纸浆氯漂白过程中二噁英的来源及生成机制研究进展
Sources and formation mechanisms of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in the process of pulp bleaching with chlorine
-
摘要: 造纸过程中会产生大量的二英，本文从动力学和热力学角度综述了国内外制浆和氯漂白过程中二英的主要来源及反应机理.二英生成的途径主要包括二苯并对二英或二苯并呋喃的直接氯化、由前驱体转化为二苯并对二英或二苯并呋喃或其类似物再氯化、由外源氯酚直接缩合.同时讨论了未漂浆卡伯值、漂白中氯的用量、体系pH值、反应时间、温度等因素对二英生成的影响，可为有效地控制造纸过程中二英的生成提供参考.Abstract: Pulp and paper industry produces large amounts of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans(PCDD/Fs). This paper reviews the mechanisms of PCDD/Fs formation in pulping and chlorine bleaching in detail from the point of kinetics and thermodynamics. There are three main mechanisms:direct chlorination of dibenzo-p-dioxin and dibenzofuran(DBD/F), chlorination of DBD/F or DBD/F analogs transferred from other precursors, and condensation from chlorophenols. Meanwhile, the Kappa number of unbleached pulp,chlorine dosage, pH, reaction time, temperature and other factors on the formation of PCDD/Fs are discussed, which provide some references to effective control of PCDD/Fs formation in the papermaking process.
-
Key words:
- papermaking /
- PCDD/Fs /
- chlorine bleaching /
- mechanisms
-
-
[1] OLSON J R,BELLIN J S,BARNES D G.Reexamination of data used for establishing toxicity equivalence factors (TEFs) for chlorinated dibenzo-p-dioxins and dibenzofurans (CDDs and CDFs)[J].Chemosphere,1989,18(1):371-381. [2] HITES R A.Dioxins:An Overview and History[J].Environmental Science&Technology,2011,45(1):16-20. [3] SANDERMA W.Polychlorinated aromatic-compounds as pollutants[J].Naturwissenschaften,1974,61(5):207-213. [4] RAPPE C,KJELLER L O,JONSSON P,et al.Chlorinated dibenzodioxins and dibenzofurans and extractable organochlorines:Studies of sediment outside a pulp plant,Report to the Swedish Environmental Protections Board[R].1987. [5] RAPPE C,ANDERSSON R,BERGQVIST P A,et al.Overview on environmental fate of chlorinated dioxins and dibenzofurans:Sources,levels and isomeric pattern in various matrices[J].Chemosphere,1987,16(8-9):1603-1618. [6] SWANSON S E,RAPPE C,MALMSTR M J,et al.Emissions of PCDDs and PCDFs from the pulp industry[J].Chemosphere,1988,17(4):681-691. [7] AMENDOLA G,BARNA D,BLOSSER R,et al.The occurrence and fate of PCDDs and PCDFs in five bleached kraft pulp and paper mills[J].Chemosphere,1989,18(1-6):1181-1188. [8] BECK H,DROΒ A,ECKART K,et al.PCDDs,PCDFs and related compounds in paper products[J].Chemosphere,1989,19(1):655-660. [9] CLEMENT R E,TASHIRO C,SUTER S,et al.Chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) in effluents and sludges from pulp and paper mills[J].Chemosphere,1989,18(1-6):1189-1197. [10] KITUNEN V H,SALKINOJA-SALONEN M S.Occurrence of PCDDs and PCDFs in pulp and board products[J].Chemosphere,1989,19(1-6):721-726. [11] BECK H,DROB A,MATHAR W,et al.Influence of different regional emissions and cardboard containers on levels of PCDD,PCDF and related compounds in cow milk[J].Chemosphere,1990,21(6):789-798. [12] FOUQUET A,MESSIER F,COLGAN D,et al.Investigation for presence of chlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in bleaching processes from pulp and paper industries[J].Chemosphere,1990,20(10):1707-1714. [13] KITUNEN V H,SALKINOJA-SALONEN M S.Distribution of PCDD/PCDFs in PE-coated paperboards an explanation for migration of PCDD/PCDFs from board products[J].Chemosphere,1991,23(11):1561-1568. [14] JONSSON P,RAPPE C,KJELLER L O,et al.Pulp-mill related polychlorinated organic-compounds in baltic sea sediment[J].Ambio,1993,22(1):37-43. [15] WHITTEMORE R C,LAFLEUR L E,GILLESPIE W J,et al.USEPA/paper industry cooperative dioxin study:The 104 mill study[J].Chemosphere,1990,20(10-12):1625-1632. [16] YUNKER M B,CRETNEY W J,IKONOMOU M G.Assessment of chlorinated dibenzo-p-dioxin and dibenzofuran trends in sediment and crab hepatopancreas from pulp mill and harbor sites using multivariate-and index-based approaches[J].Environmental Science&Technology,2002,36(9):1869-1878. [17] AGENCY U S E P.The National Study[R].Tiers,1987,3,5,6,and 7(EPA 440/4-87-003):Office of Water Regulations and Standards (WH-553),Washington,D.C.20460. [18] AMENDOLA G,BARNA D,BLOSSER R,et al.The occurrence and fate of PCDDs and PCDFs in five bleached kraft pulp and paper mills[C].Seventh International Symposium on Chlorinated Dioxins and Related Compounds.1987.Las Vegas,Nevada,USA. [19] MACDONALD R W,IKONOMOU M G,PATON D W.Historical inputs of PCDDs,PCDFs,and PCBs to a British Columbia interior lake:The effect of environmental controls on pulp mill emissions[J].Environmental Science&Technology,1998,32(3):331-337. [20] 詹怀宇,刘秋娟,陈嘉川,等.制浆原理与工程[M].第三版.北京:中国轻工业出版社,2011.ZHAN H Y,LIU Q J,CHEN J C,et al.Pulping principle and engineering[M].The third edition.Beijing:Chinese Light Industry Press,2011(in Chinese). [21] KRINGSTAD K P,LINDSTROEM K.Spent liquors from pulp bleaching[J].Environmental Science&Technology,1984,18(8):236A-248A. [22] 中国造纸协会.中国造纸工业2014年度报告[J].中华纸业,2015,36(11):28-38. China Paper Association.2014 annual report of China's paper industry[J].China Pulp&Paper Industry,2015,36(11):28-38(in Chinese).
[23] ALLEN L H,BERRY C E,FLEMING B I,et al.Evdence that oil-based additives are a potential indirect source of the TCDD and TCDF produced in the kraft bleach plants[C].Eighth International Symposium on Chlorinated Dioxins and Related Compounds.1988,Umea,Sweden. [24] ALLEN L H,BERRY R M,FLEMING B I,et al.Evidence that oil-based additives are an indirect source of the TCDD and TCDF produced in kraft bleach plants[J].Chemosphere,1989,19(1-6):741-744. [25] VOSS R H,LUTHE C E,FLEMING B I,et al.Some new insights into the origins of dioxins formed during chemical pulp bleaching[J].Pulp&Paper Canada,1988,89(12):151-162. [26] GRAY A P,DIPINTO V M,SOLOMON I J.Synthesis of specific polychlorinated dibenzofurans[J].The Journal of Organic Chemistry,1976,41(14):2428-2434. [27] BERRY R,FLEMING B,VOSS R,et al.Toward preventing the formation of dioxins during chemical pulp bleaching[J].Pulp&Paper Canada,1989,90(8):48-58. [28] VANNESS G F,TIERNAN T O,HANES M S,et al.Determination of dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) in paper pulp mill defoamer additives and in paper pulp samples[J].Chemosphere,1990,20(10-12):1611-1618. [29] LAFLEUR L,BRUNCK B,MCDONOUGH T,et al.Studies on the mechanism of PCDD/PCDF formation during the bleaching of pulp[J].Chemosphere,1990,20(10):1731-1738. [30] DALLONS V J,WHITTEMORE R C,LAFLEUR L E,et al.A study of 2,3,7,8-TCDD and 2,3,7,8-TCDF formation at 23 bleach plants[J].Pulping Conference,1990:153-160. [31] DALLONS V J,WHITTEMORE R C,LAFLEUR L E,et al.An intensive study of the formation and distrubution of 2,3,7,8-TCDD and 2,3,7,8-TCDF during bleaching of kraft pulp[J].Organohalogen Compounds,1990,3:231-234. [32] KRINGSTAD K,ABE Z,SOUSA F,et al.On the formation of PCDDs and PCDFs in the bleaching of pulp[C].CPPA Environment Conference,1988,Vancouver,Canada. [33] RAPPE C,SWANSON S,GLAS B,et al.On the formation of PCDDs and PCDFs in the bleaching of pulp[J].Pulp&Paper Canada,1989,90(8):42-47. [34] DIMMEL D R,RIGGS K B,PITTS G,et al.Formation mechanisms of polychlorinated dibenzo-p-dioxins and dibenzofurans during pulp chlorination[J].Environmental Science&Technology,1993,27(12):2553-2558. [35] RAJAN P S,CHEN C L,GRATZL J S,et al.Formation of chloro-organics during chlorine bleaching of softwood kraft pulp.1.Chlorination of lignin model compounds[J].Holzforschung,1994,48:117-124. [36] HISE R G,HINTZ H L.The effect of brownstock washing on the formation of chlorinated dioxins and furans during bleaching[J].Tappi Journal,1990,73(1):185-190. [37] HRUTFIORD B F,NEGRI A R.Chlorinated dibenzofurans and dibenzodioxins from lignin models[J].Tappi Journal,1992,75(8):129-134. [38] HRUTFIORD B F,NEGRI A R.Dioxin sources and mechanisms during pulp bleaching[J].Chemosphere,1992,25(1):53-56. [39] HISE R G,WRIGHT B T,SWANSON S E.Formation of chlorinated dioxins and furans from lignin and lignin model compounds[J].Chemosphere,1990,20(10-12):1723-1730. [40] LUTHE C E,BERRY R M,VOSS R H.Are chlorinated phenols precursors of bleach plant dioxins?[J].Chemosphere,1994,28(10):1883-1894. [41] MARWAH N,RAJAN P S,JOYCE T W,et al.Chemistry and kinetics of formation of chloro-organics in chlorine bleaching of softwood kraft pulp[C].International pulp Bleaching Conference,1991,Stockholm,Sweden. [42] HUTZINGER O,BLUMICH M J,VDBERG M,et al.Sources and fate of PCDDs and PCDFs:An overview[J].Chemosphere,1985,14(6-7):581-600. [43] LAMPARSKI L L,STEHL R H,JOHNSON R L.Photolysis of pentachlorophenol-treated wood.Chlorinated dibenzo-p-dioxin formation[J].Environmental Science&Technology,1980,14(2):196-200. [44] SVENSON A,KJELLER L O,RAPPE C.Enzyme-mediated formation of 2,3,7,8-tetrasubstituted chlorinated dibenzodioxins and dibenzofurans[J].Environmental Science&Technology,1989,23(7):900-902. [45] ÖBERG L,RAPPE C.Biochemical formation of PCDD/Fs from chlorophenols[J].Chemosphere,1992,25(1):49-52. [46] LOMNICKI S,TRUONG H,DELLINGER B.Mechanisms of product formation from the pyrolytic thermal degradation of catechol[J].Chemosphere,2008,73(4):629-633. [47] LUTHE C E,BERRY R M,VOSS R H.Formation of chlorinated dioxins during production of bleached kraft pulp from sawmill chips contaminated with polychlorinated phenols[J].Tappi Journal,1993,76(3):63-69. [48] LUTHE C E.Octachlorinated dioxin in pulps and effluents:Where does it come from?[J].Chemosphere,1996,32(12):2409-2425. [49] SANTL H,GRUBER L,ST HRER E.Some new sources of polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) in waste papers and recycled pulps[J].Chemosphere,1994,29(9-11):1995-2003. [50] SANTL H,BICHLMAIER A,GRUBER L,et al.Mass balance of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzodioxins (PCDDs) in a recycling paper mill[J].Chemosphere,1994,28(9):1633-1639. [51] ZHENG M H,BAO Z C,WANG K O,et al.Levels of PCDDs and PCDFs in the bleached pulp from Chinese pulp and paper industry[J].Bulletin of Environmental Contamination and Toxicology,1997,59(1):90-93. [52] 郑明辉,包志成,徐晓白.草浆漂白过程中二英类生成机理探讨[J].环境化学,1999,18(6):526-531. ZHENG M H,BAO Z C,XU X B.Formation mechanisms of dioxins during hypochlorite bleaching or chlorination of non-wood plant fibers pulp[J].Environmental Chemistry,1999,18(6):526-531(in Chinese).
[53] ZHENG M H,BAO Z C,ZHANG B,et al.Polychlorinated dibenzo-p-dioxins and dibenzofurans in paper making from a pulp mill in China[J].Chemosphere,2001,44(6):1335-1337. [54] WANG X L,NI Y W,ZHANG H J,et al.Formation and emission of PCDD/Fs in Chinese non-wood pulp and paper mills[J].Environmental Science&Technology,2012,46(21):12234-12240. [55] 王雪丽,倪余文,张海军,等.草浆次氯酸盐漂白过程中二英的变化[J].环境化学,2014,33(4):604-610. WANG X L,NI Y W,ZHANG H J,et al.Change of PCDD/Fs during pulp hypochlorite bleaching process[J].Environmental Chemistry,2014,33(4):604-610(in Chinese).
[56] WANG X L,ZHANG H J,NI Y W,et al.Kinetics of PCDD/Fs formation from non-wood pulp bleaching with chlorine[J].Environmental Science&Technology,2014,48(8):4361-4367. [57] LUTHE C E,BERRY R M.The role of dibenzo-p-dioxin and dibenzofuran precursors in the formation of tetrachlorinated dibenzo-p-dioxins/-furans during bleaching[J].Chemosphere,1996,32(5):881-891. [58] RENBERG L,JOHANSSON N G,CHRISTIAN B.Destruction of PCDD and PCDF in bleached pulp by chlorine dioxide treatment[J].Chemosphere,1995,30(9):1805-1811. [59] SONNENBERG L B,DIMMEL D R.Reactions of dibenzo-p-dioxin and dibenzofuran with electrophilic reagents[J].Environmental Science&Technology,1993,27(7):1334-1339. [60] 全国人民代表大会常务委员会关于批准《关于持久性有机污染物的斯德哥尔摩公约》的决定.关于持久性有机污染物的斯德哥尔摩公约[J].中华人民共和国全国人民代表大会常务委员会公报,2004(5):342-365.Decision of the standing committee of the National People's Congress on approving the"Stockholm Convention on persistent organic pollutants".Stockholm convention on persistent organic pollutants[J].The communique of standing committee of the National People's Congress of the People's Republic of China,2004 (5):342-365(in Chinese).
[61] 国家履行斯德哥尔摩公约工作协调组办公室.中华人民共和国履行《关于持久性有机污染物的斯德哥尔摩公约》国家实施计划[M].北京:中国环境科学出版社,2008.Coordination group office of national implementation for Stockholm convention.The People's Republic of China-National implementation plan for the Stockholm convention on persistent organic pollutants[M].Beijing:China Environmental Science Press,2008(in Chinese). [62] [63] BERRY R M,LUTHE C E,VOSS R H,et al.The effects of recent changes in bleached softwood kraft mill technology on organochlorine emissions:An international perspective[J].Pulp&Paper Canada,1991,92(6):T155-T165. -
点击查看大图
计量
- 文章访问数: 1248
- HTML全文浏览数: 1164
- PDF下载数: 596
- 施引文献: 0
下载:
