高温燃烧过程中Cr的氧化机理及控制方法

doi:10.16085/j.issn.1000-6613.2016.s2.001

摘要/Abstract

摘要： Cr作为一种有害元素广泛地存在于化石燃料、生活垃圾和工业固体废物中。其中，化石燃料、相当大部分的生活垃圾以及一部分的工业固体废物都通过燃烧过程来回收能量或者进行减容和无害化处理。因此，通过燃烧过程人类向自然界中排放了大量的Cr。最重要的是，热处置过程中的高温氧化环境容易使低迁移性和毒性的Cr（Ⅲ）氧化为高迁移性和毒性的Cr（Ⅵ）。所以，热处置过程中Cr的反应、行为以及产物中Cr的存在形态得到了越来越多的研究。本文综述了燃料中Cr的存在形态、燃烧过程中Cr的氧化机理、燃烧过程中Cr氧化的控制方法以及燃烧产物中Cr的固化方法四方面内容，为减少燃烧过程中的Cr对环境的危害提供理论基础。

关键词: 热处置, 铬形态, 铬氧化, 固化

Abstract: Chromium is a hazardous element widely existing in fossil fuels、municipal solid wastes and industrial solid wastes.Most fossil fuels and significant portion of solid wastes are subjected to combustion for energy recovery or safe management.Therefore,combustion processes emit huge amounts of chromium into environment.Most importantly,high temperature and oxic conditions during thermal treatment may induce oxidation of chromium from Cr(Ⅲ),which is stable and low toxic,to Cr(Ⅵ) which is mobile and highly toxic.Hence,more and more researches focus on behavior of chromium in thermal process and speciation of chromium in products.This paper includes chromium speciation in fuels,mechanism of chromium oxidation in combustion,methods for inhibiting chromium oxidation and immobilization of chromium in by-products aimed to supply theoretical basis for reducing the threat of chromium emitted in combustion process.

Key words: thermal treatment, speciation of Cr, oxidiation of Cr, immobilization

中图分类号:

X705

蒋旭光, 董浩, 吕国均, 池涌, 严建华. 高温燃烧过程中Cr的氧化机理及控制方法[J]. 化工进展, 2016, 35(S2): 1-10.

JIANG Xuguang, DONG Hao, LÜ Guojun, CHI Yong, YAN Jianhua. Mechanism of chromium oxidation during combustion and control methods[J]. Chemical Industry and Engineering Progree, 2016, 35(S2): 1-10.

参考文献

[1] SAHA Rumpa,NANDI Rumki,SAHA Bidyut.Sources and toxicity of hexavalent chromium[J].Journal of Coordination Chemistry,2011,64(10):1782-1806.
[2] IZQUIERDO M,QUEROL X.Leaching behaviour of elements from coal combustion fly ash:an overview[J].International Journal of Coal Geology,2012(94):54-66.
[3] Ecoba.Production and utilization of CCPs in 2006 in Europe[EB/OL].2006.http://www.ecoba.org/ecobaccpprod.html.
[4] Acca.2006 Coal Combustion Product(CCP).Production and survey[EB/OL].USA:2006.http://www.ACCA-USA.org.
[5] REHR A P,SMALL M J,SCOTT Matthews H,et al. Economie sources and spatial distribution of airborne chromium risks in the U.S.[J].Environmental Science and Technology,2010,44(6):2131-2137.
[6] Aea.UK emissions of air pollutants 1970 to 2008. Oxfordshire[EB/OL]. UK:2010.http://uk-air.defra.gov.uk/reports/cat07/1009030925_Report_final270805.pdf.
[7] Australian Government,National pollutant inventory.Total national facility emissions for the substance:chromium(Ⅵ)compounds.[EB/OL].Australia:http://www.npi.gov.au/npidata.
[8] 韩露,谭建红,刘思琪.铬渣的环境危害及其治理技术研究[J].广州化工,2016,44(6):10-11.
[9] CABEZA L F,TAYLOR M M,DIMAIO G L,et al. Processing of leather waste:pilot scale studies on chrome shavings.Isolation of potentially valuable protein products and chromium[J].Waste Management,1998,18(3):211-218.
[10] BERRY F J,COSTANTINI N,SMART L E.Synthesis of chromium-containing pigments from chromium recovered from leather waste[J].Waste Management,2002,22(7):761-772.
[11] CASSANO A,DRIOLI E,MOLINARI R,et al.Quality improvement of recycled chromium in the tanning operation by membrane processes[J].Desalination,1997,108(1/2/3):193-203.
[12] 马宏瑞.制革废水处理过程中污泥处置与资源化对策探讨[EB/OL].http://www.chinaleather.org/Pages/News/20131031/154621.shtml.
[13] 林炜,穆畅道,唐建华.制革污泥处理与资源化利用[J].皮革科学与工程,2005(4):57-61.
[14] HUGGINS F E,HUFFMAN G P.How do lithophile elements occur in organic association in bituminous coals[J]. International Journal of Coal Geology,2004,58(3):193-204.
[15] DREISS S J.Chromium Migration through sludge-treated soils[J].Ground Water,1986,24(3):312-321.
[16] RICHARD F C,BOURG A C M.Aqueous geochemistry of chromium-a review[J].Water Research,1991,25(7):807-816.
[17] HUGGINS F E,NAJIH M,HUFFMAN G P. Direct speciation of chromium in coal combustion by-products by X-ray absorption fine-structure spectroscopy[J].Fuel,1999,78(2):233-242.
[18] HUGGINS F E,SHAH N,HUFFMAN G P,et al.Mode of occurrence of chromium in four US coals[J].Fuel Processing Technology,2000,63(2/3):79-92.
[19] HUGGINS F E,SHAH N,HUFFMAN G P,et al.XAFS spectroscopic characterization of elements in combustion ash and fine particulate matter[J].Fuel Processing Technology,2000,65:203-218.
[20] GOODARZI F,HUGGINS F E.Monitoring the species of arsenic,chromium and nickel in milled coal,bottom ash and fly ash from a pulverized coal-fired power plant in western Canada[J].Journal of Environmental Monitoring,2001,3(1):1-6.
[21] GALBREATH K C,ZYGARLICKE C J.Formation and chemical speciation of arsenic-,chromium-,and nickel-bearing coal combustion PM2.5[J].Fuel Processing Technology,2004,85(6/7):701-726.
[22] HUFFMAN G P,HUGGINS F E,SHAH N,et al. Speciation of arsenic and chromium in coal and combustion ash by XAFS spectroscopy[J].Fuel Processing Technology,1994,39(1/2/3):47-62.
[23] STAM A F,MEIJ R,WINKEL H T,et al.Chromium speciation in coal and biomass co-combustion products[J]. Environmental Science & Technology,2011,45(6):2450-2456.
[24] GOODARZI F,HUGGINS F E.Speciation of chromium in feed coals and ash byproducts from Canadian power plants burning subbituminous and bituminous coals[J].Energy & Fuels,2005,19(6):2500-2508.
[25] SHAH P,STREZOV V,PRINCE K,et al.Speciation of As,Cr,Se and Hg under coal fired power station conditions[J].Fuel,2008,87(10/11):1859-1869.
[26] HUGGINS F E,HUFFMAN G P. Application of XAFS spec-troscopy to coal geochemistry[J].Mineral Spectroscopy:A Tribute to Roger G.Burns,1996(5):133-151.
[27] FINKELMAN R B.Modes of occurrence of potentially hazardous elements in coal-levels of confidence[J].Fuel Processing Technology,1994,39(1/2/3):21-34.
[28] HUGGINS F E,HUFFMAN G P.Modes of occurrence of trace elements in coal from XAFS spectroscopy[J]. International Journal of Coal Geology,1996,32(1/2/3/4):31-53.
[29] CHEN J,JIAO F,ZHANG L,et al.Use of synchrotron XANES and Cr-doped coal to further confirm the vaporization of organically bound Cr and the formation of chromium(Ⅵ)during coal oxy-fuel combustion[J].Environmental Science & Technology,2012,46(6):3567-3573.
[30] LOW F,DE GIROLAMO A,WU X J,et al.Inhibition of lignite ash slagging and fouling upon the use of a silica-based additive in an industrial pulverised coal-fired boiler:Part 3-Partitioning of trace elements[J].Fuel,2015,139:746-756.
[31] HU H Y,XU Z,LIU H,et al.Mechanism of chromium oxidation by alkali and alkaline earth metals during municipal solid waste incineration[J].Proceedings of the Combustion Institute,2015,35:2397-2403.
[32] PAOLETTI F.Behavior of oxyanions forming heavy metals in municipal solid waste incineration[D].Thesis Technical,2002.
[33] KIRK D W,CHAN C C Y,MARSH H.Chromium behavior during thermal treatment of MSW fly ash[J]. Journal of Hazardous Materials,2002,90(1):39-49.
[34] CHEN J,JIAO F C,ZHANG L,et al.Elucidating the mechanism of Cr(Ⅵ)formation upon the interaction with metal oxides during coal oxy-fuel combustion[J].Journal of Hazardous Materials,2013,261:260-268.
[35] VERBINNEN B,BILLEN P,VAN CONINCKXLOO M,et al.Heating temperature dependence of Cr(Ⅲ)oxidation in the presence of alkali and alkaline earth salts and subsequent Cr(Ⅵ)leaching behavior[J].Environmental Science & Technology,2013,47(11):5858-5863.
[36] MAO L Q,GAO B Y,DENG N,et al.The role of temper-ature on Cr(Ⅵ)formation and reduction during heating of chromium-containing sludge in the presence of CaO[J]. Chemosphere,2015,138:197-204.
[37] LOW Fiona,KIMPTON Justin,WILSON Siobhan A,et al.Chromium reaction mechanisms for speciation using synchrotron in-situ high-temperature X-ray diffraction[J]. Environmental Science & Technology,2015,49(13):8246-8253.
[38] PANICHEV N,MABASA W,NGOBENI P,et al. The oxidation of Cr(Ⅲ)to Cr(Ⅵ)in the environment by atmospheric oxygen during the bush fires[J].Journal of Hazardous Materials,2008,153(3):937-941.
[39] KAVOURAS P,PANTAZOPOULOU E,VARITIS S,et al.Incineration of tannery sludge under oxic and anoxic conditions:study of chromium speciation[J].Journal Of Hazardous Materials,2015,283:672-679.
[40] SWARNALATHA S,ARASAKUMARI M,GNANAMANI A,et al. Solidification/stabilization of thermally-treated toxic tannery sludge[J].Journal of Chemical Technology and Biotechnology,2006,81(7):1307-1315.
[41] SWIETLIK R,TROJANOWSKA M,LOZYNSKA M,et al.Impact of solid fuel combustion technology on valence speciation of chromium in fly ash[J].Fuel,2014,137:306-312.
[42] JIAO F,WIJAYA N,ZHANG L,et al.Synchrotron-based XANES speciation of chromium in the oxy-fuel fly ash collected from lab-scale drop-tube furnace[J]. Environmental Science & Technology,2011,45(15):6640-6646.
[43] SWARNALATHA Somasundaram,KUMAR Arumugam Ganesh,TANDAIAH Srinivasulu,et al.Efficient and safe disposal of chrome shavings discharged from leather industry using thermal combustion[J]. Journal of Chemical Technology and Biotechnology,2009,84(5):751-760.
[44] SWARNALATHA S,RAMANI K,KARTHI A G,et al. Starved air combustion-solidification/stabilization of primary chemical sludge from a tannery[J].Journal of Hazardous Materials,2006,137(1):304-313.
[45] SWARNALATHA S,SRINIVASULU T,SRIMURALI M,et al.Safe disposal of toxic chrome buffing dust generated from leather industries[J].Journal of Hazardous Materials,2008,150(2):290-299.
[46] SKRYPSKIMANTELE S,BRIDLE T R.Environmentally sound disposal of tannery sludge[J].Water Research,1995,29(4):1033-1039.
[47] CABALLERO J A,FONT R,ESPERANZA M M.Kinetics of the thermal decomposition of tannery waste[J].Journal of Analytical and Applied Pyrolysis,1998,47(2):165-181.
[48] ERDEM M,OZVERDI A.Leaching behavior of chromium in chrome shaving generated in tanning process and its stabilization[J].Journal of Hazardous Materials,2008,156(1/2/3):51-55.
[49] SEKARAN G,SHANMUGASUNDARAM K A,MARIAPPAN M. Characterization and utilisation of buffing dust generated by the leather industry[J].Journal of Hazardous Materials,1998,63(1):53-68.
[50] OLIVEIRA L C A,GUERREIRO M C,GONCALVES M,et al.Preparation of activated carbon from leather waste:a new material containing small particle of chromium oxide[J]. Materials Letters,2008,62(21/22):3710-3712.
[51] YILMAZ Onur,KANTARLI I Cem,YUKSEL Mithat,et al.Conversion of leather wastes to useful products[J]. Resources Conservation and Recycling,2007,49(4):436-448.
[52] KANTARLI Ismail Cem,YANIK Jale.Activated carbon from leather shaving wastes and its application in removal of toxic materials[J].Journal of Hazardous Materials,2010,179(1/2/3):348-356.
[53] KONG J J,YUE Q Y,HUANG L H,et al.Preparation,characterization and evaluation of adsorptive properties of leather waste based activated carbon via physical and chemical activation[J].Chemical Engineering Journal,2013,221:62-71.
[54] KATO Norio.Reduction of chromium(Ⅵ)elution from coal ash by two-stage combustion method for pulverized coal firing[J].Bunseki Kagaku,2015,64(2):125-130.
[55] DUBIKOVA M,JANKOWSKI J,WARD C R. Modelling element mobility in water-fly ash interactions:research report 61[R].Australia:C.-o.R.C.f.C.i.S. Development,2006.
[56] NARUKAWA Tomohiro,RILEY Kenneth W,FRENCH David H,et al.Speciation of chromium in Australian fly ash[J].Talanta,2007,73(1):178-184.
[57] SOCO Eleonora,KALEMBKIEWICZ Jan.Investigations on Cr mobility from coal fly ash[J].Fuel,2009,88(8):1513-1519.
[58] PINTO C A,HAMASSAKI L T,VALENZUELA-DIAZ F R,et al.Tannery waste solidification and stabilization-Thermal and mechanical characterization[J].Journal of Thermal analysis and Calorimetry,2004,77(3):777-787.
[59] FILIBELI A,BUYUKKAMACI N,SENOL H.Solidification of tannery wastes[J].Resources Conservation and Recycling,2000,29(4):251-261.
[60] DWECK J,BUCHLER P M,COELHO A C V,et al. Solidification/stabilization of a tannery waste with blended cement and Wyoming bentonite[J].Journal of Environmental Science and Health Part A——Toxic/Hazardous Substances & Environmental Engineering,2000,35(5):715-740.
[61] WANG S,VIPULANADAN C.Solidification/stabilization of Cr(Ⅵ)with cement-Leachability and XRD analyses[J]. Cement and Concrete Research,2000,30(3):385-389.
[62] PINTO C A,DWECK J,SANSALONE J J,et al.Early stages of solidification/stabilization of storm water runoff solid residuals in cement-Non-conventional DTA[J]. Journal of Thermal analysis and Calorimetry,2005,80(3):715-720.
[63] PINTO C A,DWECK J,SANSALONE J J,et al. Evaluation of S/S process of tannery waste in cement by structural and mechanical analysis[J].Advanced Powder Technology Vii,2010,660/661:1130-1136.
[64] KINDNESS A,MACIAS A,GLASSER F P. Immobilization of chromium in cement matrices[J]. Waste Management,1994,14(1):3-11.
[65] WANG S,VIPULANANDAN C.Solidification/stabilization of Fe(Ⅱ)-treated Cr(Ⅵ)-contaminated soil[J]. Environmental Engineering Science,2001,18(5):301-308.
[66] BHATTY M S Y.Fixation of metallic ions in Portland cement[M].Portland Cement Association,Skokie,IL,1986.
[67] BISHOP P L.Leaching of inorganic hazardous constituents from stabilized solidified hazardous wastes[J].Hazardous Waste & Hazardous Materials,1988,5(2):129-143.
[68] KUMARATHASAN P,MCCARTHY G J,HASSETT D J,et al.Oxyanion substituted ettringites:synthesis and characterisation and their potential role in immobilisation of As,B,Cr,Se and V.[J].Mat.Res.Soc.Syrup.Proc.,1990,178:83-104.
[69] POELLMANN H,AUER S,KUZEL H J,et al.Solid-solution of ettringites.2.Incorporation of B(OH)₄^- and CrO₄^2- in 3CaO·Al₂O₃·3CaSO₄·32H₂O[J].Cement and Concrete Research,1993,23(2):422-430.
[70] PINTO C A,VALENZUELA-DIAZ F R,SANSALONE J J,et al.X-ray diffraction study of particulate tannery waste solidified in cement[J].Advanced Powder Technology V,2006,530/531:478-484.
[71] ZAMORANI E,SHEIKH I A,DELLA ROSA M,et al. Physical properties and leachability of MLW stream containing Cr,Ni and Cd immobilised in a cement matrix.[J]. Materials Research Society Symposium Proceedings,1989,127:489-494.
[72] IVEY D G,NEUWIRTH N,CONRAD D,et al. Chemistry and microstructure of solidified waste forms[M].Boca Raton FL:Lewis Publishers,1990:5.
[73] OMOTOSO O E,IVEY D G,MIKULA R.Quantitative X-ray diffraction analysis of chromium(Ⅲ)doped tricalcium silicate pastes[J].Cement and Concrete Research,1996,26(9):1369-1379.
[74] MORAIS L C,DWECK J,CAMPOS V,et al. Characterization of sewage sludge ashes to be used as a ceramic raw material[J].Icheap-9 9th International Conference on Chemical And Process Engineering Pts 1-3,2009,17:1813-1818.
[75] MORAIS L C,DWECK J,GONCALVES E M,et al.An experimental study of sewage sludge incineration[J]. Environmental Technology,2006,27(9):1047-1051.
[76] MORONI Marilena,BRIGIDA Cristiano,POLI Stefano,et al.Fixing chromium and lead in ceramic materials:a petrological approach to inertization and recycling of toxic industrial waste[J].Periodico Di Mineralogia,2004,73:99-111.
[77] BASEGIO T,BERUTTI F,BERNARDES A,et al. Environ-mental and technical aspects of the utilisation of tannery sludge as a raw material for clay products[J]. Journal of the European Ceramic Society,2002,22(13):2251-2259.
[78] BASEGIO T,HAAS C,POKORNY A,et al.Production of materials with alumina and ashes from incineration of chromium tanned leather shavings:environmental and technical aspects[J].Journal of Hazardous Materials,2006,137(2):1156-1164.
[79] ABREU M A,TOFFOLI S M.Characterization of a chromium-rich tannery waste and its potential use in ceramics[J].Ceramics International,2009,35(6):2225-2234.