
引文
[1]陈金媛,徐圣辰.杭州市PM2.5中PAEs污染现状与特征分析[J].浙江工业大学学报,2015,43(6):600-606.
[2]王军良,梅益柔,潘军,等.钱塘江齐溪水库表层沉积物中多环芳烃的分布研究[J].浙江工业大学学报,2015,43(5):547-551.
[3]张虹,储诚普,徐颖华,等.弱碱体系中电化学合成3,6-二氯吡啶甲酸[J].浙江工业大学学报,2012,40(4):379-383.
[4]王淑惠,丁根娣,侯惠奇.水体中卤代芳烃污染状况及降解途径研究进展[J].环境工程学报,2002,3(6):13-20.
[5]ROWLANDS S A,HALL A K,MCCORMICK P G,et al.Destruction of toxic materials[J].Nature,1994,367(6460):223.
[6]XU Z,ZHANG X Y,FEI Q Z.Dechlorination of pentachlorophenol by grinding at low rotation speed in short time[J].Chinese journal of chemical engineering,2015,23(3):578-582.
[7]LU S Y,HUANG J X,PENG Z,et al.Ball milling 2,4,6-trichlorophenol with calcium oxide:dechlorination experiment and mechanism considerations[J].Chemical engineering journal,2012,195:62-68.
[8]ZHANG J,LI H B,SUN S L,et al.Density functional theory characterization and design of high-performance diarylamine-fluorenedyes with differentπspacers for dye-sensitized solar cells[J].Journal of materials chemistry,2011,22(2):568-576.
[9]WATANABE H,ISHIDA Y,HAYAZAWA N,et al.Tip-enhanced near-field Raman analysis of tip-pressurized adenine molecule.[J].Physical review B,2004,69(15):155418.
[10]RACZY N'SKA E D,KRYGOWSKI T M,ZACHARA J E,et al.Tautomeric equilibria,H-bonding andπ-electron delocalization in o-nitrosophenol.A B3LYP/6–311 + G(2df,2p)study[J].Journal of physical organic chemistry,2005,18(8):892-897.
[11]YU YF,HUANG J,ZHANG W,et al.Mechanochemical destruction of mirex co-ground with iron and quartz in a planetary ball mill[J].Chemosphere,2013,90(5):1729-1735.
[12]ZHANG K L,HUANG J,ZHANG W,et al.Mechanochemical degradation of tetrabromobisphenol A:performance,products and pathway[J].Journal of hazardous materials,2012,243(12):278-285.
[13]TANAKA Y,ZHANG Q W,SAITO F,et al.Dependence of mechanochemically induced decomposition of mono-chlorobiphenyl on the occurrence of radicals[J].Chemosphere,2005,60(7):939-943.
[14]ZHANG W,WANG H Z,HUANG J,et al.Acceleration and mechanistic studies of the mechanochemical dechlorination of HCB with iron powder and quartz sand[J].Chemical engineering journal,2014,239(3):185-191.
[15]ZHANG Q W,SAITO F,IKOMA T,et al.Effects of quartz addition on the mechanochemical dechlorination of chlorobiphenyl by using CaO[J].Environmental science&technology,2001,35(24):4933-4935.
[16]INOUE T,MIYAZAKI M,KAMITANI M.Mechanochemical dechlorination of polyvinyl chloride by co-grinding with various metal oxides[J].Advanced powder technology,2004,15(2):215-225.
[2]王军良,梅益柔,潘军,等.钱塘江齐溪水库表层沉积物中多环芳烃的分布研究[J].浙江工业大学学报,2015,43(5):547-551.
[3]张虹,储诚普,徐颖华,等.弱碱体系中电化学合成3,6-二氯吡啶甲酸[J].浙江工业大学学报,2012,40(4):379-383.
[4]王淑惠,丁根娣,侯惠奇.水体中卤代芳烃污染状况及降解途径研究进展[J].环境工程学报,2002,3(6):13-20.
[5]ROWLANDS S A,HALL A K,MCCORMICK P G,et al.Destruction of toxic materials[J].Nature,1994,367(6460):223.
[6]XU Z,ZHANG X Y,FEI Q Z.Dechlorination of pentachlorophenol by grinding at low rotation speed in short time[J].Chinese journal of chemical engineering,2015,23(3):578-582.
[7]LU S Y,HUANG J X,PENG Z,et al.Ball milling 2,4,6-trichlorophenol with calcium oxide:dechlorination experiment and mechanism considerations[J].Chemical engineering journal,2012,195:62-68.
[8]ZHANG J,LI H B,SUN S L,et al.Density functional theory characterization and design of high-performance diarylamine-fluorenedyes with differentπspacers for dye-sensitized solar cells[J].Journal of materials chemistry,2011,22(2):568-576.
[9]WATANABE H,ISHIDA Y,HAYAZAWA N,et al.Tip-enhanced near-field Raman analysis of tip-pressurized adenine molecule.[J].Physical review B,2004,69(15):155418.
[10]RACZY N'SKA E D,KRYGOWSKI T M,ZACHARA J E,et al.Tautomeric equilibria,H-bonding andπ-electron delocalization in o-nitrosophenol.A B3LYP/6–311 + G(2df,2p)study[J].Journal of physical organic chemistry,2005,18(8):892-897.
[11]YU YF,HUANG J,ZHANG W,et al.Mechanochemical destruction of mirex co-ground with iron and quartz in a planetary ball mill[J].Chemosphere,2013,90(5):1729-1735.
[12]ZHANG K L,HUANG J,ZHANG W,et al.Mechanochemical degradation of tetrabromobisphenol A:performance,products and pathway[J].Journal of hazardous materials,2012,243(12):278-285.
[13]TANAKA Y,ZHANG Q W,SAITO F,et al.Dependence of mechanochemically induced decomposition of mono-chlorobiphenyl on the occurrence of radicals[J].Chemosphere,2005,60(7):939-943.
[14]ZHANG W,WANG H Z,HUANG J,et al.Acceleration and mechanistic studies of the mechanochemical dechlorination of HCB with iron powder and quartz sand[J].Chemical engineering journal,2014,239(3):185-191.
[15]ZHANG Q W,SAITO F,IKOMA T,et al.Effects of quartz addition on the mechanochemical dechlorination of chlorobiphenyl by using CaO[J].Environmental science&technology,2001,35(24):4933-4935.
[16]INOUE T,MIYAZAKI M,KAMITANI M.Mechanochemical dechlorination of polyvinyl chloride by co-grinding with various metal oxides[J].Advanced powder technology,2004,15(2):215-225.
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