搜索
200930。，，。，，。，，。。，。，（、EA），，[1-4]。(、、、、)[5-7]，，。，，。，。，。，。，。，，Popescu。11.13，、，1，TQ172B1007-0389200903-01-06(,210029)。Achar、Coats-RedfernPopescu。。InfluenceofmathematicalmethodsonthekineticparameterscalculationofanthracitecombustionTangShengliang,CaiYuliang,DongYiming(SINOMA-NanjingCementIndustryDesignandResearchInstitute,Nanjing,JiangSu,210029)Abstract:Thecombustionkineticsofanthracitewasinvestigatedwiththermogravimetricanalyzer(TG),ReactionmechanismsandkineticparametersofanthracitecombustionweredeterminedfromTGAdatausingclassicalnon-isothermalkineticmethod(AchardifferentialmethodandCoats-Redfernintegralmethod)andmulti-ratemethod(Popescumethod),thentheinfluencesofmathematicalmethodsontheresultandthesourcesoferrorlocatingatthistreatmentprocesswerediscussed.Theresultsindicatethatanthracitecombustionisinaccordingwiththeshrinkingmechanismwithsurfacereactionratecontrolling，thethermoanalyticalresultsareinfluencedbythemathematicaltreatmentmethods,theerrorisinevitable,andthekineticparametersobtainedareapparentparameters.Keywords:anthracite；combustionkinetics；TG；analysis；error1--200931。1.2TASDTQ600。0～1300℃，100℃/min。：50μm，10mg±0.5mg，，100mL/min，20℃/min，1000℃；5℃/min，10℃/min，15℃/min30℃/min，、1000℃。1.3，TA。（1）（2），，“”f（α）G（α），，，，[8]。：dα/dT=(1/β)Aexp(-E/RT)f（α）（1）：G（α）=T0乙(A/β)exp(-E/RT)dT=(AE/βR)P(μ)（2）：，，dα/dT，P(μ)[9]。，。AcharCoats-Redfern。（3）（4）。Achar：lndαdT·f（α）乙乙=lnAβ-ERT（3）Coats-Redfern：lnG（α）T2乙乙=lnARβE乙乙-ERT（4）：α———，%；α=（m0-mt）/（m0-mf）；m0———，g；mt———，g；mf———，g；t———，min；T———，K；E———，kJ·mol-1；A———，min-1；R———，8314kJ·(mol)-1·K-1；β———，K·min-1。(α，T，dαdT)（1）f（α）G（α），（3）（4），lndαdT·f（α）乙乙lnG（α）T2乙乙1T，，E，A。2~4。Popescu[10]：，Arrhenius，，，1MadAadVadFCadQnetad%kJ·kg-1Dvmd/μm2.2526.416.8864.4623.2819.485.8021.678.6663.8723.0517.951.8232.867.1658.1621.0526.392(Achar-Brindley-Sharp)(Coats-Redfern)ElnARSDElnARSD6308.637.95-0.9870.624341.942.67-0.9790.89415107.013.19-0.97140.326127.415.9-0.98250.30118342.645.37-0.99130.567363.048.1-0.98490.79528136.615.65-0.98940.250166.319.7-0.97860.43629130.815.04-0.98840.251163.819.6-0.9770.45031119.113.64-0.98080.295159.719.5-0.9730.4762--200935[8]G（α）f（α）6Jander[1-1-α1/3]2321-α2/3[1-1-α1/3]-128n=1/41-1-α1/441-α3/429()n=1/31-1-α1/331-α2/331()n=1/21-1-α1/221-α1/218Avrami-Erofeevn=2[-ln1-α]2121-α[-ln1-α]-115Avrami-Erofeevn=3/4[-ln1-α]3/4431-α[-ln1-α]1/44(Achar-Brindley-Sharp)(Coats-Redfern)ElnARSDElnARSD6471.554.40.9890.57516.260.180.9800.88315172.520.00.9680.37196.525.280.9780.32418345.643.60.9720.483387.650.620.9750.65328215.123.70.9940.20254.628.980.9830.44229205.822.80.9950.182250.728.680.9790.44331187.120.60.9880.250243.528.080.9760.4713(Achar-Brindley-Sharp)(Coats-Redfern)ElnARSDElnARSD6307.339.920.9820.632359.247.490.9790.80615106.514.030.9630.320189.525.940.9860.34318361.250.530.9910.529392.754.990.9870.68428129.515.680.9830.259176.622.470.9790.38829120.214.510.9760.284172.822.140.9770.40431101.612.010.9430.382165.821.400.9710.436。，，。βTG，α，G（α）~1/β，，。G（α）f（α）5(，6)。22.120℃/min2，DSC3。45。2，，2/℃/%1—2—3—4/%1—5℃/min2—10℃/min3—20℃/min4—30℃/min3--20093t/min/%＞＞。4、5，，，。，，；，。，，。2.22~4：，。，528，29，31。，[11]：（1）EA，，E80～250kJ/mol，7～30；（2）R0.98；（3）0.3；（4）f（α）；（5）Kissinger，Ozawa。，。，，(56，18)，，（R）。，，[12]。？。，，Achar，（5）dα/dt，tdα/dtdα/dt。6。dα/dt=Aexp（-E/RT）f（α）（5）6，，R，、dα/dtdα/dt。15，18，R0.991,0.990，dα/dt。，。，。Achar，(6)，(7)，，。dαdT·f（α）=Aexp（-ERT）（6）ln（dαdT·f（α））=ln[Aexp（-ERT）]=lnA-ERT（7）dα/dtdαdT·f（α），Ai，ln（dαdT·f（α））Ci，/℃1—5℃/min2—10℃/min3—20℃/min4—30℃/min56dα/dtdα/dt04--20093Aexp（-ERT），Bi，Di，ΔAiBi=Ai-Bi，ΔCiDi=Ci-Di0，7。7，ΔAiBi，＋2000，ΔCiDi±5，（6），；，，，，。，，，R，SD。，TGA,，8。8，，，，，、，，，，。，，TGA,。，10％[13]。，，，，。，52928。6、7popescu，28，29，。，Popescu，。：，，。28，29，（5），，，，。，，，，，，，，。2.32~4，。，，8。8，，，，，T0（DSC），Coats-Redfernf（α）=（1-α）n。7(t)/minΔAiBiΔCiDi81/Tln（dαdT·f（α））5--200936T/℃590~600600~610610~620620~630630~640640~650650~660660~67060.90610.90860.91230.91580.90890.91430.91240.9131150.9830.9860.9860.9830.9890.9860.9880.987180.9510.9520.9550.9560.9550.9540.9530.951280.9870.9880.9880.9850.9890.9870.9870.985290.9870.9880.9880.9850.9890.9860.9870.985310.9870.9880.9880.9850.9890.9860.9870.9847T/℃430~450450~470470~490490~510510~530530~55050~570570~59060.9700.9680.9600.9430.9360.9600.9660.975150.9780.9810.9900.9950.9940.9990.9880.975180.9650.9510.9280.9250.9760.5860.926-0.951280.9980.9980.9980.9900.9880.9990.9930.993290.9980.9980.9980.9910.9890.9990.9880.978310.9980.9980.9980.9920.9930.9910.9430.805。，，。3，：（1）。（2），，。（3），，。（4），，，，，。[1]G.Hakvoort,JC.Schouten,etal.Thedeter－minationofcoalcombustionkineticswiththermo－gravimetry[J].JournalofThermalAnalysis,1989(35):335-346.[2],,.[J].,2007(2):20-25.[3],,.[J].,1994,15(4):435-440.[4],,.[J],2002(03):223-228.[5],,.[J].(),2005(5):73-78.[6]M.E.Brown,M.Maciejewski,etal.Computationalaspectsofki－neticanalysisPartA:TheICTACkineticsproject-data,methodsandresults[J].ThermochimicaActa,2000(300):125-143.[7],,.[J].,2006,(01):121-124.[8],.[J].,2008[9]Joseph.H,Flynn.The'TemperatureIntegal'-Itsuseandabuse[J].ThermochimicaActa,1997,300:83-92.[10]PopescuC.Integralmethodtoanalyzethekineticsofhet－erogeneousreactionsundernon-isother