MODELLINGPRODUCTCOMPOSITIONINSLOWPYROLYSISOF WOOD

AvdheshK.Sharma,M.R.RaviandS.Kohli MechanicalEngineeringDepartment,IndianInstituteofTechnology,Delhi110016 Email:skohli@mech.iitd.ac.in Abstract Pyrolysis product compositionhas beenmodeledat lowheatingrates (< 100 oC/min)for woodybiomassmaterialstopredictcharyield,simplifiedcompositionofvolatilespeciesand heatofpyrolysis.Thethermaldecompositionofbiomasshasbeendescribedonthebasisof decomposition of its three main constituents, viz., cellulose, hemicellulose and lignin. Completeelementalbalancealongwithdatafromtheliteratureon CO/CO2,H2O/CO2 and Lighthydrocabon/CO2 ratioshavebeenusedfordeterminingtheproductcompositionasa function of temperature. Model predictions are validated against data from published literature. Model has been used to illustrate the effect of temperature on the product compositionforpyrolysisofdifferentbiomassmaterials. Modelpredictionsshowthatthe pyrolysisprocesschangesfromendothermictoexothermicwithincreaseintemperature,with thereversalinheatofpyrolysisoccurringwhenthetaryieldfallstozero. Keywords:Pyrolysis,Biomass,VolatileComposition,Cellulose,Hemicellulose,Lignin. Nomenclature n
h
0 f

ME

ho

numberofmoles enthalpyofformationatref.state(kJ/kg) methaneequivalent(lighthydrocarbons) heatofreactionatreferencetemp

Y hhv char

massfraction highheatingvalue(kJ/kg) fractionofchar

Subscript vol volatiles cl cellulose lg lignin Introduction

DB hc pyr

drybiomass hemicellulose pyrolysis

Pyrolysis isathermochemical processprecedingthegasificationorcombustionof solid fuels.Whenlignocellulosicmaterialisexposedtohotenvironment,itundergoesthermal decompositionandgetsconvertedintovolatilegases,charandashresidues.Theseproducts of pyrolysis have wide industrial and domestic applications. The volatile gases can be crackedandpartiallycombustedinreducedairsupplytomakeproducergas,whichinturn

can be usedforpowergenerationorprocessheating.Thevolatilescanalsobeused to producemethanol.Thetarryliquid(pyrolysisoilorbiooil)canbeupgradedtohighgrade hydrocarbonliquidfuelsforICengineapplications.Thecharcanbeusedasreducingagent inmetallurgicalindustryorasdomesticcookingfuel[1].Theproductsofpyrolysisarefar toomany.RobertsandClough[2]putthisnumberatover100whileaccordingtoEmmons andAtreya[3]thenumberofspeciesinvolatilesreleasedfrompyrolysisexceeds200. Inordertomodelgasificationandflamingcombustionofvolatilesinwoodcombustion,itis necessary to express the complex mixture of the volatile matter evolving from wood pyrolysis andsubsequently bythe crackingof these volatiles,in termsof a few simple gaseous constituents. These gaseous constituents should on one hand satisfy the atomic balanceofthevariouselementspresentintheparentmaterial,andontheother,theyshould alsoaccuratelyreflecttheenergeticsofpyrolysisandsubsequentcombustion.Inliterature, certainresearchershavechosentostudythevolatileconstituentsintermsofCO,CO 2,H2, H2O,tarandlighthydrocarbons.Borosonetal.[4]andThunmanetal.[5]arethemost notableamongstthese.Borosonetal[4]carriedoutexperimentstodeterminetheproducts of primary and secondary wood pyrolysis for three different temperatures. Their main objectivewastousetheexperimentaldatatodevelopakineticmodeltopredictratesof evolutionofvariousspeciesasafunctionoftemperature. Thunmanetal.[5]usedasetofequationsincludingtheenthalpybalanceforvariousspecies tosolveforthemassfractionsofdifferentspeciesinthepyrolysisproducts.Toclosethe systemofequations,theyhadtousetheexperimentaldatafortheratioofCO/CO 2andtotal hydrocarbons(THC)/CO2. Whiletheydidcarryouttheirownexperimentsaswell,they chosetocurvefitthedataofDiBlasietal.[6].Unfortunatelythefittedcurvesdifferedfrom theexperimentaldataofThunmanetal.[5]byanorderofmagnitudebutnoexplanationwas provided for this difference. Hence the curvefitted equations could not be used in the presentwork.ThemodeldevelopedbyThunmanetal[5]couldalsonotbeusedsincethe paperstatedthattheirsystemofequationsisstiffandcanresultinunrealisticsolutions. Theydidnotpresentanysolutionfortheseequationsbutinstead,presentedasensitivity analysisofthepredictionswithrespecttodifferentparameters. Fortunately,theplotsofexperimentaldatainBorosonetal.[4]andThunmanetal.[5]ofthe CO/CO2,H2/CO2 andTHC/CO2 ratiosareinreasonableagreementwitheachother.Inthe presentwork,thedatafromformerareusedbyfittingcurvessincethedatawereavailablein theformoftableswhileinlatter,theresultsarepresentedintheformofcharts,fromwhich thedatapointsaredifficulttoreadaccurately. Whilethispaperfocusesonmodelingofvolatilecomposition,therearealargenumberof other papers on modeling of pyrolysis which focus mainly on the rate of evolution of volatiles during pyrolysis following several mechanisms: global single step, twostep sequentialandparallelcompetingreactions[1,713].DiBlasi[13]presentsacomparative

evaluationofvariousmechanismsthatexistforkineticsofpyrolysis.DiBlasi[14]usessuch a mechanism to obtain composition of volatile matter obtained by twostage pyrolysis (Biomass volatiles gases).Anexaminationofatomicbalanceinthisworkshowsthat thefinalproductsofpyrolysisdonothavethesameatomiccompositionastheoriginal reactantwood,owingtoinconsistencybetweentheempiricalformulaefortarandwood,and thepercentagecompositionofgaseousyieldineachstageofpyrolysis,whichweretaken fromdifferentsources. Totheknowledgeoftheauthors,nosingleworkpresentedintheliteraturecombinesthe consistency of atomicbalance,useofreliableempirical datatoaccountfortemperature dependenceofgascompositionattheendofthepyrolysisandtheenergeticsofthepyrolysis reactions(valuesoftheheatofpyrolysis).Thepresentwork,thus,isaneffortincombining therelevantmodelsanddataavailableinliteraturetoformulateaconsistentandsimple modelforrepresentingtheproductcompositionsofpyrolysisintermsofafewspecies,for useinbiomassgasificationandcombustionmodels.Thismodelalsohastheadvantageof beingcompatiblewithanyglobalkineticexpressionthatgivestherateofmasslossofwood: sincethepredictionsofthepresentmodelareforunitquantityofwoodpyrolysed.Thegas compositionpredictedbythepresentmodelhasbeenfoundtobeinreasonableagreement withtheliterature.Thevaluesofheatofpyrolysispredictedbythepresentmodelarealsoin thesamerangeasthosefoundintheliterature. ModellingCompositionofVolatiles Thepresentworkaimsatdevelopingamodeltopredictasimplifiedcompositionofpyrolysis productsasafunctionoftemperatureforuseingasificationandwoodcombustionmodels, wherethepyrolysisprocessisslow. Formodelingofthermaldegradationofbiomass,the presentapproachconsidersthefueltobecomposedofthreemainchemicalconstituents cellulose, hemicellulose and lignin. On dry ashfree basis, the mass fractions of these constituentsarerelatedas

Ycl + Yhc + Ylg = 1

(1)

On heating, these constituents become unstable leading to their thermal decomposition, whichisconsideredtotakeplaceintwostagesviz.,primaryandsecondarystages.During theprimarydecomposition,eachconstituentofbiomassdecomposesintocharandvolatiles, while in the secondary decomposition, the volatiles breakup into various lighter hydrocarbons. The overall pyrolysis products (volatiles and solid residues) are the combinationoftheproductsfrompyrolysisofeachofthethreemajorconstituents,viz., cellulose,hemicelluloseandlignin. Therelativequantitiesofcharandvolatilesarestronglydependentontheheatingrateand thetemperaturerangeofthepyrolysiszone[7].Attemperatureabove700Candveryrapid

heatingrateoftheorderof1000C/minorabove,thereislittlecharformation.Ontheother hand,slowheatingrateenhancescharformation.However,asreportedbyZarorandPyle [7],atheatingratesbelow100oC/min,thecharyieldfrombiomasspyrolysisisrelatively insensitivetoheatingrateandtemperature.Thus,inthepresentwork,whichisessentially for slow pyrolysis processes, the char residue has been assumed to be invariant with temperatureandheatingrates.Ifthefractionofcharthatcanbeobtainedfromcellulose, hemicelluloseandligninarechar,clchar,hcandchar,lgrespectively,thetotalcharyieldfromthe thermaldecompositionofunitmassofdryashfreebiomasscanbeexpressedas Ychar = Ycl f char ,cl + Yhc f char , hc + Ylg f char ,lg Thefractionofvolatilesfromdryandashfreebiomasscanthenbeobtainedas Yvol = 1 Ychar (3) (2)

Volatilesreleasedduringprimarydecompositionofwoodareunstable,andtheybreakup intoalargenumberofgaseousspeciesandtar.Asalreadymentioned,forcomputationof combustionorgasificationprocess,itisdesirabletoidentifytheequivalentcompositionof volatilesintermsofahandfulofspecies.FollowingThunmanetal.[5],thepresentwork considers the volatiles to be composed of 6 species viz., CO, CO2, H2, H2O, light hydrocarbons(ME),andheavyhydrocarbons(tar). Raglandetal.[15]alsosuggestedthat lighthydrocarbonsareprimarilymethane.Inthepresentwork,lighthydrocarbonshavebeen modeledasmethaneandethyleneinthemassratio3:1givingrisetoanequivalentempirical formula of C1.16H4. Hydrocarbons other than light hydrocarbons are considered under a single category called heavy hydrocarbons or tar. Lewellen et al. [16] considered tar as levoglucosan (C6H10O5) which vaporizes and decomposes with increase in temperature. Raglandetal.[15]andThunmanetal.[5]suggestthechemicalformulaoftarasC6H6.2O0.2, whichisusedinthepresentwork. Forelementalbalance,thecompositionofcharisalsoimportant.Shafizadeh[17]reported thatthehydrogenandoxygencontentinthechardecreasesharplyastemperatureincreases. Raglandetal[15]quotedthatcharcontainslittlehydrogenattemperatureabove700C.In thepresentwork,charisassumedtobepurecarbon. Thus,theprocessofpyrolyticdecompositioncanberepresentedas C6HHBOOB=nchar,ashfreeC+ nCOCO+nCO2CO2+nH2H2+nH2OH2O+nMEC1.16H4+nTARC6H6.2O0.2(4) Here,C6HHBOOBisthechemicalformulaofthedryandashfreebiomassandnrepresentsthe numberofmolesofagivenspeciesinvolvedintheprocess. Thechemicalformulaofany

biomassspeciesisobtainedfromitscellulose,hemicelluloseandlignincontentsasgivenin Table1,usingthechemicalformulaeoftheseconstituents(Table2). Table1:ProportionofCellulose,HemicelluloseandLignininWood(drybasis)[18] Typeofwood Hardwood Softwood Woodbark RiceHusk Cellulose 0.452 0.458 0.248 0.313 Hemicellulose 0.313 0.244 0.298 0.243 Lignin 0.217 0.280 0.438 0.143 Ash+ Extractives 0.027 0.017 0.016 0.319

Table2:FractionalCharYieldsfromBiomassConstituents Biomass Cellulose constituents Fractional 0.05 charyield Chemical C6H10O5 Formula Hemicellulose 0.10 C6H10O5 Lignin 0.55 C9H7.95O2.4(OCH3)0.92 Reference Tillmanetal.[19] Grobskietal.[20]

Fromelementalbalanceofequation(4) Cbalance: 6nDB,ashfreenchar,ashfree=nCO+nCO2+1.16nME+6nTAR Hbalance: nDB,ashfreeHB=2nH2+2nH2O+4nME+6.2nTAR Obalance: nDB,ashfreeOB=nCO+2nCO2+nH2O+0.2nTAR

(5)

(6)

(7)

Intheabovethreeequations, nchar,ashfree iscomputedforagivenbiomassfromitscellulose, hemicelluloseandlignincontent(Table1)andthecharcontentoftheseconstituents(Table 2). Then nCO, nCO2, nH2, nH2O, nME and nTAR are the six unknowns. Thus, three additional equationsareneededtoclosethesystem. Forthispurpose,inthiswork,themassratios CO/CO2, and ME/CO2 havebeenobtainedasafunctionoftemperaturebycurvefittothe experimentaldataofBorosonetal.[4].Thesedatawereavailableatonlythreetemperatures from873K1073K.Theformsofthecurveshavebeensochosenastoensurenonnegative valuesoverarangeof400K1200K.TheratioofH2O/CO2hasbeentakentobeunityas suggested byThunmanetal.[5],sincetheuseofdataofBorosonetal.[4]forH 2O/CO2 resultedinpredictionsofvolatilecompositionthatwerefarinvariancewithliterature.

YCO/YCO2=

1.845 +

7730.3 5019898 T T2

(8) (9) (10)

YH2O/YCO2=1 YME/YCO2=51016T5.06

Figure1showstheexperimentaldataofBorosonetal.[4]alongwiththefittedequations(8 10) as a function of temperature. The elemental balance equations (57) and empirical equations(810)aresolvedtopredictvolatilecompositionforknownvaluesoftemperature. Asthetemperatureincreases,tarcontentinthevolatilesdecreasesandgoestozeroaround 800 1000 K for different biomass substrates. Beyond this temperature, we have one unknownlesstosolvefor,andso,weneedtodroponeoftheequations.Itwasfoundthatif equation(9)isdropped,theresultsremainreasonablycontinuous,whileifeitheroftheother two equations is dropped, it results in an unrealistic jump in the predicted volatile compositionbeyondthistemperature.Henceinthepresentwork,whentarpredictionusing allsixequationsbecomeslessthanzero,itisassignedtozero,equation(9)isdroppedandthe remainingequationsaresolvedtopredictthegascomposition.
3 2.5 MassRatio 2 1.5 1 0.5 0 400 600 800 Temperature(K) 1000 1200 CO/CO2[4] Curvefit(eq.8) ME/CO2[4] Curvefit(eq.10)

Figure1.CurveFitsforCO/CO2andME/CO2datafromBorosonetal.[4]

Oncethepyrolysisproductcompositionisknown,heatofpyrolysiscanbedeterminedusing the enthalpyof formation of thereactants andproductsof the overallreaction given by equation(4).Here,heatsofformationofotherconstituentsthantararedirectlyknown[21], sincecharisassumedtobepurecarbon,withzeroheatofformation.Inordertoobtainheat of formation of tar, the following steps are followed: first, the gross calorific value of biomass(inkJ/kg)isobtainedusingtheIGTexpressionpresentedbyDogruetal.[22]:

hhvDB = 341C DB + 1323H DB + 68S DB 15.3ashDB 120(ODB + N DB )

(11)

whereCDB,HDB,SDB,ashDB,ODBandNDBarethemassbasedpercentagecompositionsofC,H, S,ash,OandNindrybiomassrespectively.IthasbeenreportedbyRaglandetal.[15]that thehigherheatingvaluesofdifferentwoodspeciesonamoisturefreebasisvarybylessthan 15%, and hence, the above expression is expected to reflect the energetics of biomass combustionfairlywell. Sincethisheatofcombustioncanbepartitionedamongthechar, gasesandtarproducedbypyrolysis,andsincetheheatofcombustionofthecharandgas constituentsarewelldocumentedincombustiontexts[21],theheatofcombustionoftarcan becomputed. Knowingtheatomiccompositionoftar (C6H6.2O0.2) andthestoichiometric equationforitscompleteoxidation,theheatofformationoftarcanbecomputed.Raglandet al. [15] computed the heating values of methane equivalent and tar using the above methodologyforatypicalwoodcompositionandreportedtheheatingvaluesofbothtobe41 MJ/kg.Then,theheatofpyrolysiscanbecomputedusingtheexpression
o hpyr = ho f

+ Ychar ho f DB

( )

char

+ Yvol Yi ho f
i =1

i =6

( )

(12)

Herei=1to6correspondrespectivelytoCO,CO2,H2,,H2O,MEandTar.Itmustbenoted herethatthismethodislikelytoproduceheatsofcombustionandheatingvaluesoverarange aroundthisvalue,althoughinthemodeltheirchemicalcompositionisassumedfixed. ResultsandDiscussion Theabovemodelpredictsspeciesconcentrationsinvolatilematterandcharyieldatknown valuesoftemperatureforagivenbiomass.Themodelneedsthepercentagesof cellulose, hemicelluloseandlignininbiomassasinput.Itusesthefractionofcharobtainedduetothe breakupofeachofthesethreeconstituentsfromTable2,whilethespeciesconcentrationsin volatilematteraredeterminedasdescribedabove. Itwasdifficulttofinddataforvalidationofthemodel.Veryfewresearchershavefocusedon determining the equivalent composition of pyrolysis products in terms of a few simple species.TheexperimentalworkofBorosonetal.[4]hasalreadybeenusedinthemodel formulation.Raglandetal.[15]havereportedexperimentalresultsofotherresearchersfor drywoodundercombustionconditionswithoutgivingexactcompositionofthewoodand temperatureofpyrolysis.Themodelpredictionsfromthepresentworkhavebeencompared withtheseresults.Forcomparison,thewoodcompositionhasbeenassumedtobethatof softwood[18].Theresultsobtainedusingthepresentmodelattemperaturesof700K,750K and800KarecomparedwiththeexperimentalresultsreportedbyRaglandetal.[15]in figure 2. The model is found to underpredict tar and overpredict CO 2 while the other constituents viz., CO, H2O, ME and char are in the same range as the corresponding experimentalvalues.Giventhefactthattheexactwoodcompositionandtemperaturefor experimentaldataarenotknown,thisagreementisfairlygood.

The effect of pyrolysis temperature on predicted composition of volatiles from different feedstockshasbeenshowninfigures37.Theresultsforcellulosearepresentedinfigure3. It isseen thatwithincreaseintemperature,thetaryieldinpyrolysisproductsdecreases significantly,whilecarbonmonoxideandlighthydrocarbon(methaneequivalent)increase. CO2andmoistureinthevolatilesshowadecrease,whilethehydrogencontentislowatall temperatures.Figure4forhemicelluloseshowsanalmostsimilartrend.Sinceitisonlythe charcontentwhichisdifferentbetweenthesetwosubstrates(Table2),thedifferencesinthe volatilecompositionandtheirvariationwithtemperaturearealsoslight.
30 25 Percentage 20 15 10 5 0 700K 750K 800K exp

CO

CO2

H2

H2O

ME

Tar

Char

Figure2.Comparisonofmodelpredictionsforsoftwoodatdifferenttemperatureswith experimentaldatafromliterature[15]

50.0 40.0 Percentage 30.0 20.0 10.0 0.0

CO CO2 H2 H2O ME Tar

500

700

900

1100

Temperature(K)

Figure3.PredictedvariationofvolatilecompositionforCellulosewithtemperature When the present modelisused withpurelignin,itresultsinnegativetar, whichwhen enforcedtozero,resultsinCO2 andH2Oratiosbeingdifferentfromunity,sinceinthese cases equation (9), which demands that CO2 and H2O be equal, is not used. A similar situationariseswithcertaintypesofbiomassathightemperatures.Thiscanbeseeninfigure 5forsoftwood.Attemperaturesofaround950Kandhigher,thetarbecomeszeroandhence CO2 andH2Ocurvesdonotcoincideanymore.AtthesametimetheCOpercentagealso

startsreducingattemperatureshigherthanthosegivingzerotar.Sameistrueforwoodbark andricehusk(Figures6and7).Itisalsoseenthatincaseofwoodbark,tarbecomeszeroat muchlowertempandcorrespondinglytheCOpercentagereachesalowerpeak.Thecurves forsoftwoodandricehuskshowaverysimilartrend.However,itmustbenotedthatthese resultsarefordry,ashfreebiomass.Ricehuskhasamuchhigherashcontent(Table1)and henceforaunitquantityofdryricehusk,thevolatileyieldwillbemuchlowerthanthatfrom softwood[23].

50.0 40.0 Percentage 30.0 20.0 10.0 0.0

CO CO2 H2 H2O ME Tar

500

700

900

Temperature(K)

Figure4.PredictedvariationofvolatilecompositionforHemicellulosewithtemperature

40.0 30.0 20.0 10.0 0.0

Percentage

CO CO2 H2 H2O ME Tar

500

700

900

1100

Temperature(K)

Figure5.PredictedvariationofvolatilecompositionforSoftwood[18]withtemperature

40.0 30.0 20.0 10.0 0.0

Percentage

CO CO2 H2 H2O ME Tar

500

700

900

1100

Temperature(K)

Figure6.Predictedvariationofvolatilecompositionforwoodbark[18]withtemperature
40.0 30.0 20.0 10.0 0.0

Percentage

CO CO2 H2 H2O ME Tar

500

700

900

1100

Temperature(K)

Figure7.PredictedvariationofvolatilecompositionforRiceHusk[18]withtemperature
1600 1400 HeatofPyrolysis(kJ/kg) 1200 1000 800 600 400 200 200400 400 Temperature(K) 0 600 800 1000 1200 Softwood HardWood

Figure8.PredictedvariationofHeatofPyrolysisofsoftwoodand hardwood[18]withtemperature

Figure8showstheeffectoftemperatureontheheatofpyrolysisforsoftwoodandhardwood. Predictionsshowaslightlyendothermicbehaviourataround500K,andtheheatofpyrolysis increasesslightlywithincreaseintemperature.Whentarreducestozero,thepredictedheat ofpyrolysisshowsanunrealisticjump,andthenwithincreaseintemperature,thepyrolysis phenomenonchangesfromendothermictoexothermicbehaviour.Althoughthejumpinheat ofpyrolysisisunrealistic,thereisanagreementwithLeeetal[24],whohaveshownthat thereisacrossoverfromendothermictoexothermicbehaviourasheatingrateisincreased. ThevaluesofheatofpyrolysisarealsointhesamerangeasquotedbyRobertsandClough [2].Itcanbeconcludedthatabetterexperimentaldatashouldbeusedinplaceofequations (810)tohandlethepointwheretarreducestozero,toavoidthejumpinthepredictedheatof pyrolysis.However,thepredictionsindicatethatthecrossoverfromendothermicbehaviour to exothermic behaviour happens when all the tar gets cracked: this happens at higher heatingratesorathighertemperatures. Thus,thepredictedenergeticsofpyrolysisofthe present model could be said to be in qualitative agreement with literature, while more detailedexperimentaldatamayberequiredtoensureaquantitativeagreement. Conclusions Amodelforpredictingthesimplifiedvolatilecomposition,charyieldsandheatofpyrolysis has been presented for the case of slow pyrolysis of ligno cellulosic materials. The formulationisbasedonoverallelementalbalancesupplementedbyempiricalcorrelationsfor ratiosofdifferentspecies.Themodelhasbeenvalidatedbycomparingitspredictionswith published experimental data on pyrolysis product composition for a typical biomass feedstock.Predictionsoftheeffectoftemperatureonthepyrolysisyieldofdifferentbiomass materialshavebeencarriedout.Predictionsshowthatthepyrolysisbehaviourchangesfrom mildlyendothermictoslightlyexothermicwithincreaseintemperature,whenthetaryield reducestozero. References [1] Gronli M G and Melaaen M C, 2000, Mathematical model for mood pyrolysis comparisonofexperimentalmeasurementswithmodelpredictions,Energy&Fuels,14, 791800. [2] Roberts A F and Clough G, 1963, 9th Symposium on Combustion, The Combustion Institute,Pitts,14711480. [3]EmmonsHWandAtreyaA,1983,ThescienceofwoodcombustioninWoodHeatfor Cooking, edited by K. Krishna Prasad and Verhaart, Bangalore, Indian Academy of Sciences,259268. [4]BorosonML,HowardJB,LongwellJP,andPetersWA,1989,Productyieldsand kineticsfromthevapourphasecrackingofwoodpyrolysistars,AIChEJournal,35,120 128.

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