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:2007-09-1015 4200712JournalofBeijingInstituteofPetro-chemicalTechnologyVol.15 No.4Dec.2007熊杰明 王 焱 吴新民 龚良发(,102617) (FeSO4·7H2O),,。,、。HCT1(TG)、(DTA),;α,45,、,。 ;; O643 ,,1t3.5～4.0t。200kt,[1-4]。,。,、,、、,6,,[5-6]。,。,(),,[7]。,。,,Achar、Coats-Redfern,,[8-10],,。,,ΔαΔTdαdT,。,αf(α)G(α),。,T,,f(α)G(α),。[8]E1=61.115kJ/mol、E2=66.781kJ/mol,2、3,,50℃,。,α。,,,Matlab,α,,。1 1.1 ,,。1.2 TG、DTA(TG)、(DTA)HCT-1;α-Al2O3,DTA±50μV,TG10mg;DTG10mV/min;N2,N235mL/min;5～15℃/min,23mg,。2 2.1 β=10℃/min,(TG)、(DTA),1。1。1 TG-DTA(β=10℃/min)45℃3,;115℃3,:FeSO4·7H2O45℃FeSO4·4H2O+3H2OFeSO4·4H2O115℃FeSO4·H2O+3H2O2.2 2.2.1 β=10℃/min,w=23.35mg,TG-T1。49.2℃～105℃500,,,4011。,TG-T。18.0153,151.909,:α=-TG3×18.0153151.909+7×18.0153×23.35(1) [10]:G(α)=Aβ(T-T0)exp-ERT(2),A,s-1;E,kJ/mol;R,R=8.314J/mol·k;T0,K;[10]45G(α),,3::G1(α)=α2(3) :G2(α)=α+(1-α)ln(1-α)(4) :G3(α)=1-23α-(1-α)23(5)αG(α),1。1 β=10℃/minT/℃TG/mg αeG1eG2eG3eG1cG2cG3cα1cα2cα3c49.2-0.01000.002200.00000.000000000.00000.000052.7-0.04990.01100.00010.00010.00000.00060.00010.00000.02470.01410.000057.3-0.12980.02860.00080.00040.00010.00220.00050.00010.04740.03150.029860.7-0.23010.05070.00260.00130.00030.00440.00100.00010.06660.04440.029864.7-0.36000.07930.00630.00320.00070.00880.00230.00030.09360.06710.051468.6-0.53020.11680.01360.00710.00160.01580.00470.00070.12550.09540.078072.0-0.72990.16080.02590.01370.00310.02530.00840.00140.15890.12680.109476.4-0.97000.21370.04570.02470.00560.04460.01710.00300.21120.17910.158379.7-1.24010.27320.07460.04130.00950.06670.02820.00530.25830.22790.207784.5-1.55010.34150.11660.06640.01540.11620.05670.01150.34090.31730.298587.7-1.88010.41420.17160.10090.02380.16550.08860.01900.40680.39020.375091.5-2.24010.49350.24350.14900.03560.24810.14790.03380.49810.49190.482895.2-2.69990.59480.35380.22880.05590.36290.23980.05830.60240.60680.604998.8-3.29000.72480.52530.36970.09370.51910.37850.09750.72050.73150.7352102.4-3.95000.87020.75720.60520.16350.73460.58990.16100.85710.86260.8663 :1、2、3,c、e、。16200715 45G(α)[10],1αeG(α)Ge;Matlabnlinfit,,A、E,G(α)GcGeDG,。JG=∑ni=1Ge-Gc2 (n)DG=1n∑ni=1(Ge-Gc)20.5=1nJG0.5DG,3DGG(α)((3)～(5)),2。2A、E。G2。22,3,A、E。2 G(α)A/sE/(kJ·mol-1)DGDαG13.8058×101189.440.00680.0107G26.5087×1015120.560.00790.0239G32.0683×1018142.580.00280.0391 :Dαα,Dα=1n∑ni=1(αe-αc)20.52 G(α) 2.2.2 G,T,2DG,αcDα=1n∑ni=1(αe-αc)20.5。αe,Dα,,。3αcDα12,α-Tαe3。2Dα3,G1。3,DGG3,。3 α 2.2.3 ,,。,JG=∑ni=1(Ge-Gc)2,DG,。G1,Jα=∑ni=1(αe-αc)2,Dα=1n∑ni=1(αe-αc)20.5=1nJα0.5。G1(α)=α2=Aβ(T-T0)exp-ERT,α=Aβ(T-T0)exp(-ERT)0.5。JG、Jα。3,Jα,Dα。E2.03%,A45.10%。,,Jα。,(),Dα=0.0221。2.3 ,、G4(α)=1-(1-α)1/32,β=10℃/min,E=174.110.66kJ/mol,A=1.1624×1013s-1,Dα=0.01142,4,。3 JG、JαT/℃αeαGαα49.20.00220052.70.01100.02470.023757.30.02860.04740.045660.70.05070.06660.064464.70.07930.09360.090868.60.11680.12550.1223720.16080.15890.155476.40.21370.21120.207379.70.27320.25830.254384.50.34150.34090.337187.70.41420.40680.403491.50.49350.49810.495495.20.59480.60240.601098.80.72480.72050.7209102.40.87020.85710.8601A/1011s3.80586.9328E/(kJ·mol-1)89.4491.29Dα0.01070.0103 :αG、ααJG、Jα。4 α3 (1)TG、DTA,;(2),;(3),α,E=90.82kJ/mol,A=5.8894×1011s-1,Dα=0.0113;E=110.66kJ/mol,A=1.1624×1013s-1,Dα=0.01142。[1] ,.[J].,2003,21(5):74-76.[2] ,,.[J].,2001,21(6):363-365.[3] ,,,.[J].,2000,18(3):42-44.[4] ,,,.[J].,2000,20(2):32-35.[5] ,,.—[J].,2004,1(1):6-8.[6] ,.[J].,1999,31(5):29-31.[7] Swamy,M.S.R.THERMALDECOMPOSI-TIONOFIRON(Ⅱ)SULPHATEHEPTA-HYDRATEINTHEPRESENCEOFALKALIMETALCARBONATES[J].JournalofThermalAnalysis,1982,25(02):347-354.[8] ,, ,.[J].(),1999,21(02):164-173.[9] ,, ,.REValCl36H2ORENdSm[J].,2006,22(08):942-946.[10] ,.[M].:,2001:47.18200715KineticStudyontheThermalDecompositionofFerrousSulphateHeptahydrateXiongJieming WangYan WuXinmin GongLiangfa(DepartmentofChemicalEngineering,BeijingInstituteofPetrochemicalTechnology,Beijing102617)Abstract Alargeamountofbyproductferroussulfateheptahydrate(FeSO4·7H2O)isproducedintheproductionofwhitetitaniumpigment(TiO2),anditscomprehensiveutilizationisveryim-portant.Thekineticstudyonthethermaldecompositionofaboveheptahydratecanprovidefun-damentalandimportantimformationfortheproductionofferroussulfatemonohydrate,iron-ox-ide,etc.Thethermogravimetry(TG)andthedifferentialthermalanalysis(DTA)duringthethermaldecompositionhasbeencarriedouttodeterminatethemechanismandkineticmodel.Ac-cordingtothe(addspace)standarddeviationsofconversionrateofdifferentmodels,itisconclu-dedthattheonedimensiondiffusemodelandthreedimensionsphericalsymmetrymodelweremorefitforthefirstandsecondstepsofwaterlossrespectively,andthecorrespondingmodelpa-rametershavebeenattained,andtheresultshowsthattheabovemodelsmatchtheexperimentaldataverywell.Keywords ferroussulphateheptahydrate;thermaldecomposition;kinetic194.