褐煤焦油制取有机碱—中油含酚废水脱酚萃取剂研究
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摘要
酚类物质是工业废水中常见的高毒性、难降解有机污染物,同时又是有机化工的基本原料,具有很高的经济价值。因此,经济高效的治理和回收废水中的酚类物质,对环境保护和经济发展极为重要。
本论文采用络合萃取法处理含酚废水,选择云南解化集团煤气化过程产生的副产品褐煤焦油中油(170℃～230℃)作为含酚废水脱酚萃取剂,其含酚量在30～36%之间,是酚类物质的良好溶剂,且富含有机碱成分,与苯酚易形成络合物。
采用先碱洗后酸洗的方案对中油进行精制处理,在有机碱存在条件下,形成吡啶碱-中油含酚废水络合萃取体系,并将其对苯酚模拟废水进行萃取脱酚以及反萃取再生试验研究,确定萃取和再生操作过程的最佳工艺条件。碱洗过程得到酚钠盐,可回收有价值的酚类物质;酸洗过程产生的酸渣用氨水分解,分离出吡啶盐基,再经过蒸馏的方法提取有机碱馏分。
结果表明,中油经20%NaOH溶液1∶1碱洗脱酚,再用92%硫酸1∶5抽提后,精制得到的中油萃取剂油品酚含量＜5%,能满足后续脱酚操作的要求。胶质以及沥青质基本去除,比重、黏度均有降低,化学性质较稳定;油品的杂质少、透明度高、嗅味得到明显改善。对酸渣进行分解蒸馏提取吡啶碱过程,温度范围在110℃～130℃和130℃～180℃之间的馏出液为吡啶碱及其同系物。
萃取脱酚过程,采用吡啶-中油作为脱酚萃取剂,对4000mg/L苯酚模拟废水进行单级萃取试验研究。通过单因素影响试验以及正交试验考察萃取剂组成以及操作条件如pH、萃取相比、温度、反应时间、振荡强度对含酚废水脱酚效率的影响。研究发现,当有机碱-中油络合萃取剂中吡啶含量为6%,pH值为7左右,油水相比1.4∶1、反应温度50℃、摇床转速160r/min、反应时间5min,是萃取脱酚操作的最佳工艺条件,对苯酚模拟水样萃取效率在90%以上,水相酚浓度降至300mg/L左右。此外,通过多级错流萃取试验,综合考虑萃取效率以及工业能耗,拟定采用单级萃取操作。
萃取平衡曲线表明,随着苯酚模拟水样酚浓度的提高,吡啶碱-中油萃取体系的脱酚效率也逐渐提高,可见该萃取体系适合应用于高浓度含酚废水的治理。
论文采用15%NaOH溶液对中油萃取剂进行反萃取再生试验。研究发现,反萃取的最佳操作条件为碱油相比1∶1.5、温度55℃、摇床转速140r/min、反应时间3min,中油萃取剂的再生效率可超过99%,且中油损耗量较小,可满足萃取剂的工业循环使用的要求。
Phenols are organic pollutants of high priority concerns because of their toxicity and possible accumulation in the environment.But they are also the mainly materials in organic chemical industry.Therefore,it is very important to reduce and reclaim phenols from wastewater economically and effectively.
Complexation extraction method is used to remove phenols from wastewater in this paper.A new type of extraction agent----coal tar(170℃～230℃),which comes from lignite gasification process in Jiehua Chem Group Co.,Ltd,is developed.The concentration of phenols is about 30%～36%in the coal tar,and there is a large amount of pyridines which can form complexant with phenols.
In this thesis,pyridines is joined into coal tar treated by NaOH and H_2SO_4,then forms as pyridines-coal tar complexation extraction system which is used to remove phenols from wastewater,and try to ascertain the best technical condition of extraction and reverse extraction process.Reclaim phenols after alkali washing process,and distill the organic alkali compounds from acid residues decomposed by ammonia.
The results show that,treated coal tar washed by 20%NaOH under the volume proportion of 1:1 and then washed by 92%H_2SO_4 under the volume proportion of 1:5,have many advantages than the original coal tar.The concentration of phenols is less than 5%, most of the colloids and asphaltum have been wiped off,and the density and viscosity is lower.The treated coal tar is more stabilization,as well as less impurity,higher diaphaneity and smell better.In the distillation experiment,the organic alkali compounds is finded between the temperature of 110℃～130℃and 130℃～180℃.
The dependence of extraction efficiency on the component of extraction agents,pH, phase ratio R(extractant/aqueous),reaction temperature,time and rotor speed was investigated in the singularity factor extraction experiment.And the mutual-factors experimental results show that,when the proportion of pyridines to the treated coal tar is 6%,pH=7,R=1.4:1,reaction temperature is 50℃,rotor speed is 160 r/min and reaction time for about 5 min,the removal efficiency of phenols will be up to 90%,and the concentration of phenols will drop to 300mg/L.The extraction efficiency balance curve proved that pyridines-coal tar complexation extraction system is good at the wastewater treatment containing high concentration phenols.
In the extractant regeneration experiment,15%NaOH is used to reverse extract the phenols from coal tar.The best technical condition of reverse extraction process is that phase ratio being 1:1.5(alkali/coal tar),reaction temperature being 55℃,rotor speed being 140 r/min and reaction time being about 3 min,the reverse extraction efficiency will be more than 99.5%.It is also sufficed to the industry need.
本论文采用络合萃取法处理含酚废水,选择云南解化集团煤气化过程产生的副产品褐煤焦油中油(170℃～230℃)作为含酚废水脱酚萃取剂,其含酚量在30～36%之间,是酚类物质的良好溶剂,且富含有机碱成分,与苯酚易形成络合物。
采用先碱洗后酸洗的方案对中油进行精制处理,在有机碱存在条件下,形成吡啶碱-中油含酚废水络合萃取体系,并将其对苯酚模拟废水进行萃取脱酚以及反萃取再生试验研究,确定萃取和再生操作过程的最佳工艺条件。碱洗过程得到酚钠盐,可回收有价值的酚类物质;酸洗过程产生的酸渣用氨水分解,分离出吡啶盐基,再经过蒸馏的方法提取有机碱馏分。
结果表明,中油经20%NaOH溶液1∶1碱洗脱酚,再用92%硫酸1∶5抽提后,精制得到的中油萃取剂油品酚含量＜5%,能满足后续脱酚操作的要求。胶质以及沥青质基本去除,比重、黏度均有降低,化学性质较稳定;油品的杂质少、透明度高、嗅味得到明显改善。对酸渣进行分解蒸馏提取吡啶碱过程,温度范围在110℃～130℃和130℃～180℃之间的馏出液为吡啶碱及其同系物。
萃取脱酚过程,采用吡啶-中油作为脱酚萃取剂,对4000mg/L苯酚模拟废水进行单级萃取试验研究。通过单因素影响试验以及正交试验考察萃取剂组成以及操作条件如pH、萃取相比、温度、反应时间、振荡强度对含酚废水脱酚效率的影响。研究发现,当有机碱-中油络合萃取剂中吡啶含量为6%,pH值为7左右,油水相比1.4∶1、反应温度50℃、摇床转速160r/min、反应时间5min,是萃取脱酚操作的最佳工艺条件,对苯酚模拟水样萃取效率在90%以上,水相酚浓度降至300mg/L左右。此外,通过多级错流萃取试验,综合考虑萃取效率以及工业能耗,拟定采用单级萃取操作。
萃取平衡曲线表明,随着苯酚模拟水样酚浓度的提高,吡啶碱-中油萃取体系的脱酚效率也逐渐提高,可见该萃取体系适合应用于高浓度含酚废水的治理。
论文采用15%NaOH溶液对中油萃取剂进行反萃取再生试验。研究发现,反萃取的最佳操作条件为碱油相比1∶1.5、温度55℃、摇床转速140r/min、反应时间3min,中油萃取剂的再生效率可超过99%,且中油损耗量较小,可满足萃取剂的工业循环使用的要求。
Phenols are organic pollutants of high priority concerns because of their toxicity and possible accumulation in the environment.But they are also the mainly materials in organic chemical industry.Therefore,it is very important to reduce and reclaim phenols from wastewater economically and effectively.
Complexation extraction method is used to remove phenols from wastewater in this paper.A new type of extraction agent----coal tar(170℃～230℃),which comes from lignite gasification process in Jiehua Chem Group Co.,Ltd,is developed.The concentration of phenols is about 30%～36%in the coal tar,and there is a large amount of pyridines which can form complexant with phenols.
In this thesis,pyridines is joined into coal tar treated by NaOH and H_2SO_4,then forms as pyridines-coal tar complexation extraction system which is used to remove phenols from wastewater,and try to ascertain the best technical condition of extraction and reverse extraction process.Reclaim phenols after alkali washing process,and distill the organic alkali compounds from acid residues decomposed by ammonia.
The results show that,treated coal tar washed by 20%NaOH under the volume proportion of 1:1 and then washed by 92%H_2SO_4 under the volume proportion of 1:5,have many advantages than the original coal tar.The concentration of phenols is less than 5%, most of the colloids and asphaltum have been wiped off,and the density and viscosity is lower.The treated coal tar is more stabilization,as well as less impurity,higher diaphaneity and smell better.In the distillation experiment,the organic alkali compounds is finded between the temperature of 110℃～130℃and 130℃～180℃.
The dependence of extraction efficiency on the component of extraction agents,pH, phase ratio R(extractant/aqueous),reaction temperature,time and rotor speed was investigated in the singularity factor extraction experiment.And the mutual-factors experimental results show that,when the proportion of pyridines to the treated coal tar is 6%,pH=7,R=1.4:1,reaction temperature is 50℃,rotor speed is 160 r/min and reaction time for about 5 min,the removal efficiency of phenols will be up to 90%,and the concentration of phenols will drop to 300mg/L.The extraction efficiency balance curve proved that pyridines-coal tar complexation extraction system is good at the wastewater treatment containing high concentration phenols.
In the extractant regeneration experiment,15%NaOH is used to reverse extract the phenols from coal tar.The best technical condition of reverse extraction process is that phase ratio being 1:1.5(alkali/coal tar),reaction temperature being 55℃,rotor speed being 140 r/min and reaction time being about 3 min,the reverse extraction efficiency will be more than 99.5%.It is also sufficed to the industry need.
引文
[1]中国水利部.水资源调查评价结果[J].2007
[2]胡皮.中国的水污染和饮用水安全[J].中国减灾,2007,8:19
[3]国家环境保护总局.中国环境状况公报[J].2000-2007
[4]国家环境保护总局.中国绿色国民经济核算研究报告[J].2007
[5]Li Xiaokun.Water Environmental Issue in Three Gorges Reservoir Area and It's Protective Countermeasures[J].Research of Soil and Water Conservation,2007,14(4):19-23
[6]United State Enviromental Protection Authority.Toxic Substances Control ACT (TSCA).USEPA,Washington,DC,1979
[7]赵天亮,宁平,陈芳媛.含酚废水治理技术研究进展[J].环境与健康杂志,2007,24(8):648-649
[8]王红娟,奚红霞,夏启斌,等.含酚废水处理技术的现状与开发前景[J].工业水处理,2002,22(6):6-9
[9]Lungen Hans Bodo.The situation of the Chinese coke making industry[J].Stahlund Eisen,2005,125(11):S72-S74
[10]国蓉,程光旭,赵勇平,等.Texaco煤气化工艺技术经济指标的评价方法与评价系设计[J].化工进展,2003,22(9):1001-1004
[11]许世森,刘刚,任永强,等.新型两段式煤气化工艺进料系统的研发[J].热力发电,2007,36(5):80-82
[12]屈丽娟.流化床煤气化技术的研究进展[J].煤炭转化,2007,30(2):82-85
[13]于光元,李亚东.煤气化技术工艺分析[J].洁净煤技术,2005,11(4):39-42
[14]任源,韦朝海,吴超飞,等.焦化废水水质组成及其环境学与生物学特性分析[J].环境科学学报,2007,27(7):1094-1100
[15]许佩瑶,侯素霞,王淑娜.煤加压气化废水处理方法的现状及展望[J].燃料与化工,2006,37(2):31-34
[16]Liu Shuqin,Wang Yongtao,Li Yu,et al.Thermodynamic equilibrium study of trace element transformation during underground coal gasification[J].Fuel Processing Technology,2006,(2):209-215
[17]Li Ym,Cu GW,Zhao I.Treatment of coke-plant wastewater by biofilm systems for removal of organic compounds and nitrogen[J].Chemosphere,AUG 2003,52(6):997
[18]Ghosh S,De S.Energy analysis of a cogeneration plant using coal gasification and solid oxide fuel cell[J].Energy,2006,(2-3):345-363
[19]普煜,陈棵,宁平.鲁奇炉渣在废水净化中的应用研究[J].工业水处理,2007,27(5):59-62
[20]Van Leenwen J,Badriyha B,Vaczi S.Investigation into ozonation of coal coking processing wastewater for cyanide,thiocyanate and organic removal[J].OzoneSci.&engineering,AUG2003,25(4):273
[21]Gogate PR,Pandit AB.A review of imperative technologies for wastewater treatment Ⅱ:hybrid methods[J].Advances in Environmental Research.2004,8(3-4):553
[22]乔元梅,任艳霞.焦化废水处理方法综述[J].过滤与分离,2007,17(3):46-48.
[23]戴树桂.环境化学[M].高等教育出版社,2004,6
[24]吴泳.环境·污染·治理[M].科学出版社,2004,4
[25]斯琴高娃,乌云,田艳飞.浅析苯酚对环境的污染[J].内蒙古石油化工,2006,(12):50-51
[26]吴勇民,李甫,黄成雨.含酚废水处理新技术及其发展前景[J].环境科学与管理,2007,32(3):150-153
[27]Gonzalez MMJ,Luque S,Lvarez JRA,et al.Recovery of phenol from aqueous solutions using hollow fiber contactors[J].Membr Sci,2003,213:181-193
[28]Teh C.Lo.Handbook of Solvent Extraction[M].Wiley,NewYork,1983
[29]Li.Z,Wu.MH,Jiao.Z,et al.Extraction of phenol from wastewater by N-octanoylpyrrolidine[J].Journal of Hazardous Materials,2004,B114:111-114
[30]朱慎林,朴香兰,王桂明.绿色溶剂碳酸二甲酯处理含酚废水研究[J].化学工程,2002,30(4):49-51
[31]Chufen Yang,Yu Qian,Lijuan Zhang.Sovent extraction Process Development and On-site trial-Plant for Phenol Removal from Industrial Coal-gasification Wastewater [J].Chemical Engineering Journal,2006,117:179-185
[32]顾满刘,占晶,刘扬等.炼油厂碱渣废水络合萃取法脱酚试验研究[J].环境科学 与技术,2006,29(11):31-33
[33]胡俊杰,李学字,魏春城.络合萃取法处理高浓度含酚废水的研究[J].IM&P化工矿物与加工,2001,12:6-7
[34]Jin-Quan Xu,Wu-Hua Duan,Xiu-Zhu Zhou,et al.Extraction of phenol in wastewater with annular centrifugal contactors[J].Journal of Hazardous Materials,B131(2006)98-102
[35]汪家鼎.溶剂萃取[M].北京:清华大学出版社,2002
[36]Min Xiao,Jiti Zhou,Yue Tan,et al.Treatment of highly-concentrated phenol wastewater with an extractive membrane reactor using silicone robber[J].Desalination 195(2006)281-293
[37]杨明平,付勇坚,彭荣华.改性粉煤灰吸附处理焦化厂含酚废水的研究[J].煤化工,2005,(2):49-52
[38]聂锦旭,肖贤明,刘立凡.改性膨润土絮凝剂处理含酚废水的试验研究[J].工业水处理,2006,26(1):31-32
[39]姜军清,黄卫红,陆晓华.活性碳纤维处理含酚废水研究[J].工业水处理,2001,21(3):20-22
[40]Guo LY,Shen J,Wang HR.Adsorption of phenol frOm wastewater by activated carbon fiber[J].Industdal water&Wasterwater,2007,38(3):70-73
[41]谢兰英,李忠,奚红霞.超临界条件下苯酚在NKA-Ⅱ树脂上吸附相平衡[J].化工学报,2002,4:8-10
[42]喻淼,褚意新.含酚废水的治理方法及其进展[J].天中学刊,2004,19(5):35-37
[43]Suri R.P.S,Paraskewich M.R.Jr,Zhang QB.Effect of process variables on sono -chemical destruction of aqueous tdchloroethylene[J].Environmental Engineering Science,1999,16(5):345-352
[44]陈家财,朱昌平,高亚.超声降解含酚废水的研究进展[J].声学技术,2007,26(2):341-347
[45]Michael R.Hoffmann,Inez Hua,Ralf Hochemer.Application of ultrasonic irradiation for the degradation of chemical contaminants in water[J].Ultrasonics Sonochemistry,1996,3(3):163-172
[46]Gogate P.R,Pandit A.B.Engineering design methods for cavitation reactors Ⅰ: Sonochemical reactors[J].AICHE,2000a,46:372-393
[47]Sami Sarfaraza,Swapna Thomasa,U.K Tewari.Anoxic treatment of phenolic wastewater in sequencing batch reactor[J].Water Research,2004,38:965-971
[48]Christian P.Ultrasound and environment degradation of chloroaromatic derivative [J].Environment Sci.Tec,1998,32:1316-1318
[49]贾太轩,冯世宏,杜慧玲.含酚废水的氧化法处理[J].天津化工,2009,19(2):12-14
[50]王文明,王捷,张彦芳.二氧化氯处理含酚废水的工艺研究[J].黑龙江环境通报,2000,24(2):49-50
[51]金小元,陈金龙,李爱民等.二氧化氯催化氧化处理含酚废水的研究[J].离子交换与吸附,2003,18(1):61-66
[52]Lin Sheng H,Wang Chuen S.Treatment of high-strength phenolic wastewater by a new two-step method[J].Journal of Hazardous Matelials,2002,90(2):205-216
[53]陈拥军,窦和瑞,杨氏等.催化湿式氧化法在苯酚废水预处理中的应用研究[J].工业水处理,2002,22(6):19-22
[54]周文俊,钱仁渊,金鸣林.催化湿式氧化法处理含酚废水[J].南京工业大学学报,2004,26(1):63-67
[55]夏璐,王双飞,龚铸.含酚废水光催化降解的试验研究[J].环境科学与技术,2005,28(6):68-69
[56]孙惠明,刘辉.光催化氧化法对含酚废水处理的初探[J].山西化工,2001,21(2):50-51
[57]杨国栋,石晓枫,杨布亚.光催化含酚废水的研究[J].农业环境保护,1999,18(1):19-21
[58]Yves P,Daniel B,Kim MB,et al.Solarphotocatalytic process for the purification of water state of development and barries to ommercialization[J].Solar Energy,1996,56:429-437
[59]Dydov L.,Rddy E.P,France P,et al.Sonophotocatalytic Destruction of Orangnic Contaminants in Aqueous Systems on TiO_2 Powders[J].Applied Catalysis B:Environmental.2001,32:95-105
[60]Dionysios D.Continuous-mode Photocatalytic Degradation of Chlorinated Phenols and Pesticides in Water Using a Bench-scale TiO_2 Rotating Disk Reactor[J].Applied Catalysis,2000,B(24):139-155
[61]Arana J,Tello R.E,Rodriguez J.M.D,et al.Highly concentrated phenolic wastewater treatment by the photo-Fenton relation,mechanism study by FTIR-ATR[J].Chemo -phere,2001,44:1017-1023
[62]程丽华,黄君礼,高会旺.Fenton试剂对水中酚类物质的去除效果研究[J].环境科学与技术,2004,27(4):3-4
[63]赵欣,甘海明,王继徽等.H_2O_2-Fe~(2+)氧化法处理邻甲苯酚生产含酚废水的研究[J].湖南大学学报(自然科学版),2000,27(6):90-93
[64]陈美玲.含酚废水处理技术的研究现状及发展趋势[J].化学工程师,2003,95(2):48-51.
[65]Modell M.Processing Methods for the Oxidation of Organics in Supercritical water [J].U.S.P.4543190,sept24,1985
[66]Lin J.G.,Chang C.N.Decomposition of 2-chlorphenol in aqueous solution by ultrasound/H_2O_2 Process[J].Water Science and Technology,1996,33:75-80
[67]李辉,薛军,冯婧微.超临界水氧化处理含酚废水试验研究[J].辽宁化工,2005,34(60):233-234
[68]Shen F,Chen XM,Gao P,et al.Electrochemical removal of fluoride ions from industrial wastewater[J].Chemical Engineering Science,2003,58(6):987-993
[69]吴星五.电化学法水处理新技术降解有机废水[J].环境科学学报,2000,20(增):80-84
[70]杨润昌.含酚废水湿式电化学氧化处理研究[J].湘潭大学自然科学学报,2001,23(3):55-58
[71]Korbahti B.K,Tanyolac A..Continuous Electrochemical Treatment of Phenolic Wastewater in a Tubular Reactor[J].Water Research,2003,37:1505-1514
[72]Fockedey E,Lierde AV.Electrochemical destruction of aniline and 4-chloroaniline for waste-water treatment using a carbon-PTFE O_2-fed cathode[J].Water Research,2002,36:4169-4175
[73]Canizares P,Domingues J.A,Roderigo M.A,et al.Effect of the Current Intensity in the Electrochemical Oxidation of Aqueous Phenol Wastes at an Activated Carbon and Steel Anode[J].Ind Eng Chem Res,1999,38:3779-3785
[74]张芳,李光明,杨惠康等.电催化氧化技术在含酚废水处理中的应用[J].化工进展,2005,24(8):860-864
[75]马发才.哈尔滨气化厂煤气废水萃取脱酚及深度处理研究[D](硕士论文).哈尔滨工业大学,2005,10
[76]Min Zhang,Joo Hwa Tay,Y Qian,et al.Coke Plant Wastewater Treatment by fixed Biofilm System for COD and NH_3-N Removal[J].Wat.Res.,1998,32(2):519-527
[77]Sami Sarfaraza,Swapna Thomasa.U.K Tewari.et al.Anoxic treatment of phenolic wastewater in sequencing batch reactor[J].Water Research,2004,38:965-971
[78]Chin-Han Chan,Poh-Eng Lim.Evaluation of sequencing batch reactor performance with aerated and unaerated fill periods in treating phenol-containing wastewater [J].Bioresource Technology,2006,5:33-38
[79]张伟.生物法处理含酚废水的研究[J].油气田环境保护,1999,9(2):23-25
[80]肖庚富,王家玲.曝气浸没固定生物膜法及其在污水处理中的应用[J].环境科学与技术,1993,63(4):1-5
[81]A.Venu Vino,G.Venkat Reddy.Simulation of biodegradation process of phenolic wastewater at higher concentrations in a fluidized-bed bioreactor[J].Biochemical Engineering Journal,2005,24:1-10
[82]Wlodzimierz Sokol,Wojciech Korpal.Determination of the optimal operational parameters for a three-phase fluidised bed bioreactor with a light biomass support when used in treatment of phenolic wastewaters[J].Biochemical Engineering Journal,2004,20:49-56
[83]沈齐英,刘录,申林波.三相生物流化床处理炼油厂含酚废水的试验研究[J].环境污染治理技术与设备,2003,7:64-66
[84]乌锡康.有机化工废水治理技术[M].北京:化学工业出版杜,1999
[85]Klibanov A.M.Peroxidase catalyzed removal of phenols from coal conversion wastewater[J].Science,1983,221:259-261
[86]王建龙.生物固定化技术与水污染控制[M].北京:科学出版社,2002
[87]刘长风,刘桂萍,刘永生.固定化技术在含酚废水处理中的研究进展[J].化学工程师,2005,122(11):40-42
[88]朱柱,李和平,郑泽根.固定化细胞技术处理含酚废水的研究[J].重庆环境科学,2000.22(6):64-67
[89]KaiChee Loh,Taishung Chung,WeiFern Ang.Immoblized-cell membrane bioreactor for high-strength phenol wastewater[J].Environ.Eng.,2000,126(1):75-79
[90]Qu XF,Zheng JT,Zhang YZ.Catalytic ozonation of phenolic wastewater with activated carbon fiber in a fluid bed reactor[J].Colloid Interface Sci,2007,309:429-435
[91]Andrew M,Stephen L.H.An overview of semiconductor photo-catalisis[J].Photo -chem.Photobio.Achem.,1997,108(1):1-3
[92]Yoneyama H,Okawa Y,Takeda N.Influence of carbon black as adsorbent used in TiO_2 photocalalysis fihns on photodegradation behaviors of propyzamide[J].Catal.,1998,177(2):240-246
[93]Tsukasal,Norihikot,Yoneyama H.Effect of activated carbon contention TiO2 loaded activated carbon on photodegration behaviors of dichloromethane[J].Photochem.Photobio.Achem.,1997.103(3):153-157
[94]Suzuki Mitsuo.Photocatalysis material comprises of activated carbon and titanium dioxide ultrafine particles[P].JP 155125/96,1996
[95]Chiyoda-KU.Activated carbon which comprises activated carbon particles and titanium dioxide fine particles present on or in the surfaces thereof and has a lightness L value of not more than 50[P].EP 0725036 AI.1996
[96]钟理,严益群.高级氧化过程的研究与进展[J].现代化工,1997.(12):16-19.
[97]毛绍春,高文键,李春林.UV/Fenton/TiO_2法处理含酚废水的研究[J].云南大学学报(自然科学版),2004,26(增刊):154-156
[98]戴猷元,张瑾编著.有机废水萃取处理技术(修订版)[M].北京:化学工业出版社,2006.3
[99]秦国栋,李国泰,郭焕美等.萃取蒸馏法处理葵二酸含酚废水[P].中国专利:02110255.42002-4-5
[100]李珍,吴明红,焦正.含酚废水萃取剂N-辛酰吡咯烷及其合成方法[P].中国专利:2004100117957.6.2004-4-27
[101]国家环境保护总局.《水和废水监测分析方法》(第四版)[M].北京:中国环境 科学出版社,2002
[102]肖瑞华主编.煤焦油化工学[M].北京:冶金工业出版社2006,1
[103]王亮,王蓉辉,曹祖宾.煤焦油的综合利用[J].燃料与化工,2005,36(5):52-53
[104]贺永德主编.现代煤化工技术手册[M].北京:化学工业出版社,2004.
[105]姜玉山.国内外煤焦油加工工业的发展探析[M].煤炭加工和综合利用,2005,(3):40-43
[106]王春江,李平.煤焦油加工技术现状与发展趋势[J].化工科技市场,2007,30(4):11-13
[107]MeAteer,Colin H,Brown J.Pyridine base synthesis[P].US.P:5780635,1998-07-14
[108]常景泉.鲁奇气化煤焦油中重吡啶碱类的提取与精制煤化工[J].2004,12(115):39-41
[2]胡皮.中国的水污染和饮用水安全[J].中国减灾,2007,8:19
[3]国家环境保护总局.中国环境状况公报[J].2000-2007
[4]国家环境保护总局.中国绿色国民经济核算研究报告[J].2007
[5]Li Xiaokun.Water Environmental Issue in Three Gorges Reservoir Area and It's Protective Countermeasures[J].Research of Soil and Water Conservation,2007,14(4):19-23
[6]United State Enviromental Protection Authority.Toxic Substances Control ACT (TSCA).USEPA,Washington,DC,1979
[7]赵天亮,宁平,陈芳媛.含酚废水治理技术研究进展[J].环境与健康杂志,2007,24(8):648-649
[8]王红娟,奚红霞,夏启斌,等.含酚废水处理技术的现状与开发前景[J].工业水处理,2002,22(6):6-9
[9]Lungen Hans Bodo.The situation of the Chinese coke making industry[J].Stahlund Eisen,2005,125(11):S72-S74
[10]国蓉,程光旭,赵勇平,等.Texaco煤气化工艺技术经济指标的评价方法与评价系设计[J].化工进展,2003,22(9):1001-1004
[11]许世森,刘刚,任永强,等.新型两段式煤气化工艺进料系统的研发[J].热力发电,2007,36(5):80-82
[12]屈丽娟.流化床煤气化技术的研究进展[J].煤炭转化,2007,30(2):82-85
[13]于光元,李亚东.煤气化技术工艺分析[J].洁净煤技术,2005,11(4):39-42
[14]任源,韦朝海,吴超飞,等.焦化废水水质组成及其环境学与生物学特性分析[J].环境科学学报,2007,27(7):1094-1100
[15]许佩瑶,侯素霞,王淑娜.煤加压气化废水处理方法的现状及展望[J].燃料与化工,2006,37(2):31-34
[16]Liu Shuqin,Wang Yongtao,Li Yu,et al.Thermodynamic equilibrium study of trace element transformation during underground coal gasification[J].Fuel Processing Technology,2006,(2):209-215
[17]Li Ym,Cu GW,Zhao I.Treatment of coke-plant wastewater by biofilm systems for removal of organic compounds and nitrogen[J].Chemosphere,AUG 2003,52(6):997
[18]Ghosh S,De S.Energy analysis of a cogeneration plant using coal gasification and solid oxide fuel cell[J].Energy,2006,(2-3):345-363
[19]普煜,陈棵,宁平.鲁奇炉渣在废水净化中的应用研究[J].工业水处理,2007,27(5):59-62
[20]Van Leenwen J,Badriyha B,Vaczi S.Investigation into ozonation of coal coking processing wastewater for cyanide,thiocyanate and organic removal[J].OzoneSci.&engineering,AUG2003,25(4):273
[21]Gogate PR,Pandit AB.A review of imperative technologies for wastewater treatment Ⅱ:hybrid methods[J].Advances in Environmental Research.2004,8(3-4):553
[22]乔元梅,任艳霞.焦化废水处理方法综述[J].过滤与分离,2007,17(3):46-48.
[23]戴树桂.环境化学[M].高等教育出版社,2004,6
[24]吴泳.环境·污染·治理[M].科学出版社,2004,4
[25]斯琴高娃,乌云,田艳飞.浅析苯酚对环境的污染[J].内蒙古石油化工,2006,(12):50-51
[26]吴勇民,李甫,黄成雨.含酚废水处理新技术及其发展前景[J].环境科学与管理,2007,32(3):150-153
[27]Gonzalez MMJ,Luque S,Lvarez JRA,et al.Recovery of phenol from aqueous solutions using hollow fiber contactors[J].Membr Sci,2003,213:181-193
[28]Teh C.Lo.Handbook of Solvent Extraction[M].Wiley,NewYork,1983
[29]Li.Z,Wu.MH,Jiao.Z,et al.Extraction of phenol from wastewater by N-octanoylpyrrolidine[J].Journal of Hazardous Materials,2004,B114:111-114
[30]朱慎林,朴香兰,王桂明.绿色溶剂碳酸二甲酯处理含酚废水研究[J].化学工程,2002,30(4):49-51
[31]Chufen Yang,Yu Qian,Lijuan Zhang.Sovent extraction Process Development and On-site trial-Plant for Phenol Removal from Industrial Coal-gasification Wastewater [J].Chemical Engineering Journal,2006,117:179-185
[32]顾满刘,占晶,刘扬等.炼油厂碱渣废水络合萃取法脱酚试验研究[J].环境科学 与技术,2006,29(11):31-33
[33]胡俊杰,李学字,魏春城.络合萃取法处理高浓度含酚废水的研究[J].IM&P化工矿物与加工,2001,12:6-7
[34]Jin-Quan Xu,Wu-Hua Duan,Xiu-Zhu Zhou,et al.Extraction of phenol in wastewater with annular centrifugal contactors[J].Journal of Hazardous Materials,B131(2006)98-102
[35]汪家鼎.溶剂萃取[M].北京:清华大学出版社,2002
[36]Min Xiao,Jiti Zhou,Yue Tan,et al.Treatment of highly-concentrated phenol wastewater with an extractive membrane reactor using silicone robber[J].Desalination 195(2006)281-293
[37]杨明平,付勇坚,彭荣华.改性粉煤灰吸附处理焦化厂含酚废水的研究[J].煤化工,2005,(2):49-52
[38]聂锦旭,肖贤明,刘立凡.改性膨润土絮凝剂处理含酚废水的试验研究[J].工业水处理,2006,26(1):31-32
[39]姜军清,黄卫红,陆晓华.活性碳纤维处理含酚废水研究[J].工业水处理,2001,21(3):20-22
[40]Guo LY,Shen J,Wang HR.Adsorption of phenol frOm wastewater by activated carbon fiber[J].Industdal water&Wasterwater,2007,38(3):70-73
[41]谢兰英,李忠,奚红霞.超临界条件下苯酚在NKA-Ⅱ树脂上吸附相平衡[J].化工学报,2002,4:8-10
[42]喻淼,褚意新.含酚废水的治理方法及其进展[J].天中学刊,2004,19(5):35-37
[43]Suri R.P.S,Paraskewich M.R.Jr,Zhang QB.Effect of process variables on sono -chemical destruction of aqueous tdchloroethylene[J].Environmental Engineering Science,1999,16(5):345-352
[44]陈家财,朱昌平,高亚.超声降解含酚废水的研究进展[J].声学技术,2007,26(2):341-347
[45]Michael R.Hoffmann,Inez Hua,Ralf Hochemer.Application of ultrasonic irradiation for the degradation of chemical contaminants in water[J].Ultrasonics Sonochemistry,1996,3(3):163-172
[46]Gogate P.R,Pandit A.B.Engineering design methods for cavitation reactors Ⅰ: Sonochemical reactors[J].AICHE,2000a,46:372-393
[47]Sami Sarfaraza,Swapna Thomasa,U.K Tewari.Anoxic treatment of phenolic wastewater in sequencing batch reactor[J].Water Research,2004,38:965-971
[48]Christian P.Ultrasound and environment degradation of chloroaromatic derivative [J].Environment Sci.Tec,1998,32:1316-1318
[49]贾太轩,冯世宏,杜慧玲.含酚废水的氧化法处理[J].天津化工,2009,19(2):12-14
[50]王文明,王捷,张彦芳.二氧化氯处理含酚废水的工艺研究[J].黑龙江环境通报,2000,24(2):49-50
[51]金小元,陈金龙,李爱民等.二氧化氯催化氧化处理含酚废水的研究[J].离子交换与吸附,2003,18(1):61-66
[52]Lin Sheng H,Wang Chuen S.Treatment of high-strength phenolic wastewater by a new two-step method[J].Journal of Hazardous Matelials,2002,90(2):205-216
[53]陈拥军,窦和瑞,杨氏等.催化湿式氧化法在苯酚废水预处理中的应用研究[J].工业水处理,2002,22(6):19-22
[54]周文俊,钱仁渊,金鸣林.催化湿式氧化法处理含酚废水[J].南京工业大学学报,2004,26(1):63-67
[55]夏璐,王双飞,龚铸.含酚废水光催化降解的试验研究[J].环境科学与技术,2005,28(6):68-69
[56]孙惠明,刘辉.光催化氧化法对含酚废水处理的初探[J].山西化工,2001,21(2):50-51
[57]杨国栋,石晓枫,杨布亚.光催化含酚废水的研究[J].农业环境保护,1999,18(1):19-21
[58]Yves P,Daniel B,Kim MB,et al.Solarphotocatalytic process for the purification of water state of development and barries to ommercialization[J].Solar Energy,1996,56:429-437
[59]Dydov L.,Rddy E.P,France P,et al.Sonophotocatalytic Destruction of Orangnic Contaminants in Aqueous Systems on TiO_2 Powders[J].Applied Catalysis B:Environmental.2001,32:95-105
[60]Dionysios D.Continuous-mode Photocatalytic Degradation of Chlorinated Phenols and Pesticides in Water Using a Bench-scale TiO_2 Rotating Disk Reactor[J].Applied Catalysis,2000,B(24):139-155
[61]Arana J,Tello R.E,Rodriguez J.M.D,et al.Highly concentrated phenolic wastewater treatment by the photo-Fenton relation,mechanism study by FTIR-ATR[J].Chemo -phere,2001,44:1017-1023
[62]程丽华,黄君礼,高会旺.Fenton试剂对水中酚类物质的去除效果研究[J].环境科学与技术,2004,27(4):3-4
[63]赵欣,甘海明,王继徽等.H_2O_2-Fe~(2+)氧化法处理邻甲苯酚生产含酚废水的研究[J].湖南大学学报(自然科学版),2000,27(6):90-93
[64]陈美玲.含酚废水处理技术的研究现状及发展趋势[J].化学工程师,2003,95(2):48-51.
[65]Modell M.Processing Methods for the Oxidation of Organics in Supercritical water [J].U.S.P.4543190,sept24,1985
[66]Lin J.G.,Chang C.N.Decomposition of 2-chlorphenol in aqueous solution by ultrasound/H_2O_2 Process[J].Water Science and Technology,1996,33:75-80
[67]李辉,薛军,冯婧微.超临界水氧化处理含酚废水试验研究[J].辽宁化工,2005,34(60):233-234
[68]Shen F,Chen XM,Gao P,et al.Electrochemical removal of fluoride ions from industrial wastewater[J].Chemical Engineering Science,2003,58(6):987-993
[69]吴星五.电化学法水处理新技术降解有机废水[J].环境科学学报,2000,20(增):80-84
[70]杨润昌.含酚废水湿式电化学氧化处理研究[J].湘潭大学自然科学学报,2001,23(3):55-58
[71]Korbahti B.K,Tanyolac A..Continuous Electrochemical Treatment of Phenolic Wastewater in a Tubular Reactor[J].Water Research,2003,37:1505-1514
[72]Fockedey E,Lierde AV.Electrochemical destruction of aniline and 4-chloroaniline for waste-water treatment using a carbon-PTFE O_2-fed cathode[J].Water Research,2002,36:4169-4175
[73]Canizares P,Domingues J.A,Roderigo M.A,et al.Effect of the Current Intensity in the Electrochemical Oxidation of Aqueous Phenol Wastes at an Activated Carbon and Steel Anode[J].Ind Eng Chem Res,1999,38:3779-3785
[74]张芳,李光明,杨惠康等.电催化氧化技术在含酚废水处理中的应用[J].化工进展,2005,24(8):860-864
[75]马发才.哈尔滨气化厂煤气废水萃取脱酚及深度处理研究[D](硕士论文).哈尔滨工业大学,2005,10
[76]Min Zhang,Joo Hwa Tay,Y Qian,et al.Coke Plant Wastewater Treatment by fixed Biofilm System for COD and NH_3-N Removal[J].Wat.Res.,1998,32(2):519-527
[77]Sami Sarfaraza,Swapna Thomasa.U.K Tewari.et al.Anoxic treatment of phenolic wastewater in sequencing batch reactor[J].Water Research,2004,38:965-971
[78]Chin-Han Chan,Poh-Eng Lim.Evaluation of sequencing batch reactor performance with aerated and unaerated fill periods in treating phenol-containing wastewater [J].Bioresource Technology,2006,5:33-38
[79]张伟.生物法处理含酚废水的研究[J].油气田环境保护,1999,9(2):23-25
[80]肖庚富,王家玲.曝气浸没固定生物膜法及其在污水处理中的应用[J].环境科学与技术,1993,63(4):1-5
[81]A.Venu Vino,G.Venkat Reddy.Simulation of biodegradation process of phenolic wastewater at higher concentrations in a fluidized-bed bioreactor[J].Biochemical Engineering Journal,2005,24:1-10
[82]Wlodzimierz Sokol,Wojciech Korpal.Determination of the optimal operational parameters for a three-phase fluidised bed bioreactor with a light biomass support when used in treatment of phenolic wastewaters[J].Biochemical Engineering Journal,2004,20:49-56
[83]沈齐英,刘录,申林波.三相生物流化床处理炼油厂含酚废水的试验研究[J].环境污染治理技术与设备,2003,7:64-66
[84]乌锡康.有机化工废水治理技术[M].北京:化学工业出版杜,1999
[85]Klibanov A.M.Peroxidase catalyzed removal of phenols from coal conversion wastewater[J].Science,1983,221:259-261
[86]王建龙.生物固定化技术与水污染控制[M].北京:科学出版社,2002
[87]刘长风,刘桂萍,刘永生.固定化技术在含酚废水处理中的研究进展[J].化学工程师,2005,122(11):40-42
[88]朱柱,李和平,郑泽根.固定化细胞技术处理含酚废水的研究[J].重庆环境科学,2000.22(6):64-67
[89]KaiChee Loh,Taishung Chung,WeiFern Ang.Immoblized-cell membrane bioreactor for high-strength phenol wastewater[J].Environ.Eng.,2000,126(1):75-79
[90]Qu XF,Zheng JT,Zhang YZ.Catalytic ozonation of phenolic wastewater with activated carbon fiber in a fluid bed reactor[J].Colloid Interface Sci,2007,309:429-435
[91]Andrew M,Stephen L.H.An overview of semiconductor photo-catalisis[J].Photo -chem.Photobio.Achem.,1997,108(1):1-3
[92]Yoneyama H,Okawa Y,Takeda N.Influence of carbon black as adsorbent used in TiO_2 photocalalysis fihns on photodegradation behaviors of propyzamide[J].Catal.,1998,177(2):240-246
[93]Tsukasal,Norihikot,Yoneyama H.Effect of activated carbon contention TiO2 loaded activated carbon on photodegration behaviors of dichloromethane[J].Photochem.Photobio.Achem.,1997.103(3):153-157
[94]Suzuki Mitsuo.Photocatalysis material comprises of activated carbon and titanium dioxide ultrafine particles[P].JP 155125/96,1996
[95]Chiyoda-KU.Activated carbon which comprises activated carbon particles and titanium dioxide fine particles present on or in the surfaces thereof and has a lightness L value of not more than 50[P].EP 0725036 AI.1996
[96]钟理,严益群.高级氧化过程的研究与进展[J].现代化工,1997.(12):16-19.
[97]毛绍春,高文键,李春林.UV/Fenton/TiO_2法处理含酚废水的研究[J].云南大学学报(自然科学版),2004,26(增刊):154-156
[98]戴猷元,张瑾编著.有机废水萃取处理技术(修订版)[M].北京:化学工业出版社,2006.3
[99]秦国栋,李国泰,郭焕美等.萃取蒸馏法处理葵二酸含酚废水[P].中国专利:02110255.42002-4-5
[100]李珍,吴明红,焦正.含酚废水萃取剂N-辛酰吡咯烷及其合成方法[P].中国专利:2004100117957.6.2004-4-27
[101]国家环境保护总局.《水和废水监测分析方法》(第四版)[M].北京:中国环境 科学出版社,2002
[102]肖瑞华主编.煤焦油化工学[M].北京:冶金工业出版社2006,1
[103]王亮,王蓉辉,曹祖宾.煤焦油的综合利用[J].燃料与化工,2005,36(5):52-53
[104]贺永德主编.现代煤化工技术手册[M].北京:化学工业出版社,2004.
[105]姜玉山.国内外煤焦油加工工业的发展探析[M].煤炭加工和综合利用,2005,(3):40-43
[106]王春江,李平.煤焦油加工技术现状与发展趋势[J].化工科技市场,2007,30(4):11-13
[107]MeAteer,Colin H,Brown J.Pyridine base synthesis[P].US.P:5780635,1998-07-14
[108]常景泉.鲁奇气化煤焦油中重吡啶碱类的提取与精制煤化工[J].2004,12(115):39-41