机械化学法降解持久性有机污染物—五氯酚
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摘要
长期以来,持久性有机污染物(Persistent Organic Pollutants,以下简称POPs)的处理是环境治理中的难点,氯酚类芳香化合物是其中的典型代表。由于其具有稳定的化学性质,很难自然降解,对生态系统产生了强烈的干扰,严重危害人类安全和健康。传统降解POPs的方法由于反应条件苛刻、处理费用高、工艺流程复杂、易产生二次污染等原因使其商业化推广受到了限制。
本试验用机械化学法处理POPs的典型代表五氯酚(Pentachlorophenol,以下简称PCP),在机械力的作用下,通过钢球与废物颗粒不断地碰撞,将机械能传给废物与金属粉末颗粒,使其不断变细,从而增强PCP分子中的惰性卤素原子反应活性,使其与碱性脱卤试剂发生化学反应,并转化为可溶于水的金属卤化物。具体的实验过程是：在常温常表压下,将PCP与金属氧化物及球磨介质钢球混合放入球磨机中球磨,球磨一定时间后出料,用AgNO3标准溶液滴定含氯离子的研磨产物溶出液,根据消耗AgNO3溶液的量计算氯的脱出率,以此来反映PCP的降解效果。
实验结果表明：
1、PCP与金属氧化物的摩尔比越大,脱氯率越高,并确定了本实验的最佳摩尔比为1:60,脱氯效果达到98%以上。
2、脱氯率随球磨时间的增加而增大。随着球磨时间的延长,产物的颜色由浅变深至黑色,可能有单质碳产生。本实验中最佳的球磨时间为2.5h,有2/3左右的有机氯转化为无机氯。
3、金属氧化物的种类对PCP的降解有直接的影响,本实验表明,在同等条下,CaO作为磨料对PCP的降解效果要好于MgO。
4、通过价键理论证实,CaO和MgO作为脱卤试剂更容易在机械力作用下,引发PCP的化学降解反应。
通过本课题的研究,机械化学法相比于传统的化学方法处理PCP,具有工艺流程简单、工作条件温和、短时间内就可以达到理想的处理效果、而且不涉及传统化工单元的操作,具有广泛的商业化应用前景。
Fore a long time, the treatment of the Persistent Organic Pollutants(POPs) is difficult in environment governance, chlorophenols aromatic compounds is one of the typical. It might cause disturbance in ecosystem and threaten human being's health because of its difficulty to be decomposed owing to the stable chemical property. Traditional methods of degradation of POPs is difficult to commercialize for they have so many disadvantages, including severe restriction on reaction condition, extortionate handing cost, complicated technological process and secondary pollution etc.
We used mechanochemical method to degrade the Pentachlorophenol (PCP) that one is the typical of the POPs in this experiment. Ball and waste particles became thin and occurred continuously collision under the action of mechanical forces, consequently, the inert halogen atomic's reactivity of PCP would be boosted up, halogen atoms removed from organic carbon chains and transform to Metal halide, through the reaction between PCP and dehalogenation reagent occurred. The specific experiment process:PCP, metallic oxide and ball-grinder medium steel beads are ground together in a ball-grinder under ordinary temperature and pressure, which is a mechanochemical way of degrading PCP. A AgNO3 standard solution was used to titrate the Cl--containing solution made from grinding product. The dechlorination rate, which can show the degradation result of PCP, was calculated through the amount of AgNO3 standard solution.
The results are presented as follows:
1. The bigger the Metal Oxide/PCP molar ratio was, the better the dechlorination rate was:when the molar ratio is 60:1, the dechlorination rate was almost over 98%. So, the best molar ratio is 60:1 in this experiment.
2. PCP dechlorination rate increased as grinding time. With increased the ball milling time, the product showed a black hue after 2.5h's grinding, which might be a sigh of formation of elemental carbon. In this experiment, the best ball milling time is 2.5h, and the radio of organochlorine transformed to inorganic chlorine was almost 2/3.
3. Metal oxide species has a direct impact on the degradation of PCP. CaO is better than MgO as a grinding material for dechlorination in the same time.
4. Confirmed by valence bond theory, CaO and MgO as a dehalogenation reagent can trigger the chemical degradation of PCP more easily under the action of mechanical forces.
Due to its simple technological process, normal reaction condition, noticeable effect can get good treatment effect in short time, does not involved the operation of the traditional chemical unit, the mechano-chemical de-halogenations of halogenated organic has received attentions as a promising technology to destroy solid waste containing persistent organic pollutants.
本试验用机械化学法处理POPs的典型代表五氯酚(Pentachlorophenol,以下简称PCP),在机械力的作用下,通过钢球与废物颗粒不断地碰撞,将机械能传给废物与金属粉末颗粒,使其不断变细,从而增强PCP分子中的惰性卤素原子反应活性,使其与碱性脱卤试剂发生化学反应,并转化为可溶于水的金属卤化物。具体的实验过程是：在常温常表压下,将PCP与金属氧化物及球磨介质钢球混合放入球磨机中球磨,球磨一定时间后出料,用AgNO3标准溶液滴定含氯离子的研磨产物溶出液,根据消耗AgNO3溶液的量计算氯的脱出率,以此来反映PCP的降解效果。
实验结果表明：
1、PCP与金属氧化物的摩尔比越大,脱氯率越高,并确定了本实验的最佳摩尔比为1:60,脱氯效果达到98%以上。
2、脱氯率随球磨时间的增加而增大。随着球磨时间的延长,产物的颜色由浅变深至黑色,可能有单质碳产生。本实验中最佳的球磨时间为2.5h,有2/3左右的有机氯转化为无机氯。
3、金属氧化物的种类对PCP的降解有直接的影响,本实验表明,在同等条下,CaO作为磨料对PCP的降解效果要好于MgO。
4、通过价键理论证实,CaO和MgO作为脱卤试剂更容易在机械力作用下,引发PCP的化学降解反应。
通过本课题的研究,机械化学法相比于传统的化学方法处理PCP,具有工艺流程简单、工作条件温和、短时间内就可以达到理想的处理效果、而且不涉及传统化工单元的操作,具有广泛的商业化应用前景。
Fore a long time, the treatment of the Persistent Organic Pollutants(POPs) is difficult in environment governance, chlorophenols aromatic compounds is one of the typical. It might cause disturbance in ecosystem and threaten human being's health because of its difficulty to be decomposed owing to the stable chemical property. Traditional methods of degradation of POPs is difficult to commercialize for they have so many disadvantages, including severe restriction on reaction condition, extortionate handing cost, complicated technological process and secondary pollution etc.
We used mechanochemical method to degrade the Pentachlorophenol (PCP) that one is the typical of the POPs in this experiment. Ball and waste particles became thin and occurred continuously collision under the action of mechanical forces, consequently, the inert halogen atomic's reactivity of PCP would be boosted up, halogen atoms removed from organic carbon chains and transform to Metal halide, through the reaction between PCP and dehalogenation reagent occurred. The specific experiment process:PCP, metallic oxide and ball-grinder medium steel beads are ground together in a ball-grinder under ordinary temperature and pressure, which is a mechanochemical way of degrading PCP. A AgNO3 standard solution was used to titrate the Cl--containing solution made from grinding product. The dechlorination rate, which can show the degradation result of PCP, was calculated through the amount of AgNO3 standard solution.
The results are presented as follows:
1. The bigger the Metal Oxide/PCP molar ratio was, the better the dechlorination rate was:when the molar ratio is 60:1, the dechlorination rate was almost over 98%. So, the best molar ratio is 60:1 in this experiment.
2. PCP dechlorination rate increased as grinding time. With increased the ball milling time, the product showed a black hue after 2.5h's grinding, which might be a sigh of formation of elemental carbon. In this experiment, the best ball milling time is 2.5h, and the radio of organochlorine transformed to inorganic chlorine was almost 2/3.
3. Metal oxide species has a direct impact on the degradation of PCP. CaO is better than MgO as a grinding material for dechlorination in the same time.
4. Confirmed by valence bond theory, CaO and MgO as a dehalogenation reagent can trigger the chemical degradation of PCP more easily under the action of mechanical forces.
Due to its simple technological process, normal reaction condition, noticeable effect can get good treatment effect in short time, does not involved the operation of the traditional chemical unit, the mechano-chemical de-halogenations of halogenated organic has received attentions as a promising technology to destroy solid waste containing persistent organic pollutants.
引文
[1]夏明珠,严荷莲.二氧化碳的分离与综合利用[J].现代化工,1999,19(5):46-48
[2]王铁宇.我国持久性有机污染物状况及宏观对策[J].环境污染治理技术与设备,2004,5(11):21-22.
[3]曹启民.中国持久性有机污染物污染现状及治理技术进展[J].中国农学通报,2006,22(2):361.
[4]李政禹.国际上持久性有机污染物的控制动向及其对策[J].现代化工,1999,19(7):5-8.
[5]李宝惠.淘汰持久性有机污染物(POPs)最新进展[J].山东环境,2001,101:40-41.
[6]WeberK, GoerkeH. Organochlorine compounds in fish off the Antarctic Peninsula [J]. Chemosphere, 1996,33:404-410.
[7]黄俊,余刚,钱易.我国持久性有机污染物问题与研究对策[J].环境保护.2001,11:3-6.
[8]华小梅,单正军.我国农药生产、使用状况及其影响因子分析[J].环境科学进展.1996.4(2):23-25.
[9]Duursma E K, Carroll J. Environmental compartments sedi2 ments and assessment of processes between air, water, sedi2 ments and biota [M]. Germany:Spring-er,1996.
[10]Sink konen S. Paasivirta J. Degradation half-lief times of PCDDs, PCDFs and PCBs for environment fate modeling [J]. Chemosphere,2000,40 (9-77):943-949.
[11]苗秀生,储少岗等.全球性环境污染物多氯联苯的结构一活性相关性研究进展[J].北学进展,1996,8(4).
[12]龚钟明,曹军,李本刚.天津地区土壤中六六六的残留分布特征[J].中国环境科学,2003,23(3):311-314.
[13]David O什么是持久性有机污染物?持久性有机污染物控制研究会论文集[D].北京：国家环保局,2001.9.
[14]AARONTF, GRYAS, KERTHAH. Persistent organic pollutants (POPs) in a small herbivorous, Arctic marine zooplankton (Calanus hyperboreus):trends from April to July and the influence of lipids and trophic transfer [J]. Mar Pollut,2001(43):39-41.
[15]苏丽敏,袁星.持久性有机污染物(POPs)及其生态毒性的研究现状与展望[J].重庆环境科学,2003,25(9)：62-64.
[16]惠秀娟.环境毒理学[M].北京：化学工业出版社,2003,65-157.
[17]费维扬,艾宁,陈健.温室气体C02的捕集和分离[J].气体净化,2005,5(2):1-4.
[18]Ryckman DP, weseloh DV, Hamr GA, et al. Spatial and temporal trends in ogranochlorine contamination and bill deformities in Double-Creased cormorants from the Canadian Great Lakes [J] Environ Mont Assess,1998,53(1):169-195.
[19]Jones KC, de Voogt P. Persistent organic pollutants (POPs):state of the science [J]. Environ Pollut. 1999,100:209-221.
[20]Jane H, ChrisC, RichardW. MOMsand POPs [R]. Washington, D.C.:ENVIRONMENTAL WORKING GROUP,2000.
[21]EPA. SPECIAL REPORT ON ENVIRONMENT ENDOCRINE DIS-RUPTION:AN EFFECTS ASSESSMENT AND ANALYSIS [R]. Washington, D. C.:EPA,1997.
[22]薛建华,王近中,辛佩珠,等.氯仿,氯苯和多氯联苯对染毒家兔红细胞脂质过氧化和膜流动性的影响[J].中华预防医学杂志,1994,28(5)：294-296-
[23]徐科峰1,李忠1,何莼1,奚红霞1,赵月春2.持久性有机污染物(POPs)对人类健康的危害及其治理技术进展[J].四川环境2003年第22卷第4期：29-33.
[24]张海兵.剧毒物二恶英吸附技术的基础研究[D].广州：2001.
[25]Th.Wallenhorst et al, PCDD/F in ambient air and deposi-tion in Baden_Wurttemberg, Germany [J]. Chemospere,1997,34(5-7):1369-1378.
[26]Th. Kouimtzis. PCDD/Fs and PCBs in airborne particu-late matter of the greater Thessaloniki area, N. Greece [J]. Chemosphere,2002,47:193-205.
[27]Thoralf Kuchler et al, Application of GC-MS_MS for the analysis of PCDD/Fs in sewage effluents [J]. Chemosphere,2000,40:213-220.
[28]张祖麟.闽江口持久性有机污染物—多氯联苯的初步研究[J].环境科学学报,2002,22(6)：788-791.
[29]康跃惠,盛国英.珠江澳门河口沉积物柱样中有机氯农药的垂直分布特征[J].环境科学,2001,22(1)：81-85.
[30]L. G. BELLUCCI et al, Polychlorinated Dibenzo_p_dioxins and Dibenzofurans in Surficial Sediments of the Venice La-goon (Italy) [J]. Marine Pollution Bulletin,2000,40(1):65-76.
[31]Shunji Hashimoto et al, Simple sampling and analysis of PCDDs and PCDFs in Japanese seawater [J], Chemospere,1995,30(10):1979-1986.
[32]罗孝俊,杨卫东,党志.有机物污染的土壤治理方法及研究进展[J].矿物岩石地球化学通报,2000,19(2)：130-135.
[33]M. Manz, K._D.et al, Persistent organic pollutants in ag-ricultural soils of central Germany [J]. The Science of the Total Environment,2001,277:187-198.
[34]李国刚,李红莉.持久性有机污染物在中国的环境检测现状[J].中国环境检测,2004(4):53-60.
[35]M.Schuhmacher et al, PCDD/F concentration in milk of nonoccupationally exposed women living in Southern Catal-onia, Spain [J]. Chemospere,1999,38(5):995-1004.
[36]金重阳,郑玉峰等.国内持久性有机污染物的污染现状与对策建议[J].环境保护科学,2002,28(111).
[37]GullettB K, TouatiA. PCDD/F emissions from forest fire simu 21 ations [J]. Atmospheric Environment,2003,37(6):803-813.
[38]施汉昌,赵胤慧,冀静平.氯酚废水的生物处理技术的研究与进展[J].化学通报,1998,(8):1-5.
[39]江苏省环境监测中心.突发性污染事故中危险品档案库[DB/OL]. http://www.ep.net.cn/msds/, 2006-05-07.
[40]金相灿,机化合物污染化学-有毒有机物污染化学[J].北京：清华大学出版社,1990.
[41]Crosby D G. Environmental chemistry of pentachlorophenol, In:Pure&APP.Chem,1981,53: 1051-1080.
[42]曾光明,黄国和,袁兴中,等.堆肥环境生物与控制[J].北京：科学出版社,200.
[43]郭家钢,郑江,中国血吸虫病流行与防治[J].疾病控制杂志.2000,4(4)：289-293.
[44]肖东楼,余晴,党辉,等.2003年全国血吸虫病疫情通报[J].中国血吸虫病防治杂志,2004,16(6):401-403.
[45]陈国新,环境科学基础知识,上海：复旦大学出版社,1992,247-257.
[46]夏北成,环境污染物生物降解,北京：化学工业出版社,2002,266-276.
[47]任引津,张寿林,急性化学物中毒救援手册,上海：上海医科大学出版社,1994.
[48]Chiou Caryt T, Mcgroddy Susan E,Kile Daniel E.Partition characteristics of polycyclic aromatic hydro-carbons on soils and sediments [J]. Environ Sci Technol,1998,32(2):264-269.
[49]何江,关伟,李桂海,等.几种酚类化合物在黄河水体沉积物上吸附行为的实验研究[J].农业环境科学学报,2005,24(3)：480-485.
[50]迟杰,黄国兰,杨彬.五氯酚在表面微层水与表层水间的分配行为[J].环境科学,1999,20(6):18-21.
[51]谢玲玲,周培疆,刘丽君等.五氯苯酚在武汉东湖底质颗粒物上的吸附研究[J].环境保护,2005,51(4)：448-452.
[52]Junya Suegara, Byung-Dae Lee, Maria P. Espino et al. Photodegration of pentachlorophenol and its degration pathways predicted using density functional theory [J]. Chemosphere,2005, (61):341-346.
[53]Piccini P, Pichat P, GuillardC. Phototransformations of solid PentaehloroPhenol. Journal of photoehemistry and photobiology A,1998,119(2):137-142.
[54]楼静,金泥沙.五氯酚废水生化处理技术研究进展.环境科学与管理,2007,12:1 13-115.
[55]黄艺,敖晓兰,赵曦.五氯酚生物降解机理与外生菌根真菌对五氯酚可降解性.生态环境,2006,15(5)：1080-1085.
[56]张国平,Nicell J A,邹永廖,等.辣根过氧化物酶处理五氯酚过程的毒性特征[J].科学通报,2000,45(12)：1267-1271.
[57]Premalatha A, Rajakumar G Suseela.Pentachlorophenol degradation by Pseudomonas aeruginosa [J]. World Journal of Microbiology and Biotechnology,1994,10(3):334-337.
[58]王芳,林少彬,陈亚妍.氯酚在鲫鱼体内的分布存在形式与生物富集研究.卫生研究[J],1999,28(3)：169-171.
[59]张寿明,李金彪.金川选矿厂3#系统磨矿分级多参数测控[J].金属矿山,1996(5):34-37.
[60]李希明,陈家镛.机械化学在资源和材料化工及环保中的应用.化工冶金,2000,21(4):443-448.
[61]宋晓岚,邱冠周,杨华明.机械化学及其应用研究进展.金属矿山,2004年第11期：34-38.
[62]Kacova T K. Mechanical Activation of Minerals [M]. Elsevier,1989.155.
[63]Lin I J, Nadiv S, Grodzian J M. Minerals. Sci. Eng.1975,7(4):313-336.
[64]Baron P, Lin I J, Nadiv S, et al. J. Thermal Analysis,1994,42:217.
[65]Northwood D O Lewis D. Am. Mineral,1968,5:2089.
[66]Grohm H, Paudert R. Z. Chem.1963,3:89.
[67]Boldrev V.Particle Technology [M]. Nurnberg,1986.79.
[68]Heinicke G.Tribochemistry[M].Berlin, Akademie Verlag,1984.97.
[69]Rowlands SA, HallAK, McCormick PG, etal. Destruction of toxic materials [J]. Nature,1994,367: 223.
[70]Tsuyoshi Inoue, Miyuki Miyazaki, Masataka Kamitani. et.al.De-chlorination of Polyvinyl Chloride by its grinding with KOH and NaOH [J]. AdvancedPowderTechno.2005,16(1):27-34.
[71]Birke V. Economic and ecologically favorable destruction of poly-halogenated pollutions applying the DMCR [C]. Contaminated Soil2000. Proceedings of the seventh internationalFZK/TNO conference on contaminated soil 18-22 september 2000, Leipzig, Germany, ThomasTelford Publishing, London. 1330-1331.
[72]http://www.tribochem.Com [EB/OL].
[73]肖松文,肖晓.持久性有机污染物机械化学无害化处理的研究进展[J].矿冶工程,2006,26(2):53-57.
[74]Jones KC, de Voogt P. Persistent ogranic pollutants (POPs):state of the science [J]. Environ Pollut, 1999,100(3):209-221.
[75]Zhang Q, Saito F. Mechanochemical dechlorination of chlorinated compounds Journal of Materials Science [J].2004,39(2),5497-5501.
[2]王铁宇.我国持久性有机污染物状况及宏观对策[J].环境污染治理技术与设备,2004,5(11):21-22.
[3]曹启民.中国持久性有机污染物污染现状及治理技术进展[J].中国农学通报,2006,22(2):361.
[4]李政禹.国际上持久性有机污染物的控制动向及其对策[J].现代化工,1999,19(7):5-8.
[5]李宝惠.淘汰持久性有机污染物(POPs)最新进展[J].山东环境,2001,101:40-41.
[6]WeberK, GoerkeH. Organochlorine compounds in fish off the Antarctic Peninsula [J]. Chemosphere, 1996,33:404-410.
[7]黄俊,余刚,钱易.我国持久性有机污染物问题与研究对策[J].环境保护.2001,11:3-6.
[8]华小梅,单正军.我国农药生产、使用状况及其影响因子分析[J].环境科学进展.1996.4(2):23-25.
[9]Duursma E K, Carroll J. Environmental compartments sedi2 ments and assessment of processes between air, water, sedi2 ments and biota [M]. Germany:Spring-er,1996.
[10]Sink konen S. Paasivirta J. Degradation half-lief times of PCDDs, PCDFs and PCBs for environment fate modeling [J]. Chemosphere,2000,40 (9-77):943-949.
[11]苗秀生,储少岗等.全球性环境污染物多氯联苯的结构一活性相关性研究进展[J].北学进展,1996,8(4).
[12]龚钟明,曹军,李本刚.天津地区土壤中六六六的残留分布特征[J].中国环境科学,2003,23(3):311-314.
[13]David O什么是持久性有机污染物?持久性有机污染物控制研究会论文集[D].北京：国家环保局,2001.9.
[14]AARONTF, GRYAS, KERTHAH. Persistent organic pollutants (POPs) in a small herbivorous, Arctic marine zooplankton (Calanus hyperboreus):trends from April to July and the influence of lipids and trophic transfer [J]. Mar Pollut,2001(43):39-41.
[15]苏丽敏,袁星.持久性有机污染物(POPs)及其生态毒性的研究现状与展望[J].重庆环境科学,2003,25(9)：62-64.
[16]惠秀娟.环境毒理学[M].北京：化学工业出版社,2003,65-157.
[17]费维扬,艾宁,陈健.温室气体C02的捕集和分离[J].气体净化,2005,5(2):1-4.
[18]Ryckman DP, weseloh DV, Hamr GA, et al. Spatial and temporal trends in ogranochlorine contamination and bill deformities in Double-Creased cormorants from the Canadian Great Lakes [J] Environ Mont Assess,1998,53(1):169-195.
[19]Jones KC, de Voogt P. Persistent organic pollutants (POPs):state of the science [J]. Environ Pollut. 1999,100:209-221.
[20]Jane H, ChrisC, RichardW. MOMsand POPs [R]. Washington, D.C.:ENVIRONMENTAL WORKING GROUP,2000.
[21]EPA. SPECIAL REPORT ON ENVIRONMENT ENDOCRINE DIS-RUPTION:AN EFFECTS ASSESSMENT AND ANALYSIS [R]. Washington, D. C.:EPA,1997.
[22]薛建华,王近中,辛佩珠,等.氯仿,氯苯和多氯联苯对染毒家兔红细胞脂质过氧化和膜流动性的影响[J].中华预防医学杂志,1994,28(5)：294-296-
[23]徐科峰1,李忠1,何莼1,奚红霞1,赵月春2.持久性有机污染物(POPs)对人类健康的危害及其治理技术进展[J].四川环境2003年第22卷第4期：29-33.
[24]张海兵.剧毒物二恶英吸附技术的基础研究[D].广州：2001.
[25]Th.Wallenhorst et al, PCDD/F in ambient air and deposi-tion in Baden_Wurttemberg, Germany [J]. Chemospere,1997,34(5-7):1369-1378.
[26]Th. Kouimtzis. PCDD/Fs and PCBs in airborne particu-late matter of the greater Thessaloniki area, N. Greece [J]. Chemosphere,2002,47:193-205.
[27]Thoralf Kuchler et al, Application of GC-MS_MS for the analysis of PCDD/Fs in sewage effluents [J]. Chemosphere,2000,40:213-220.
[28]张祖麟.闽江口持久性有机污染物—多氯联苯的初步研究[J].环境科学学报,2002,22(6)：788-791.
[29]康跃惠,盛国英.珠江澳门河口沉积物柱样中有机氯农药的垂直分布特征[J].环境科学,2001,22(1)：81-85.
[30]L. G. BELLUCCI et al, Polychlorinated Dibenzo_p_dioxins and Dibenzofurans in Surficial Sediments of the Venice La-goon (Italy) [J]. Marine Pollution Bulletin,2000,40(1):65-76.
[31]Shunji Hashimoto et al, Simple sampling and analysis of PCDDs and PCDFs in Japanese seawater [J], Chemospere,1995,30(10):1979-1986.
[32]罗孝俊,杨卫东,党志.有机物污染的土壤治理方法及研究进展[J].矿物岩石地球化学通报,2000,19(2)：130-135.
[33]M. Manz, K._D.et al, Persistent organic pollutants in ag-ricultural soils of central Germany [J]. The Science of the Total Environment,2001,277:187-198.
[34]李国刚,李红莉.持久性有机污染物在中国的环境检测现状[J].中国环境检测,2004(4):53-60.
[35]M.Schuhmacher et al, PCDD/F concentration in milk of nonoccupationally exposed women living in Southern Catal-onia, Spain [J]. Chemospere,1999,38(5):995-1004.
[36]金重阳,郑玉峰等.国内持久性有机污染物的污染现状与对策建议[J].环境保护科学,2002,28(111).
[37]GullettB K, TouatiA. PCDD/F emissions from forest fire simu 21 ations [J]. Atmospheric Environment,2003,37(6):803-813.
[38]施汉昌,赵胤慧,冀静平.氯酚废水的生物处理技术的研究与进展[J].化学通报,1998,(8):1-5.
[39]江苏省环境监测中心.突发性污染事故中危险品档案库[DB/OL]. http://www.ep.net.cn/msds/, 2006-05-07.
[40]金相灿,机化合物污染化学-有毒有机物污染化学[J].北京：清华大学出版社,1990.
[41]Crosby D G. Environmental chemistry of pentachlorophenol, In:Pure&APP.Chem,1981,53: 1051-1080.
[42]曾光明,黄国和,袁兴中,等.堆肥环境生物与控制[J].北京：科学出版社,200.
[43]郭家钢,郑江,中国血吸虫病流行与防治[J].疾病控制杂志.2000,4(4)：289-293.
[44]肖东楼,余晴,党辉,等.2003年全国血吸虫病疫情通报[J].中国血吸虫病防治杂志,2004,16(6):401-403.
[45]陈国新,环境科学基础知识,上海：复旦大学出版社,1992,247-257.
[46]夏北成,环境污染物生物降解,北京：化学工业出版社,2002,266-276.
[47]任引津,张寿林,急性化学物中毒救援手册,上海：上海医科大学出版社,1994.
[48]Chiou Caryt T, Mcgroddy Susan E,Kile Daniel E.Partition characteristics of polycyclic aromatic hydro-carbons on soils and sediments [J]. Environ Sci Technol,1998,32(2):264-269.
[49]何江,关伟,李桂海,等.几种酚类化合物在黄河水体沉积物上吸附行为的实验研究[J].农业环境科学学报,2005,24(3)：480-485.
[50]迟杰,黄国兰,杨彬.五氯酚在表面微层水与表层水间的分配行为[J].环境科学,1999,20(6):18-21.
[51]谢玲玲,周培疆,刘丽君等.五氯苯酚在武汉东湖底质颗粒物上的吸附研究[J].环境保护,2005,51(4)：448-452.
[52]Junya Suegara, Byung-Dae Lee, Maria P. Espino et al. Photodegration of pentachlorophenol and its degration pathways predicted using density functional theory [J]. Chemosphere,2005, (61):341-346.
[53]Piccini P, Pichat P, GuillardC. Phototransformations of solid PentaehloroPhenol. Journal of photoehemistry and photobiology A,1998,119(2):137-142.
[54]楼静,金泥沙.五氯酚废水生化处理技术研究进展.环境科学与管理,2007,12:1 13-115.
[55]黄艺,敖晓兰,赵曦.五氯酚生物降解机理与外生菌根真菌对五氯酚可降解性.生态环境,2006,15(5)：1080-1085.
[56]张国平,Nicell J A,邹永廖,等.辣根过氧化物酶处理五氯酚过程的毒性特征[J].科学通报,2000,45(12)：1267-1271.
[57]Premalatha A, Rajakumar G Suseela.Pentachlorophenol degradation by Pseudomonas aeruginosa [J]. World Journal of Microbiology and Biotechnology,1994,10(3):334-337.
[58]王芳,林少彬,陈亚妍.氯酚在鲫鱼体内的分布存在形式与生物富集研究.卫生研究[J],1999,28(3)：169-171.
[59]张寿明,李金彪.金川选矿厂3#系统磨矿分级多参数测控[J].金属矿山,1996(5):34-37.
[60]李希明,陈家镛.机械化学在资源和材料化工及环保中的应用.化工冶金,2000,21(4):443-448.
[61]宋晓岚,邱冠周,杨华明.机械化学及其应用研究进展.金属矿山,2004年第11期：34-38.
[62]Kacova T K. Mechanical Activation of Minerals [M]. Elsevier,1989.155.
[63]Lin I J, Nadiv S, Grodzian J M. Minerals. Sci. Eng.1975,7(4):313-336.
[64]Baron P, Lin I J, Nadiv S, et al. J. Thermal Analysis,1994,42:217.
[65]Northwood D O Lewis D. Am. Mineral,1968,5:2089.
[66]Grohm H, Paudert R. Z. Chem.1963,3:89.
[67]Boldrev V.Particle Technology [M]. Nurnberg,1986.79.
[68]Heinicke G.Tribochemistry[M].Berlin, Akademie Verlag,1984.97.
[69]Rowlands SA, HallAK, McCormick PG, etal. Destruction of toxic materials [J]. Nature,1994,367: 223.
[70]Tsuyoshi Inoue, Miyuki Miyazaki, Masataka Kamitani. et.al.De-chlorination of Polyvinyl Chloride by its grinding with KOH and NaOH [J]. AdvancedPowderTechno.2005,16(1):27-34.
[71]Birke V. Economic and ecologically favorable destruction of poly-halogenated pollutions applying the DMCR [C]. Contaminated Soil2000. Proceedings of the seventh internationalFZK/TNO conference on contaminated soil 18-22 september 2000, Leipzig, Germany, ThomasTelford Publishing, London. 1330-1331.
[72]http://www.tribochem.Com [EB/OL].
[73]肖松文,肖晓.持久性有机污染物机械化学无害化处理的研究进展[J].矿冶工程,2006,26(2):53-57.
[74]Jones KC, de Voogt P. Persistent ogranic pollutants (POPs):state of the science [J]. Environ Pollut, 1999,100(3):209-221.
[75]Zhang Q, Saito F. Mechanochemical dechlorination of chlorinated compounds Journal of Materials Science [J].2004,39(2),5497-5501.