紫外光结合Fenton法处理炸药废水研究
摘要
炸药工业是重污染源之一,由于所排生产废水中含梯恩梯(TNT)、黑索今(RDX)等多种剧毒物质,污染物量虽不多,但若不采取适当措施可造成严重的局部环境污染,对人类及环境造成严重危害。Fenton 法对有机物废水处理有一定的作用,而将紫外光与Fenton 法结合的高级氧化技术在处理高浓度、难降解、有毒、有害废水方面表现出比其他方法多的优势,本论文对紫外光(UV)结合 Fenton 法处理含 TNT 及 RDX 炸药废水作了探索性的研究。
在实验中,首先用正交实验法确定了对影响紫外光结合 Fenton 法处理 TNT 及 RDX废水的各个因素的最佳条件,并对各影响因素做了单因素的实验分析,同时用 Fenton法对 TNT 及 RDX 进行了对比实验。实验结果表明:
(1) UV/Fenton 法处理含 TNT 及 RDX 的废水,处理效果很好,终水样可达国家一级排放标准,实验证明这种方法处理含 TNT 及 RDX 的废水是可行的。
(2) Fenton 法及光助 Fenton 法对 TNT 及 RDX 都具有较强的降解效果,但是光助Fenton法的处理效果明显比Fenton法好,而且光助Fenton法既降低了Fe~(2+)的用量,保持 H_2O_2较高的利用率,同时也降低了 H_2O_2的用量。
(3) 通过对影响 UV/Fenton 法的各影响因素进行分析,得出了处理 25mL、80mg/L的 TNT 或 RDX 的各因素的最佳反应条件为:pH 为 3,H2O2 的加入量为1.5mL,Fe~(2+)的加入量为 1.0mL,反应时间为 2 个小时。在此条件下 TNT 的去除率达 99%以上,CODCr为 20.1mg/L ,对 RDX 的去除率达 97 %以上,COD_(Cr) 为 36.4mg/L。
The explosive industry is one of heavy pollution. Because arranges in the productionwastewater contained TNT and RDX are poisonous and baneful. Although the pollutantquantity are not many, but if does not take the suitable measure, it will be possible to causethe serious partial environmental pollution and it will must do much harm to the humanity andthe environments. The Fenton reagent has the certain function to organic wastewater. Theadvanced oxidation processes of unified UV and Fenton reagent is better than other processesin the treating high potency, difficult degraded, virulent and harmful wastewater. In this paperthe trails of degradations of TNT and RDX explosive wastewater by unified Fenton reagentand UV are made.
In the first step of the experiment, by orthogonal test the best response condition totreat TNT and RDX wastewater by UV/Fenton was obtained. And the influence factor wasanalyzed in the single factor experimental. Meanwhile the contrast experiment has carried onbetween the Fenton reagent and UV/Fenton. The experimental results are as follows:
(1)The processing effect is excellent by UV/Fenton processing to treat TNT and RDXwastewater, and the final water sample reaches a national level to discharge thestandard. The experiment proved this method processing contained TNT and the RDXwaste water is feasible e.
(2) The Fenton agent and the UV/Fenton all have the better degeneration effect to TNTand RDX. And UV/Fenton processing is obviously better than Fenton processing infunction, which reduced the amount of Fe~(2+), maintained availability ratio of H_2O_2,and reduced the amount of H2O2 at the same time.
(3) Through analyzing the influence factor of UV/Fenton treating 25mL、80mg/L TNT orRDX the optimum response condition has obtained: pH is 3, the volume of H2O2 is1.5 milliliter, the volume of Fe2+ is 1.5 milliliter and the reaction time is 2h.Under this
condition the removing rate of TNT reaches above 99%, CODCr is 20.1mg/L, theremoving rate of RDX reaches above 97%, CODCr is 36.4mg/L.
在实验中,首先用正交实验法确定了对影响紫外光结合 Fenton 法处理 TNT 及 RDX废水的各个因素的最佳条件,并对各影响因素做了单因素的实验分析,同时用 Fenton法对 TNT 及 RDX 进行了对比实验。实验结果表明:
(1) UV/Fenton 法处理含 TNT 及 RDX 的废水,处理效果很好,终水样可达国家一级排放标准,实验证明这种方法处理含 TNT 及 RDX 的废水是可行的。
(2) Fenton 法及光助 Fenton 法对 TNT 及 RDX 都具有较强的降解效果,但是光助Fenton法的处理效果明显比Fenton法好,而且光助Fenton法既降低了Fe~(2+)的用量,保持 H_2O_2较高的利用率,同时也降低了 H_2O_2的用量。
(3) 通过对影响 UV/Fenton 法的各影响因素进行分析,得出了处理 25mL、80mg/L的 TNT 或 RDX 的各因素的最佳反应条件为:pH 为 3,H2O2 的加入量为1.5mL,Fe~(2+)的加入量为 1.0mL,反应时间为 2 个小时。在此条件下 TNT 的去除率达 99%以上,CODCr为 20.1mg/L ,对 RDX 的去除率达 97 %以上,COD_(Cr) 为 36.4mg/L。
The explosive industry is one of heavy pollution. Because arranges in the productionwastewater contained TNT and RDX are poisonous and baneful. Although the pollutantquantity are not many, but if does not take the suitable measure, it will be possible to causethe serious partial environmental pollution and it will must do much harm to the humanity andthe environments. The Fenton reagent has the certain function to organic wastewater. Theadvanced oxidation processes of unified UV and Fenton reagent is better than other processesin the treating high potency, difficult degraded, virulent and harmful wastewater. In this paperthe trails of degradations of TNT and RDX explosive wastewater by unified Fenton reagentand UV are made.
In the first step of the experiment, by orthogonal test the best response condition totreat TNT and RDX wastewater by UV/Fenton was obtained. And the influence factor wasanalyzed in the single factor experimental. Meanwhile the contrast experiment has carried onbetween the Fenton reagent and UV/Fenton. The experimental results are as follows:
(1)The processing effect is excellent by UV/Fenton processing to treat TNT and RDXwastewater, and the final water sample reaches a national level to discharge thestandard. The experiment proved this method processing contained TNT and the RDXwaste water is feasible e.
(2) The Fenton agent and the UV/Fenton all have the better degeneration effect to TNTand RDX. And UV/Fenton processing is obviously better than Fenton processing infunction, which reduced the amount of Fe~(2+), maintained availability ratio of H_2O_2,and reduced the amount of H2O2 at the same time.
(3) Through analyzing the influence factor of UV/Fenton treating 25mL、80mg/L TNT orRDX the optimum response condition has obtained: pH is 3, the volume of H2O2 is1.5 milliliter, the volume of Fe2+ is 1.5 milliliter and the reaction time is 2h.Under this
condition the removing rate of TNT reaches above 99%, CODCr is 20.1mg/L, theremoving rate of RDX reaches above 97%, CODCr is 36.4mg/L.
引文
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[2]丁忠浩.有机废水处理技术及应用.北京:化学工业出版社,2002:1~20
[3]孙荣康,瞿美林,陆才正.火炸药工业的污染及其防治.北京:兵器工业出版社,1990:318~447
[4]Robidoux P Y,Bardai G,Paquet L,et al.Phytotoxicity of 2,4,6-trinitrotoluene (TNT) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX) in spiked artificial and natural forest soils.Arch.Environ.Contam.Toxicol.2003,44,198~209
[5]Kulpa C.F. and Boopathy R.(1994)Biocrasformation of 2,4,6-trinitrotoluene(TNT)by a Methanococcus sp.(strain B)isolated from a lake sediment.Caun.Microdiol.40:273~277
[6]O.A.Kpomos.大气和水中有害物质之最大容许浓度.东京:东京讲谈社,1979
[7]A.L.Selman,US Army Man.Tech.J.1976,1(1),29~34
[8]F.J.Goldstein,ADA055683,1978
[9]中国卫生部发布.职业性慢性三硝基甲苯中毒诊断标准及处理原则编制说明.1982
[10]何铁林.水处理化学品手册. 北京:化学工业出版社,2000:604
[11]郭新超.周军,黄永勤等.物化法处理炸药废水研究进展.工业给排水,2001,27(7):45~48
[12]唐受印.戴友芝,汪大翚等.废水处理工程.第二版.北京:化学工业出版社,2004:313~336
[13]吴耀国,焦剑,赵大为等.炸药废水处理的高级氧化技术.含能材料.2003,11(3):166~169
[14]许正,夏连胜,赵君科.液中放电应用于 TNT 废水的降解.环境污染与防治,1999,21(6):20~22
[15]北京水环境技术与设备研究中心等主编.三废处理工程技术手册(废水卷).北京:化学工业出版社,2000:236
[16]王起来等.硝铵炸药.北京:国防工业出版社,1984: 123~125
[17]唐婉莹,周审范,胡伟等.TNT 废水治理技术研究新进展.江苏环境科技.1997,4:9~12
[18]梯恩梯工业水污染物排放标准.中华人民共和国国家标准.GB4274-84
[19]黑索今工业水污染物排放标准.中华人民共和国国家标准.GB4275-84
[20]刘国伟. 三硝基甲苯废水的吸附处理和循环利用.煤矿环境保护.2002,16(3):23
[21]欧阳吉庭,刘晓春,冯长根等.臭氧紫外法处理 TNT 水溶液的研究.北京大学学报.1999,19(5):656~665
[22]Sarah L Vanderloop,Makram T Suidan,Moustafa A Moteleb,et al.Two-stage biotransfomation of TNT under nitrogen-rich and nitrogen-limiting conditions. Wat Envir Res,1998,70(2):189~196
[23]范广裕,骆文仪.用磺化煤作吸附剂处理含 TNT 废水的研究.北京理工大学学报,1997,17(4):52~53
[24]艾翠玲.含黑索今的混合炸药废水可处理性研究.含能材料.2004,12(1):30~33
[25]常冠钦.难降解有机废水生化处理的研究.北京科技大学硕士学位论文.2001,68
[26]何德文,肖羽堂,周中范.白腐真菌处理难生物降解的有机废水研究.工业水处理,2000,20(3):16~18
[27]郝艳霞,李健生,王连军,等.膜萃取法在 TNT 废水处理中的应用.南京理工大学学报,2001,15(5):543~546
[26]乌锡康,金青萍.有机水污染治理技术.上海:华东化工学院出版社.1989:233~239
[28]Schmelling D C,Gray K A. photocatalytic transformation and mineralization of 2,4,6-trinitrotoluene (TNT) in TiO2 slurries.Water Res. 1995,29:2651
[29]Bose P,Gaze W H ,Massox D S. Degradation of RDX by various advanced oxidation processes.Water Res.1998,32(4):997~1004
[30]Li Z.M,Confort S D.Snea P I .Destruction of TNT by Fenton oxidation.Journal of Environmental Quality.1997,26(4):480~487
[31]徐中其,戴航,陆晓华.难降解有机废水处理技术. 江苏环境科技. 2000,13(1):32~36
[32]Hao Oliver J,Phull Kotu K,Chen Jin M. Wet oxidation of TNT red water and bacterial toxicity of treated water. Wat Res. 1994,28(2):283~290
[33]Fenton H G H . The oxidation of polyhydric alcohols in the presence of iron.Chem Soc . 1899,75:1~11
[34]Ruppert G , Bauer R , Heisler G . The Photo-Fenton reaction an effective photochemical wastewater treatment process. Photochem .Photobiol , A : Chem . 1993,73 : 75~78
[35]郭照冰,郑正,袁守军等. 超声与其他技术联合在废水处理中的应用.工业水处理. 2003,23(7):8~12
[36]许海燕,刘亚菲,唐文伟等. 超声、电解与 Fenton 试剂联合处理焦化废水的试验研究.2005,8,7.http//www.hwcc.com.cn
[37]孙满,赵淑婷,王永广. 电解-Fenton 法处理中药废水.油气田地面工程. 2004(12):28
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