摘要
为解决城市污泥热解的能量自给不足和热解产物不能有效利用等问题,采用连续式固定床热解装置和热重分析仪对城市污泥及其与煤混合物的混合热解特性及两段催化热解特性进行了研究,探讨了污泥与煤混合热解的协同作用机制及挥发性产物的催化裂解机理,分析了最优工况的能量供需平衡,讨论了固相产物的应用途径,研制了一套中试规模的污泥热解装置。研究结果表明:在污泥热解过程中添加煤进行混合热解可解决污泥单独热解自身能量不足的问题,并能有效改善产物特性,且两者在热解过程中存在协同效应;Ni/分子筛复合催化剂可促进热解液转化为洁净可燃性气体或化工原料合成气;污泥炭可当污水处理剂、燃料或土壤改良剂使用;中试热解设备实现了装置各系统的集成一体化和热解液或热解气燃烧的系统能量自给,且中试与小试的运行条件或产物特性差别不大。
To meet self-energy required in sewage sludge drying and pyrolysis and sought forways on utilization of pyrolysis products, co-pyrolysis behavior and two-stage catalysisbehavior of sewage sludge and mixture with coal were carried out by thermo-gravimetricanalysis (TGA), one-stage or two-stage continuous pyrolysis furnace.The interaction ofsewage with coal, catalysis cracking of volatile phase, energy balance analysis andproducts utilization were discussed. The results showed it can meet self-energy requiredby co-pyrolysis of sewage sludge with coal and improve products yield, it also verifiedthe presence of interaction of sludge with coal in co-pyrolysis process. Ni/molecular sievecatalysts can turn pyrolysis liquids into clean combustible gas; sludge-char can be used assewage treatment agent, fuel and soil improvement. While the optimal operatingconditions and product characteristics with the bench experiment are nearly coincident, itwas feasible that pilot-scale sludge pyrolysis device systems could be assembled together.
引文
[1] J.A.Morillo,B.Antizar-Ladislao,M.Monteoliva-Sanchez,et al.Bioremediation andbiovalorisation of olive-mill wastes.Applied microbiology and biotechnology,2009,82:25-39
[2]何晶晶,顾国维,李笃中,等.城市污泥处理与利用,科学出版社,北京,2003
[3] Chu C P,Lee D J,Chang C Y.Thermal pyrolysis characteristics of polymer flocculated wasteactivated sludge.Water Res,2001,25(1):49-56
[4]尹军,谭学军.污水污泥处理处置与资源化利用.北京:化工工业出版社,2005
[5] Turovskiy I S,Mathai P K.Wastewater sludge processing.Hoboken,New Jersey:John Wileyand Sons,Inc.2006
[6]朱锡锋.生物质热解原理与技术.合肥:中国科学技术大学出版社,2006
[7]蔡璐,陈同斌,高定,等.中国大中型城市的城市污泥热值分析.中国给水排水.2010,26(15):106-108
[8]李海波,柳青,孙铁珩,等.中国城市污泥资源化利用研究进展.三峡环境与生态,2008,1(2):42-47
[9]李艳霞,陈同斌,罗维,等.中国城市污泥有机质及养分含量与土地利用,生态学报.2003,23(11):2464-2473
[10]邱兆富,周琪.国内城市污水污泥的特点及处理处置对策.中国沼气.2004,22(2):22-25
[11]黄海峰,陈立柱,王军.废物利用与循环经济北京:中国轻工业出版社,2013
[12]Eurostat. Sewage sludge production and dispoal. Available from: http://appsso.eurostat.ec.europa.eu/nui/.2011-05-25
[13] Inguanzo M.,Dom A.nguez,Mene J.A..On the pyrolysis of sewage sludge:the influenceof pyrolysis conditions on solid,liquid and gas fractions.Journal of Analytical and AppliedPyrolysis,2002,63:209–222.
[14] Casajusa C.,Abregob J.,Mariasa F.Product distribution and kinetic scheme for the fxedbed thermal decomposition of sewage sludge.Chemical Engineering Journal,2009,145(3):412–419.
[15]孙立,张晓东.生物质热解与气化原理与技术.北京:化学工业出版社,2013:122-123
[16] P.Basu.Biomass Gasification and Pyrolysis Practical Design Theory.北京:科学出版社,2011
[17]贾相如,金保升,李睿.基于TG-FTIR联用的污水污泥热解实验研究.锅炉技术.2009,40(3):77-80.
[18]胡艳军,宁方勇,钟英杰.城市污水污泥热解特性及动力学规律研究.热能动力工程.2012,27(2):253-258.
[19]汪询.污泥热化学处理的试验研究.武汉理工大学学报,2002,24(6):35-37
[20]何晶晶,顾国维,李笃中,等.城市污泥处理与利用.北京:科学出版社,2003
[21]管志超,胡艳军,钟英杰.不同升温速率下城市污水污泥热解特性及动力学研究.环境污染与防治.2012(3):35-39.
[22]唐海,欧阳龙.焦化废水处理剩余污泥热解特性分析.给水排水,2013,39(7):142-145
[23]陈江,杨金福,蔡泓林等.污泥的热解特性实验研究.浙江工业大学学报,2005,33(3):315-318
[24]韩晓强,陈晓平.分布活化能模型在污泥热解特性研究中的应用.燃烧科学与技术,2006,12(2):147-150
[25] Gabriel Gasco,Ana M6ndez.Preparation of carbon-based adsorbents from sewage sludgepyrolysis to remove metals from water.Desalination,2005:245-251.
[26]余刚,刘希涛,郑叶青等译,北京:中国环境科学出版社,2005
[27]何国伟,叶志平,万爱亮,等.牛仔布加工厂印染污泥制备吸附剂的实验研究.环境工程学报.2009,3(7):1245-1248
[28] Shen L,Zhang D K.An experimental study of oil recovery from sewage sludge bylow-temperature pyrolysis in a fluidized-bed.Fuel,2003,82:465-472
[29] Lutz H,Romeiro G A,Damasceno R N,et al.Low temperature conversion of someBrazilian municipal and industrial sludges.Bioresource Technology,2000,74:103-107
[30] Bridle,T.R.and Campbell,H.W..Use of Pyrolysis to Recover Energy and Nutrientsfrom Biosolids.Oil from Sludge:A Technology Update.Proceedings9th Annual AQTEConference,Montreal,Canada.1986
[31]于洪江,杨金凯.污泥低温碳化技术的中试研究.中国建设信息(水工业市场).2009(03)
[32]何品晶,顾国维,邵立明,等.污水污泥低温热解处理技术研究.中国环境科学.1996(04):254-257
[33]罗鹏,张双全,李娜等.城市污泥与低变质煤共热解制备吸附剂. http://www.PaperEdu.cn,1-5
[34]唐汝江.污水污泥与煤混合燃烧和热解的试验研究(硕士学位论文).华中科技大学,2005.
[35]刘汉湖,张双圣,张双全,等.污泥与煤共热解制备吸附剂及其对活性艳红X-3B的吸附性能.环境科学研究,2011,24(6):704-710
[36]张强,张强,吴颜,等.李伟锋污泥与煤共热解过程中磷元素的挥发规律研究.燃料化学学报,2012,40(6):666-671
[37]张丽.污泥催化裂解试验研究.南京:南京大学,2011
[38]胡湛波.二噁英类污染底泥的热解无害化研究.上海:上海交通大学,2007
[39]郭树才,任瑞玲.抚顺泥炭两段热解研究.大连工学院学报,1986,24(2):35-38
[40]苏攀.两段气化炉内钙盐催化过程研究.武汉:华东理工大学,2012
[41]李权柄,汪华林,张振华等.两段式热解厨余垃圾实验研究.环境工程学报,2009,3(1):175-178
[42]吴仕生.煤低焦油两段气化的基础研究.大连:大连理工大学,2011
[43]陈源,陈烈强.废旧阻燃HIPS塑料的真空热解.华南理工大学学报(自然科学版),2009,37(6):58-62
[44] H.W.Campbell,A.H.Dirkzwager,Sewage Sludge Treatment&Use,London:ElsevierApplied Science,1989,281-290
[45] T.R.Bridle,I.Hammerton and C.K.Hertle,Control of heavy metals andorganochlorinesusing the oil from sewage process,Water Science Technology,1990,22(12):249-258
[46] L.F.Calvo,M.Otero,B.M.Jenkins,et al.Heating Process Characteristics and Kineticsof Sewage Sludge in Different Atmospheres.Thermochimica Acta.2004,409(2):127-135
[47] M.Inguanzo,A.Dom′nguez,J.A.Mene′ndez,et al.On the Pyrolysis of Sewage Sludge:The Infuence of Pyrolysis Conditions on Solid,Liquid and Gas Fractions.Journal ofAnalytical and Applied Pyrolysis.2002,63:209-222
[48] S.Luo,B.Xiao,Z.Hu,et al.Effect of Particle Size on Pyrolysis of Single-ComponentMunicipal Solid Waste in Fixed Bed Reactor. International Journal of HydrogenEnergy.2010,35(1):93-97
[49] J.J.Wang Xiaohu.Effect of Heating Rate on the Municipal Sewage Sludge PyrolysisCharacter.Energy Proceed.2012
[50]A.Fullana,J.A.Conesa,R.Font,et al.Pyrolysis of Sewage Sludge:NitrogenatedCompounds and Pretreatment Effects.Journal of Analytical and Applied Pyrolysis.2003,68-69:561-575
[51] M.Otero,L.F.Calvo,M.V.Gil,et al.Co-Combustion of Different Sewage Sludgeand Coal:A Non-Isothermal Thermogravimetric Kinetic Analysis.Bioresour Technol.2008,99(14):6311-6319
[52] S.Vyazovkin,A.K.Burnham,J.M.Criado,et al.Ictac Kinetics CommitteeRecommendations for Performing Kinetic Computations on Thermal AnalysisData.Thermochimica Acta.2011,520(1-2):1-19
[53] M.E.Sánchez,J.A.Menéndez,A.Domínguez,et al.Effect of Pyrolysis Temperatureon the Composition of the Oils Obtained from Sewage Sludge. Biomass andBioenergy.2009,33(6-7):933-940
[54] A.Debdoubi,A.Amarti,E.Colacio,et al.The Effect of Heating Rate on Yields andCompositions of Oil Products from Esparto Pyrolysis.international Journal of EnergyResearch.2006,30(15):1243-1250
[55]闫云飞,张力,李丽仙.工业废水污泥的热解及升温速率对热解的影响.环境工程学报.2012,06(3):896-902.
[56]邵敬爱,陈汉平,晏蓉,等.热解温度对污泥热解半焦产率与特性影响的研究.可再生能源.2008,26(5):31-34.
[57] M.Inguanzo,A.Dom′nguez,J.A.Mene′ndez,et al.On the Pyrolysis of Sewage Sludge:The Infuence of Pyrolysis Conditions on Solid,Liquid and Gas Fractions.Journal ofAnalytical and Applied Pyrolysis.2002,63:209-222
[58] X.Ren,B.Liang,M.Liu,et al.Effects of Pyrolysis Temperature,Time and Leaf Litterand Powder Coal Ash Addition on Sludge-Derived Adsorbents for Nitrogen Oxide.BioresourTechnol.2012,125:300-304
[59]万立国,田禹,张丽君,等.污水污泥高温热解技术研究现状与进展.环境科学与技术.2011,34(6):109-114.
[60] A.Domínguez,J.A.Menéndez,J.J.Pis.Hydrogen Rich Fuel Gas Production from thePyrolysis of Wet Sewage Sludge at High Temperature.Journal of Analytical and AppliedPyrolysis.2006,77(2):127-132
[61]程晓波,仇翀,尹炳奎.污泥碳化制备活性炭.化工环保.2010,30(5):446-449.
[62] A.Elaziouti,N.Laouedj,A.A.Segheir.Preparation and Evaluation of New Adsorbent(Paper Sludge)in the Treatment of Waste Water of Textile Industry.Journal of the KoreanChemical Society.2010,54(1):115-119
[63] C.Jindarom,V.Meeyoo,B.Kitiyanan,et al.Surface Characterization and Dye AdsorptiveCapacities of Char Obtained from Pyrolysis/Gasification of Sewage Sludge.ChemicalEngineering Journal.2007,133(1-3):239-246
[64] M.J.Martin,E.Serra,A.Ros,et al.Carbonaceous Adsorbents from Sewage Sludgeand Their Application in a Combined Activated Sludge-Powdered Activated Carbon(as-Pac) Treatment.Carbon.2004,42(7):1389-1394
[65] S.Rio,L.Le Coq,C.Faur,et al.Preparation of Adsorbents from Sewage Sludge by SteamActivation for Industrial Emission Treatment. Process Safety and EnvironmentalProtection.2006,84(4):258-264
[66]张艳丽,肖波,胡智泉,等.污泥热解残渣水蒸气气化制取富氢燃气.可再生能源.2012(1):67-71.
[67] M.He,B.Xiao,S.Liu,et al.Syngas Production from Pyrolysis of Municipal Solid Waste(Msw) with Dolomite as Downstream Catalysts.Journal of Analytical and AppliedPyrolysis.2010,87(2):181-187
[68]孙立,张晓东.生物质热解与气化原理与技术.北京:化学工业出版社,2013:124-125
[69] N.-Y.Wang,C.-H.Shih,P.-T.Chiueh,et al.Environmental Effects of Sewage SludgeCarbonization and Other Treatment Alternative. Energies.2013,6(2):871-883
[70] Caballero,J.A.,Front,R.,Marcilla,A.,et al.Characterization of sewage sludgesby primary and secondary pyrolysis.J.Anal.Appl.Pyrolysis.1997,40–41:433–450.
[71]张立国,刘蕾,张秋云,等.市政污水污泥催化热解特性研究.华南师范大学学报(自然科学版).2011(04):94-97.
[72] M.Seredych,C.Strydom,T.J.Bandosz.Effect of Fly Ash Addition on the Removal ofHydrogen Sulfide from Biogas and Air on Sewage Sludge-Based CompositeAdsorbents.Waste Manag.2008,28(10):1983-1992
[73] Shao,R.Yan,H.Chen,H.Yang,et al.Catalytic Effect of Metal Oxides on Pyrolysisof Sewage Sludge.Fuel Processing Technology.2010,91(9):1113-1118
[74] D.K.Park,S.D.Kim,S.H.Lee,et al.Co-Pyrolysis Characteristics of Sawdust andCoal Blend in Tga and a Fixed Bed Reactor.Bioresour Technol.2010,101(15):6151-6156
[75] L.Zhang,S.Xu,W.Zhao,et al.Co-Pyrolysis of Biomass and Coal in a Free FallReactor.Fuel.2007,86(3):353-359
[76]田禹,左薇,陈琳,等.城市污水污泥过程减量及资源化利用理论与技术.北京:科学出版社,2012
[77] A.Domínguez,J.A.Menéndez,J.J.Pis.Hydrogen Rich Fuel Gas Production from thePyrolysis of Wet Sewage Sludge at High Temperature.Journal of Analytical and AppliedPyrolysis.2006,77(2):127-132
[78]刘秀如,吕清刚,矫维红.一种煤与两种城市污水污泥混合热解的热重分析.燃料化学学报.2011,39(1):8-13.
[79]] X.-g.Li,B.-g.Ma,L.Xu,et al.Thermogravimetric Analysis of the Co-Combustionof the Blends with High Ash Coal and Waste Tyres.Thermochimica Acta.2006,441(1):79-83
[80] Z.Shuang-quan,Y.Xiao-ming,Y.Zhi-yuan,et al.Study of the Co-Pyrolysis Behaviorof Sewage-Sludge/Rice-Straw and the Kinetics.Procedia Earth and Planetary Science.2009,1(1):661-666
[81] I.Fonts,G.Gea,M.Azuara,et al.Sewage Sludge Pyrolysis for Liquid Production:AReview.Renewable and Sustainable Energy Reviews.2012,16(5):2781-2805
[82] Y.D.He,Y.B.Zhai,C.T.Li,et al.The Fate of Cu,Zn,Pb and Cd During the Pyrolysisof Sewage Sludge at Different Temperatures.Environ Technol.2010,31(5):567-574
[83] G.van Rossum,B.Potic,S.R.A.Kersten,et al.Catalytic Gasification of Dry and WetBiomass.Catalysis Today.2009,145(1-2):10-18
[84] D.A.Bulushev,J.R.H.Ross.Catalysis for Conversion of Biomass to Fuels Via Pyrolysisand Gasification:A Review.Catalysis Today.2011,171(1):1-13
[85] C.Perego,D.Bianchi.Biomass Upgrading through Acid–Base Catalysis.ChemicalEngineering Journal.2010,161(3):314-322
[86] D.G.Vlachos,J.G.Chen,R.J.Gorte,et al.Tsapatsis.Catalysis Center for EnergyInnovation for Biomass Processing:Research Strategies and Goals.Catalysis Letters.2010,140(3-4):77-84
[87] Peder Brandt,Ulrik Henriksen.Decomposition of tar in gas from Updraft gasifiers byThermal Cracking//Proceedings of1st World Conference on Biomass for Energy andIndustry,2000.
[88] Pekka A Simell,Jukka K Leppalahti,Esa A Kurkela.Tar-decomposition Activity ofCarbonate Rocks Under High CO2Partial Pressure.Fuel,1995,74(6):938-945.
[89] Czernik,C.,French,R.,Feik,C.,et al.Hydrogen by Catalytic Steam Reformingof Liquid Byproducts from Biomass Thermoconversion Processes. Industrial andEngineering Chemistry Research,2002,41(7):4209-4215.
[90] Garcia,L.,French,R.,Czenik,S.,et al.Catalytic steam reforming of bio-oils forthe production of hydrogen:effects of catalyst composition,Applied Catalysis A:General,2000,(201):225-239.
[91] Van Rossum,G.,Kersten,S.R.A.,et al.Catalytic and noncatalytic gasification ofpyrolysis oil,Submitted to Ind.Eng.Chem.Rs.,available online:DOI:10.1021/ie061337y.
[92] E.Agrafioti,G.Bouras,D.Kalderis,et al.Biochar Production by Sewage SludgePyrolysis.Journal of Analytical and Applied Pyrolysis.2013,101:72-78
[93] C.Jindarom,V.Meeyoo,B.Kitiyanan,et al.Surface Characterization and Dye AdsorptiveCapacities of Char Obtained from Pyrolysis/Gasification of Sewage Sludge.ChemicalEngineering Journal.2007,133(1-3):239-246
[94] K.M.Smith,G.D.Fowler,S.Pullket,et al.Sewage Sludge-Based Adsorbents:AReview of Their Production,Properties and Use in Water Treatment Applications.WaterRes.2009,43(10):2569-2594
[95] L.Yu,Q.Zhong.Preparation of Adsorbents Made from Sewage Sludges for Adsorption ofOrganic Materials from Wastewater.J Hazard Mater.2006,137(1):359-366
[96] M.Otero,F.Rozada,A.Morán,et al.Removal of Heavy Metals from Aqueous Solutionby Sewage Sludge Based Sorbents: Competitive Effects.Desalination.2009,239(1-3):46-57
[97] J.Zou,Y.Dai,X.Wang,et al.Structure and Adsorption Properties of SewageSludge-Derived Carbon with Removal of Inorganic Impurities and High Porosity.BioresourTechnol.2013,142:209-217
[98] V.M.Monsalvo,A.F.Mohedano,J.J.Rodriguez.Adsorption of4-Chlorophenol byInexpensive Sewage Sludge-Based Adsorbents. Chemical Engineering Research andDesign.2012,90(11):1807-1814
[99] M.Otero,F.Rozada,L.F.Calvo,et al.Elimination of Organic Water Pollutants UsingAdsorbents Obtained from Sewage Sludge.Dyes and Pigments.2003,57(1):55-65
[100]余兰兰,余宏伟.污泥改性制备烟气脱硫吸附剂的研究.现代化工.2010,30(1):47-50.
[101]王犇,孟韵.污水处理厂污泥制备吸附剂对燃煤烟气中汞的吸附性能研究.现代化工.2009,29(12):53-56.
[102] A.Anfruns,M.J.Martin,M.A.Montes-Morán.Removal of Odourous Vocs UsingSludge-Based Adsorbents.Chemical Engineering Journal.2011,166(3):1022-1031
[103]A.Ansari,A.Bagreev,T.J.Bandosz.Effect of Adsorbent Composition on H2s Removalon Sewage Sludge-Based Materials Enriched with Carbonaceous Phase.Carbon.2005,43(5):1039-1048
[104] W.Yuan,T.J.Bandosz.Removal of Hydrogen Sulfide from Biogas on Sludge-DerivedAdsorbents.Fuel.2007,86(17-18):2736-2746
[105] P.Manara,A.Zabaniotou.Towards Sewage Sludge Based Biofuels Via ThermochemicalConversion–a Review.Renewable and Sustainable Energy Reviews.2012,16(5):2566-2582
[106] N.Y.Wang,C.H.Shih,P.T.Chiueh,et al.Environmental Effects of Sewage SludgeCarbonization and Other Treatment Alternatives.Energies.2013,6(2):871-883
[107] J.A.Conesa,R.Font,A.Fullana,et al.Comparison between Emissions from the Pyrolysisand Combustion of Different Wastes.Journal of Analytical and Applied Pyrolysis.2009,84(1):95-102
[108] B.TR,P.D.Energy and Nutrient Recovery from Sewage Sludge Via Pyrolysis.Water SCITechnol.2004,50:169-175
[109]中华人民共和国科技部.http://www.most.gov.cn/gnwkjdt/,2012-05
[110] Y.D.He,Y.B.Zhai,C.T.Li,et al.The Fate of Cu,Zn,Pb and Cd During thePyrolysis of Sewage Sludge at Different Temperatures.Environ Technol.2010,31(5):567-574
[111]宋学顶,陈德珍,王中慧,等.污水污泥裂解目标产物及残焦促进植物生长的研究.环境科学.2011,32(9):2604-2609.
[112] G.Gascó,J.Paz-Ferreiro,A.Méndez.Thermal Analysis of Soil Amended with SewageSludge and Biochar from Sewage Sludge Pyrolysis.Journal of Thermal Analysis andCalorimetry.2011,108(2):769-775
[113]翁焕新,傅凤霞,刘瓒,等.污泥干化使重金属形态变向稳定的原因分析.环境科学学报.2010,30(7):1401-1409.
[114]何念.污泥热解特性及其焦产物中痕量元素淋滤实验研究:(硕士学位论文).华中科技大学,2011.
[115] I.H.Hwang,Y.Ouchi,T.Matsuto.Characteristics of Leachate from Pyrolysis Residueof Sewage Sludge.Chemosphere.2007,68(10):1913-1919
[116] R.C.Kistler,F.Widmer,P.H.Brunner.Behavior of Chromium,Nickel,Copper,Zinc,Cadmium,Mercury,and Lead During the Pyrolysis of Sewage Sludge.Environ SciTechnol.1987,21(7):704-708
[117]武汉高泽环保技术工程有限公司.http://wenku.baidu.com/view.html.
[118] Kistler R.C.,Widmer F.,Brunner P.H.Behavior of chromium,nickel,copper,zinc, cadmium, mercury, and lead during the pyrolysis of sewagesludge.Environ.Sci.Technol,1987,21(7):704-708