重金属元素在燃煤产物中的分布特征及迁移机理

AbstractThedistributioncharacteristicsofheavymetalsindifferentcoalcombustionproductsisstudiedwithadvancedanalysismethods(SEM,ICP-MSetc)inthispaper.Multi-disciplinarytheoriesincludingcoalpetrology,mineralogy,silicatephysicalchemistryandcoalcombustionhavebeenadoptedinthisthesistodiscussthechangingbehaviorofthemineralsinthecourseofpulverizedcoalcombustionandthemainfactorswhichaffecttheevaporationofheavymetalsareanalyzed.Concludedthattheevolutionofflyashandtheenrichmentofheavymetalsonflyashweretworespectsofthesameprocess.Heavymetalsreactedwithflyashandproducedstablearseniccompounds,heavymetalscomeintocrystallatticeofclayminerals,heavymetalswasabsorbedbyflyashandcondensedorcoagulatedonthesurfaceofflyashwereconsideredtobethefourmainformsoftheenrichmentofheavymetalbyflyash.Atlast,thebehaviorofevaporationmigrationandenrichmentofheavymetalsinthecourseofpulverizedcoalcombustionisdescribedpreliminarilyandsystematicallybasedonthemodesofoccurrenceofheavymetalsincoal.KEYWORD:pulverizedcoalcombustionflyashheavymetalsmodesofoccurrencemigrationandconvertion:111.1(InhalableparticulatematterIP)PM10PM10PM10PM10AsSePbCrPAHsPCDD/FsVOCsPM10[1]PM10PM10[1][2]20006168%19983220.289/68%308WHO(0.09mg/)95%21.21.2.1Seni[3]-OH-COOH-SH=NHBBaCuMnSrZn-OH-COOHH[4][5][6][7]As,Cd,Co,Cu,Hg,Mo,Ni,Pb,SeZnSwaine1984;NortonMarkuszewski,1990AsTumatiDevito1990FeAsS,Al3+Finkelman1994ZnSSwaine1995DreherFinkelman[8]10%70%80%,5%10%1%5%15%Finkelman[9]317.54%67.48%32.86%82.27%(Pb2010-6)(K+)Swaine(1990)Finkelman(1994)[Mg,FeCr2O4]1.2.2Smith(1987)GermaniZoller1988Meij(1989)Ba,Ce,Mg,ThAs,Cd,Pb,Se,ZnHg,BrCercharZnPbCrNiCoKauppinenPakkanen0.05mNatusch4[10]1.2.3Meij(1985)Al,BaThAs,Cd,SeHgFHalstead(1987)Cr,Hg,Ni,Uthesilicatemineralcoffinite(U(SiO)1-x)(UO2CoffiniteUO2Frandsan(1990)Gibbs[12]--2002[13]1999AsCdAsCd,-1.2.41998CdPb5CoCuNi[14]CaOJyg-Cheng[15-16]800700Owens[17]SiO2PbO80%PbO600-1600KScotto[18]85%XXRDPbAl2SiO8CdAl2O4SiO2Al2O31.2.5K2SO4Na2SO4CaSO4KauppinenPakkanenFeKNa1.36ìg/g1.4AsSePbCrCd82-2CaO35.2%8.14%CaO2.34%2-2%SiO2Al2O3Fe2O3CaOMgOSO3Na2OK2OTiO2Loss27.2813.0510.2635.202.835.600.290.530.774.2354.3619.4210.008.140.721.200.100.311.173.7874.169.843.222.340.791.50.470.232.144.802.2.22000162-2-12-2-1a2-2-1b92-2-1C2-2-1d2-2-1e()2-2-1f()2-2-1g()2-2-1h()102-2-1i()2-2-1j()2-2-1h()2-2-1k()2-2-1l()2-2-1o()2-2-1112.32.3.12~3mm50~150μm300μm60μm~2.3.21~3mm5mm~50~200μm2.3.3(slaging)(fouling)123#2~3cm3#1cm2mm1~2mm2~5mm0.5~2mm2-32-3%SiO2Al2O3Fe2O3CaOMgOSO3Na2OK2OTiO2Loss27.2813.0510.2635.202.835.600.290.530.774.2324.0110.999.6027.242.050.240.070.280.6124.3626.9312.3614.4239.413.191.870.310.690.7517.168.1319.8025.641.5923.830.351.410.472.4D[43]d(0.5)d(0.1)d(0.9)50%10%90%S.A.Benson(1993)2-4-42-4-4[20]0.1μm-12~15μm-132-4-1~2-4-32μm,10μm5μm2-4-1142-4-22-4-31541.91m15.08m25.83mPM1032%52%45%PM10PM2.520%32%26%2.51633.13-1-13-1-172193-1-1ICP-MSAsSePbCdCr3-1-1µm9-105.8-9.04.7-5.83.3-4.72.1-3.31.1-2.10.65-1.10.43-0.650.433173.23.2.1(As)3d104s24p3+3+5As3+As5+3-2-1-1µg/g12minmaxAMGMminmaxAMGMminMax3AM40.13200018.165.090.2132000276.614.260.5805.011999219973Swaine(1990)4V.Valkovic(1980)minmaxAMGM0.003mg/L0.05mg/L8µg/gMeij1986RERE=[(Cte)output/(Cte)coal][%ashcoal/100](Cte)outputg/g(Cte)coalg/g%ashcoal16.8%10.36%26.18%18Meij19860.7-1.3RE1.3RE0.73-2-1-2As(µg/g)As25.127.41443826800.180.962.564.55RE=0.18RE=0.96RE=2.56RE=4.55As3-2-1-3Asµg/gESPESPESP6.620.472870.324.519.364.291.81As——————ESPESP0.320.89ESP1.851.813193-2-1-172193-1-13-2-1-43-2-1-4µg/g0123456789A82233835836788239241090113011801090A330.940.566.269.4133145157165192177A720.356.163.267.274.775.672.970.671.870.3A8A3A7(010μm19~10μm25.8~9.0μm34.7~5.8μm43.3~4.7μm52.1~3.3μm61.1~2.1μm70.65~1.1μm80.43~0.65μm90.43μm)3-2-1-2AsPM2.5As1000µg/g15010µmCug/g203-2-1-213-2-1-51.310µm123410µm1.31-56-100123456789umµg/g321[55]95%0.667N=93-2-1-3R=0.99R=0.97R=0.820.67r03-2-1-3Al2O3+SiO2FeOCaO+MgOSO3K2O+Na2O3-2-1-6%As0.180.962.564.55Al2O3+SiO23540.8339.2925.29Fe2O39.69.6814.4219.8CaO+MgO44.638.0342.627.23SO30.245.61.8723.83K2O+Na2O0.350.821.001.7622[55]=0.0595%0.95N=43-2-1-4Al2O3+SiO2CaO+MgOFeOSO3K2O+Na2O-0.70-0.820.990.850.98FeOK2O+Na2O0.95K2O+Na2OFeO3-2-1-4As3.2.2(Se)4S24P4220SeO2SeO3SeO23170.05µg/g3-2-2-13230.1-2µg/g3-10µg/g10µg/gSe0.01µg/gSe0.02µg/g3-2-2-1µg/g12minmaxAMGMminmaxAMGMminMax3AM40.188.34.442.510.1256.76.223.640.2103.011999219973Swaine(1990)4V.Valkovic(1980)minmaxAMGMSeO2SeO20.6mg/m31.2mg/m3[21]Nriagu(1988)108775t/7921980t/50%199813-2-2-2Seµg/gSe1.62.34.75.36.20.240.490.560.65RE=0.24RE=0.49RE=0.56RE=0.65(1986)75075%[22]Finkelman(1990)Argonne55080%95%2419961.42µg/g0.707µg/g80.95%()3-2-2-3µg/gESPESPESP1.365.059.2836.90.621.154.569.511.9813.9433.40.330.380.923-2-2-1Seµg/gSeAs———ESPRE=0.62RE=1.15RE=4.56RE=0.33RE=0.38RE=0.92C(µg/g)3253-2-2-4µg/g0123456789A86.14.84.76.55.56.858.3310.712.117.2A34.41.735.512.846.289.7310.413.918.020.0A74.99.61010.41213.115.716.921.225.6A8A3A7(010μm19~10μm25.8~9.0μm34.7~5.8μm43.3~4.7μm52.1~3.3μm61.1~2.1μm70.65~1.1μm80.43~0.65μm90.43μm)3-2-2-2Seµg/g3-2-2-2Se010µm1459010µm1349010µm2613-2-2-50123