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Quang-Vu Bach
Quang-Vu Bach
Wet Torrefaction of Biomass
Production and Conversion of
Hydrochar
NTNU
Norwegian University of
Science and Technology
Faculty of Engineering
Science and Technology
Department of Energy and
Process Engineering
Quang-Vu Bach
Quang-Vu Bach
Aftertherain,thesunshines.
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ExecutiveSummary
Biomass is a renewable and carbon neutral energy resource which has a high
potential for replacing fossil fuels. However, the use of biomass for energy
highly bulky and inhomogeneous. They normally have higher moisture content,
inferiorheatingvalue,andpoorergrindability,comparedtocoal.Thesedrawbacks
limit the use of biomass as fuel. Pretreatment of biomass via chipping and/or
drawbacks.Thisoperationaddsmorecoststobiomassfuels,butimprovementsin
thefuelpropertiesarelimited.
Wettorrefaction(WT)isapromisingmethodforpretreatmentofbiomassforuse
significantlythefuelpropertiesofbiomass.Inaddition,duetotheuseofwateras
reactionmedium,WTishighlysuitableforlowcostbiomasssourcessuchasforest
residues,agriculturalwastes,andaquaticenergycrops,whichnormallyhavevery
highmoisturecontent.
ThisPhDwascarriedouttotechnicallyassesstheWTprocessasapretreatment
methodforproductionofadvancedsolidbiofuel,hydrochar,fromforestresidues,a
lowcostbiomassresourceinNorway.
As the first step, stem woods from Norway spruce (softwood) and birch
(hardwood)weretestedasfeedstocks.Thischoicemadeitpossibletocomparewith
theresultsfrompreviousstudiesonDTofbiomassusingidenticalfeedstocks.WT
volume from Parr Instrument, with nitrogen as purge gas. Effects of various WT
i
process parameters on the yield and the fuel properties of hydrochar (solid fuel
obtained from biomass WT) were examined. The pyrolysis and combustion
pseudocomponentmodelswithdifferentreactionorderswereadoptedforkinetic
discussed.
In the second step, forest residues were used as feedstock, employing similar
approachesasinthefirststep.Inaddition,carbondioxidewastestedaspurgegas
andcomparedwithnitrogenforevaluatingthepossibilitytouseandrecoverheat
ofthefluegasfromcombustionplants.
Finally,thepelletabilityofhydrocharfromforestresidueswasinvestigatedand
comparedwiththatofuntreatedfeedstock.Thepelletizationwasperformedusing
asinglepelletpress.Differentcompressingpressures(20,40,80,160,240MPa)and
temperatures(120,180C)wereappliedtoproducepellets.Thepelletstrengthwas
energydensityandmechanicalstrengthofthepelletwereinvestigated.
ThemajorfindingsfromthestudiesreportedinthisPhDare:
Bothreactiontemperatureandholdingtimehavesignificanteffectsonthe
massyield,energyyield,andfuelpropertiesofthehydrochar.
Pressurealsoenhancesthetorrefactionrate;however,theeffectbecomes
marginalaboveacertainpressure.
Feedstockparticlesizeslightlyaffectstheyieldandfuelpropertiesofthe
hydrochar.
AshcontentofbiomassfuelissignificantlyreducedbyWT.
ii
Giventhesamesolidyields,WTrequiressignificantlylowertorrefaction
temperaturesandshorterholdingtimesthanDT.
Given the same solid yields, solid biomass fuels upgraded via WT have
greaterheatingvaluesthanviaDT.
inidenticalWTconditions.
conditions.
valueofhydrochar,comparetoWTinN2.
compressible and mechanically stronger than the pellets made from raw
forestresidues.
Overall,WThaspositiveeffectsonthefuelpropertiesofbiomass.
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iv
Preface
This doctoral work was carried out at the Department of Energy and Process
Tran (NTNU) and Dr. yvind Skreiberg (SINTEF Energy Research). The work is
part of the STOP (STable OPerating conditions for biomass combustion plants) project,
financed by the Research Council of Norway and industry partners through the
FMECenBio(BioenergyInnovationCentre).
Thisthesisconsistsofthefollowingpapers,whicharereferredtointhetextby
theirRomannumerals:
I. QuangVuBach,KhanhQuangTran,RogerA.Khalil,yvindSkreiberg,
GulaimSeisenbaeva.Comparativeassessmentofwettorrefaction.Energy&
Fuels2013,27,67436753.
II. QuangVuBach,KhanhQuangTran,yvindSkreiberg,RogerA.Khalil,
AnhN.Phan.Effectsofwettorrefactiononreactivityandkineticsofwoodinair
combustion.Fuel2014,137,375383.
III. QuangVuBach,KhanhQuangTran,yvindSkreiberg,ThuatT.Trinh.
Effectsofwettorrefactiononpyrolysisofwoodybiomassfuels.Submittedto
Energy.
IV. QuangVuBach,KhanhQuangTran,yvindSkreiberg.Torrefactionofforest
residuesinsubcriticalwater.SubmittedtoAppliedEnergy.
V. QuangVuBach,KhanhQuangTran,RogerA.Khalil,yvindSkreiberg.
EffectsofCO2onwettorrefactionofbiomass.EnergyProcedia,accepted.
VI. QuangVuBach,NevenaMiljenovi,KhanhQuangTran,CarlosSalas
Bringas,yvindSkreiberg.Influencesofwettorrefactiononpelletabilityand
pelletpropertiesofNorwegianforestresidues.AnnualTransactionsTheNordic
RheologySociety2014,22,6168.
v
Otherpublicationsrelatedtothetopic,butnotincludedinthisthesis:
1. QuangVuBach,MiguelValcuendeSillero,KhanhQuangTran,Jorunn
Skjermo.FasthydrothermalliquefactionofaNorwegianmacroalga:ScreeningTests.
AlgalResearch2014,6,PartB(0),271276.
2. QuangVuBach,KhanhQuangTran,RogerA.Khalil,yvindSkreiberg.Wet
torrefactionofforestresidues.EnergyProcedia,accepted.
3. QuangVuBach,RogerA.Khalil,KhanhQuangTran,yvindSkreiberg.
TorrefactionkineticsofNorwegianbiomassfuels.ChemicalEngineering
Transactions2014,37,4954.
4. KhanhQuangTran,QuangVuBach,ThuatT.Trinh;GulaimSeisenbaeva.Non
isothermalpyrolysisoftorrefiedstumpAcomparativekineticsevaluation.Applied
Energy2014,136(0),759766.
5. NevenaMiljenovi,QuangVuBach,KhanhQuangTran,CarlosSalasBringas,
yvindSkreiberg.Torrefactioninfluenceonpelletabilityandpelletqualityof
Norwegianforestresidues.Energy&Fuels2014,28,25542561.
6. RogerA.Khalil,QuangVuBach,yvindSkreiberg,KhanhQuangTran(2013).
Theperformanceofaresidentialpelletscombustoroperatingonrawandtorrefiedspruce
andsprucederivedresidues.Energy&Fuels2013,27,47604769.
vi
Acknowledgements
I would like express my gratitude to my supervisors, Professor KhanhQuang
TranandDr.yvindSkreiberg,forintroducingmetothefieldofbioenergyandfor
theirvaluableguidance,supportsandadvicesduringmyPhDperiod.
I would also like to thank Dr. Roger A. Khalil, for his contributions to my
publications.IreallyappreciatepracticalsupportsfromtheThermallab,especially
Dr.MortenGrnli,thelabmanager,andErikLangrgen.
Special thanks should be given to my colleagues and friends, who shared the
friendlyenvironmentandcoffeetimeswithmeduringthelastthreeyearsofhigh
workingpressure.
Trondheim,October2014.
QuangVuBach
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TableofContents
ExecutiveSummary..............................................................................................i
Preface....................................................................................................................v
Acknowledgements..........................................................................................vii
TableofContents................................................................................................ix
ListofFigures....................................................................................................xiii
ListofTables.......................................................................................................xv
Nomenclature...................................................................................................xvii
I. INTRODUCTION.........................................................................................1
I.1 Problemsidentification....................................................................................1
I.2 Researchobjectives...........................................................................................2
I.3 Thesisstructure..................................................................................................3
I.4 Listofpublicationsincludedinthisthesis..................................................3
II. BACKGROUND............................................................................................5
II.1 Biomassassolidfuelforheatandpowergeneration................................5
II.1.1 Plantbiomasscomposition........................................................................6
II.1.1.1 Cellulose..................................................................................................7
II.1.1.2 Hemicellulose...........................................................................................7
II.1.1.3 Lignin......................................................................................................7
II.1.1.4 Extractivesandash.................................................................................8
II.1.2 Fuelpropertiesofsolidbiomassfuel.......................................................8
II.1.2.1 Heatingvalue..........................................................................................8
II.1.2.2 Moisturecontent.....................................................................................9
II.1.2.3 Proximatecomposition............................................................................9
II.1.2.4 ElementalcompositionUltimateanalysis...........................................10
II.1.2.5 Grindability...........................................................................................13
II.1.2.6 Hydrophobicity......................................................................................13
ix
II.1.2.7 Bulkdensityandenergydensity...........................................................14
II.1.2.8 Pelletability...........................................................................................14
II.2 Thermochemicalconversionsofbiomass..................................................15
II.2.1 Pyrolysis.....................................................................................................15
II.2.2 Gasification................................................................................................17
II.2.3 Combustion...............................................................................................18
II.3 Biomasscombustiontechnologies..............................................................19
II.3.1 Fixedbedcombustion..............................................................................20
II.3.2 Fluidizedbedcombustion......................................................................21
II.3.3 Pulverizedfuelcombustion....................................................................21
II.3.4 Cocombustion..........................................................................................21
II.4 Challengesandpretreatmentneeds............................................................22
II.5 Biomasspretreatmentviatorrefaction........................................................24
II.5.1 Drytorrefactionanditschallenges........................................................24
II.5.2 Wettorrefaction........................................................................................25
II.5.3 Chemicalandphysicalpropertiesofwaterinsubcriticalcondition 28
II.5.3.1 Dielectricconstant................................................................................29
II.5.3.2 Ionproducts..........................................................................................29
II.5.3.3 Transportproperty................................................................................30
II.5.4 Degradationofbiomassinsubcriticalwaterconditions....................30
III. METHODOLOGY.......................................................................................33
III.1 Hydrocharproduction....................................................................................33
III.1.1 Materials.....................................................................................................33
III.1.2 Experimentalsetup...................................................................................34
III.1.3 Wettorrefactionprocedure.....................................................................35
III.1.4 Productsseparation..................................................................................36
III.2 Hydrocharcharacterization...........................................................................37
III.2.1 Proximateandultimateanalyses...........................................................37
III.2.2 Higherheatingvaluecalculation...........................................................37
III.2.3 Specificgrindingenergy..........................................................................37
x
III.2.4 Moistureuptaketest................................................................................38
III.2.5 Morphologyandstructurestudy...........................................................38
III.2.6 Pelletability................................................................................................39
III.2.6.1 Pelletization...........................................................................................39
III.2.6.2 Pelletdensity.........................................................................................40
III.2.6.3 Compressingtest...................................................................................40
III.2.7 Thermogravimetricanalysis....................................................................40
III.3 Kineticstudyforthermalconversionsofsolidbiomassfuels...............41
III.3.1 Kineticmodels...........................................................................................42
III.3.1.1 Pyrolysis................................................................................................42
III.3.1.2 Combustion...........................................................................................44
III.3.2 Mathematicalmodelling..........................................................................45
III.3.2.1 Modelfreemethod.................................................................................46
III.3.2.2 Globalkineticmodel..............................................................................47
III.3.2.3 Distributedactivationenergymodel.....................................................48
III.3.3 Thermogravimetricdatacollection........................................................49
III.3.4 Dataprocessing.........................................................................................50
III.3.4.1 Modelselection......................................................................................50
III.3.4.2 Kineticevaluation..................................................................................51
IV. CONCLUDINGSUMMARY....................................................................53
IV.1 Concludingsummary.....................................................................................53
IV.1.1 PaperIWettorrefactionofstemwoods..............................................53
IV.1.2 PaperIICombustionreactivityofhydrochar.....................................54
IV.1.3 PaperIIIPyrolysisreactivityofhydrochar.........................................55
IV.1.4 PaperIVWettorrefactionofforestresidues......................................56
IV.1.5 PaperVEffectsofcarbondioxideonwettorrefaction.....................57
IV.1.6 PaperVIPelletabilityandpelletpropertiesofhydrochar................58
IV.2 Recommendationforfurtherworks............................................................59
References............................................................................................................61
CollectionofPapers...........................................................................................73
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xii
ListofFigures
FigureII1.Biomassconstituentsinplantcellwall(adoptedfrom[5])...................6
FigureII2.Thermochemcialconversionroutesforbiomassfuels(adoptedfrom
[24])..............................................................................................................15
FigureII3.Commonsystemsforbiomasscombustion(adoptedfrom[8]).........20
FigureII4.Wettorrefactionandhydrothermalcarbonizationregionsina
temperaturepressurephasediagramofwater....................................27
FigureII5.Changesinphysicochemicalpropertiesofwaterat30MPaasa
functionoftemperature(adoptedfrom[97])........................................29
FigureII6.Hydrothermaldegradationofcottoncelluloseasafunctionof
reactiontimeandtemperature(adoptedfrom[105])..........................31
FigureIII1.TheParr4651reactor(adoptedfromparrinst.com)...........................35
FigureIII2.SchematicdiagramoftheWTreactorandtheexperimentalsetup. 36
FigureIII3.Singlepelletpressunit:a)pictureoftheequipment.Drawingofthe
singlepelletunit:(b)topview,(c)sectionviewAA...........................39
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xiv
ListofTables
TableII1.Mainoperatingparametersfordifferentpyrolysisprocesses(adopted
from[26])....................................................................................................16
TableII2.Mainreactionsduringbiomassgasification...........................................18
TableII3.Disadvantagesofrawbiomassmaterialsutilizedforthermochemical
conversions.................................................................................................23
TableII4.MaindifferencesbetweenWTandHTC.................................................28
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xvi
Nomenclature
Abbreviations
ASTM AmericanSocietyforTestingandMaterials
DAEM Distributedactivationenergymodel
daf Dryandashfreebasis
db Drybasis
DT Drytorrefaction
DTG Differentialthermogravimetric
EMC Equilibriummoisturecontent
GHV Grossheatingvalue
GKM Globalkineticmodel
HHV Higherheatingvalue
HTC Hydrothermalcarbonization
LHV Lowerheatingvalue
MC Moisturecontent
NHV Netheatingvalue
NLSM Nonlinearleastsquaresmethod
SEM Scanningelectronmicroscope
TG Thermogravimetric
TGA Thermogravimetricanalysis
vol Volume
wt Weight
WT Wettorrefaction
Symbols
Preexponentialfactor
Char
xvii
Meanactivationenergy
Activationenergy
Conversionfunction
Distributionfunctionofactivationenergy
or Rateconstant
Samplemassatanytime
Initialsamplemass
Finalresidualmass
Reactionorder
Objectivefuntion
Universalgasconstant,8.314J.mol1.K1
Solid
Intermediatesolid
Absolutetemperature
Timeofconversion
Volatiles
Volatilereleasedatanytime
Volatilereleasedintotal
Degreeofconversion
Standarddeviationofactivationenergy
Heatingrate
Subscript
ithcomponent
xviii
ChapterI
I. INTRODUCTION
I.1 Problemsidentification
Biomass is currently the major renewable energy source in use and has a high
potential for replacing fossil fuels. While other renewable energy sources can
produce only heat and power, biomass can also be converted to chemicals and
However,usingbiomassforenergyapplicationsisnotstraightforwardduetosome
inherent disadvantages of this fuel including its heterogeneity, low bulk density,
highmoisturecontent,lowheatingvalue,andpoorgrindability.Thesedrawbacks
addition,theyincreasethecostforhandling,transport,andstorageofthefuel.
fuel is to pretreat the fuel via torrefaction. There are two torrefaction techniques,
dryandwettorrefaction.Drytorrefaction(DT)isthermaltreatmentofbiomassin
1
technologiesproducehydrophobicsolidfuelswithmuchbettergrindability,more
homogeneityandsuperiorheatingvalue,comparedwithoriginalbiomass.
During the last decade, research and development activities on DT for energy
applications have been very active. However, similar studies for WT are still
temperature, holding time, pressure, feedstock particle size, feedstock type, and
(fuelproperties,reactivity,andpelletability)areverylimited.
I.2 Researchobjectives
ThisstudyispartoftheSTOPproject(STableOPeratingconditionsforbiomassand
research partners and industry partners through FME CenBio. The STOP project
biomass and biomass residues combustion plants through the utilisation of more
homogenousfuelwithminimisedseasonvariationandoptimisedfuelintermsof
pollutantemissions.
The first objective of this study is to investigate the effects of wet torrefaction
type,anddryingmethod)ontheyield,fuelproperties,andpelletabilityofthesolid
product. The outcome from this investigation would be helpful to establish mass
and energy balances for wet torrefaction and fundamental knowledge for further
processoptimization.
work. Results from this examination help understanding the thermal behaviour
2
and kinetics of the hydrochar for the design, modification and optimization of
thermalconversionunits.
integration,consideringthathotfluegasfromthermalpowerplantscanbeutilized
forWTcontinuousprocessesatindustrialscalestoreducethecost.
I.3 Thesisstructure
Thethesisisorganizedinfourchapters:
ChapterIgivesabriefintroductiontothethesis,whichincludesproblem
identificationandcoreobjectivesofthethesis.
biomassfuelsforenergyapplicationsarethendiscussed.
Chapter III presents the methods of study, which include methods for
studyinghydrocharproduction,characterizationandconversionkinetics.
recommendsfurtherworks.
I.4 Listofpublicationsincludedinthisthesis
1. QuangVuBach,KhanhQuangTran,RogerA.Khalil,yvindSkreiberg,
GulaimSeisenbaeva.Comparativeassessmentofwettorrefaction.Energy&
Fuels2013,27,67436753.
2. QuangVuBach,KhanhQuangTran,yvindSkreiberg,RogerA.Khalil,
AnhN.Phan.Effectsofwettorrefactiononreactivityandkineticsofwoodinair
combustion.Fuel2014,137,375383.
3
3. QuangVuBach,KhanhQuangTran,yvindSkreiberg,ThuatT.Trinh.
Effectsofwettorrefactiononpyrolysisofwoodybiomassfuels.Submittedto
Energy.
4. QuangVuBach,KhanhQuangTran,yvindSkreiberg.Torrefactionof
forestresiduesinsubcriticalwater.SubmittedtoAppliedEnergy.
5. QuangVuBach,KhanhQuangTran,RogerA.Khalil,yvindSkreiberg.
EffectsofCO2onwettorrefactionofbiomass.EnergyProcedia,accepted.
6. QuangVuBach,NevenaMiljenovi,KhanhQuangTran,CarlosSalas
Bringas,yvindSkreiberg.Influencesofwettorrefactiononpelletabilityand
pelletpropertiesofNorwegianforestresidues.AnnualTransactionsThe
NordicRheologySociety2014,22,6168.
ChapterII
II. BACKGROUND
II.1 Biomassassolidfuelforheatandpowergeneration
renewablebasis[1].Itisavailableinmanyformsandfromvarioussources:forestry
organicwastesaswellasmanure[1,2].In2013,biomasssuppliedapproximately56
EJ 1globally,accountingforroughly10%ofglobalannualenergyconsumption[3].
conversionprocesses.
Biomass stores energy from the sun via photosynthesis during its growth. In
otherwords,energyfrombiomassisindirectsolarenergy.Inaddition,biomassis
capturedduringbiomassgrowthandreleasedthesameamountwhenbiomassor
biofuel is burned. Unlike fossil fuels and other alternative energy sources such as
1EJ=1018Joules(J)=1015kilojoules(kJ)=24milliontonnesofoilequivalent(Mtoe).
1
5
wind,geothermalandtidalpower,biomassisadistributedsourceofenergy[4],i.e.
it is available all over the world and near the point of use. Hence, it reduces the
increaseenergysecurity,andsupportsustainabledevelopment.
II.1.1 Plantbiomasscomposition
together construct the plant cell wall, shown in Figure II1. Apart from those,
extractivesandasharealsopresentinbiomassinsmallfractions.Thestructureand
theroleofthesecomponentsareintroducedinthissection.
FigureII1.Biomassconstituentsinplantcellwall(adoptedfrom[5]).
6
II.1.1.1 Cellulose
Cellulose is a homopolysaccharide composed of Dglucopyranose units which
arelinkedtogetherby (14)glycosidicbondswiththedegreeofpolymerization
(DP) from 10,000 to 150,000. Cellulose molecules are virtually linear and have a
crystallinefibrousstructure.Therefore,cellulosehashighmechanicalstrength,high
morecellulosethansoftwood(38.351.3wt%versus33.041.7wt%).
II.1.1.2 Hemicellulose
Unlike cellulose, hemicellulose is a heteropolysaccharide with lower DP, only
150200, and has different side groups on the chain molecule. It is essentially
strengtheningthecellwallbyinteractionwithcelluloseand/orlignin.Thestructure
andcompositionofhemicellulosevariesfordifferentwoodspeciesandcelltypes.
differentreactivityofxylanbasedandmannanbasedcompoundstotemperature.
II.1.1.3 Lignin
Lignin is an amorphous, highly complex, mainly aromatic polymer made of
phenylpropaneunits.Thereisawidevariationofligninstructureswithindifferent
woodspecies.Thelignincontentofhardwoodisusuallyintherangeof20.831.3%,
whereas the lignin content of softwood varies between 26.8 and 32.1%. Softwood
7
residues. The lignin content of hardwood is composed primarily of syringyl and
guaiacylresidues,withfeweramountsofphydroxyphenylresiduals.
II.1.1.4 Extractivesandash
Besides three main components above making up 9598% of plant biomass, a
smallportionoflowmolecularweightorganiccompounds(knownasextractives)
andinorganicmineralcontents(knownasash)canalsobefoundinbiomass.
Extractives are highly heterogeneous and can be divided into three subgroups:
aliphatic compounds (mainly fats and waxes), terpenes and terpenoids, and
phenolic compounds [6]. These components can be extracted from the wood by
eitherorganicsolventorwater.Particularly,somebiomassspeciesmaycontainup
to30wt%tannins.
Ash is the inorganic part left after combustion of biomass fuel. The inorganic
materials in the plant are absorbed from the water or the soil during its growth.
Normally, ash content in wood is less than 1%. The composition of ash will be
presentedlaterinsectionII.1.2.3.
II.1.2 Fuelpropertiesofsolidbiomassfuel
II.1.2.1 Heatingvalue
Heatingvalueisthemostimportantindicatorforthefuelpropertiesofbiomass.
quantityofbiomassfuel,normallyexpressedinMJ/kg.Heatingvaluepresentsthe
energycontainedinthefuel.Therearetwocommontypesofheatingvalue:
assuming that the combustion products are cooled down to the initial
vaporizationinthecombustionproducts.
8
Net or lower heating values (NHV or LHV) is calculated by subtracting
combustion.
Biomassheatingvalueisgreatlyaffectedbyitschemicalcomposition,moisture
and ash content. The heating value can be measured directly employing a bomb
calorimeter or estimated from elemental analysis data via empirical formulas. For
comparison,theheatingvaleofbiomassfuelsisgenerallyreportedonadrybasis
(db)ordryandashfreebasis(daf).
II.1.2.2 Moisturecontent
Moisture content (MC) is defined as the mass percentage of the water in wet
biomass.Waterinwoodybiomassexistsintwomainforms:freewaterfoundinthe
lumensorvoidsofthewoodandboundwaterheldbetweenmicrofibrilsinthecell
wall[7].Mostrawwoodscontainapproximately4070%ofwater.
MChasasignificanteffectontheengineeringofthethermochemicalconversion
process. The heating value of woody fuel decreases with increasing MC. High
moisture fuel burns less readily and produces less useful heat because energy is
wasted to vaporize the water. For correct and efficient operations of boilers or
stoves,astrictrangeoffeedstockMCmayberequired.Moreover,thepresenceof
duringstorage.Also,transportationandhandlingcostsrisewithincreasingMCin
fuel.
II.1.2.3 Proximatecomposition
Atypicalmethodtocategorizethecompositionofbiomassfuelistheproximate
analysis, in which the percentages of volatile matter, fixed carbon and ash in dry
solid biomass fuel are determined. This analysis is normally carried out in a
9
laboratoryfurnace,wherethetemperatureispreciselycontrolledandtheanalysis
isfollowingtherelevantinternationalstandards,e.g.ASTM.
Proximateanalysisshowstheratioofvolatilematterandfixedcarboninbiomass
fuel, an important ratio for the combustion behavior of a fuel. The ash content
influencestheenergycontentanddeterminesthecleannessofafuel.Rawbiomass
fuelcontainsmorevolatilematterbutlessfixedcarbonthancoal.
II.1.2.4 ElementalcompositionUltimateanalysis
Anothermethodtopresentthecompositionofbiomassistodeterminethemass
fraction of elements present in the fuel. For major elements (C, H, N, S, O), an
analysis, for which a CHNS analyzer normally employed. Based on this analysis,
theheatingvalueofbiomassfuelcanbecalculatedfromtheelementalcomposition
viaempiricalcorrelations.However,itshouldbenotedthatthepresencesofother
minor elements and ash forming elements are also important. The ash forming
elements have negative effects on the heating value of biomass fuel. They also
influentthereactivityofthefuelduringthecombustion;andcauseproblemsinthe
elementsincludemajor(Si,Ca,Mg,Na,K,P),minor(Fe,Al,Mn,Cu,Zn,Co,Mo,
As, Ni, Cr, Pb, Cd, V, Hg) and inorganically bound (Cl, S) [8]. Due to very small
minorandtracemetalelementsrequirehighsensitiveanalysisequipmentsuchas
EDX/EDS (Energy Dispersive XRay Spectroscopy), etc. On the other hand, the
presencesofClandScanbedetectedbyionchromatography(IC).
Carbon(C)isthemostimportantelementnotonlyforbiomassbutalsoforany
organicmaterial.Ithasamajorcontributiontotheoverallheatingvalueofbiomass
fuel. Carbon comes from the atmospheric CO2 and becomes part of the plants
10
duringphotosynthesis.ItismainlyreleasedbacktotheatmosphereinformofCO2
between4857wt%(daf),whilethevalueforherbaceousbiomassisslightlylower
[9].
Hydrogen(H)isanotherimportantelementofbiomass,andcanbefoundinthe
valueofbiomass.Duringcombustion,hydrogenisconvertedtoH2O.Thecontent
ofhydrogeninwoodybiomassisaround68%(daf)[9].
Oxygen(O)isamajorelementinbiomassfuels,presentinallbiomasschemical
compositions.However,oxygenhasanegativeeffecttoreducetheheatingvalueof
biomass. The content of oxygen in woody biomass is about 3245 wt% (daf). Its
contentisusuallynotmeasureddirectly,butcalculatedbysubtractingthefractions
ofallotherelementsinthefuelfrom100%.
Nitrogen(N)isthemostimportantnutrientforplantsbutitscontributiontothe
heatingvalueofbiomassisalmostzero.Itisabsorbedviathesoilorthefertilizers
by the plant during its growth. The total nitrogen content in woody biomass is
normally0.10.7wt%(daf).Duringcombustion,nitrogenispartlyemittedinoxide
forms (NO, NO2, N2O), which have negative effects on the global climate and
humanhealth.
Sulfur (S) has only a small fraction (less than 0.1%) in woody biomass and
presents in some organic structures like aminoacids, proteins and enzymes. Like
nitrogen, it is an important nutrient for plant growth but has very small
contributiontotheheatingvalueofbiomass.Duringcombustion,sulfurismainly
transformedtoSO2,whichcontributestoaerosolandsmogformation,acidrainand
corrosionproblems.
11
Potassium (K) and Sodium (Na): these alkaline metals have very low melting
points, which can reduce ash melting temperature and cause problems in
fouling.Thecombinationoftheseelementswithchlorinemakestheproblemsmore
critical.Moreover,thevaporizationandsubsequentcondensationofvolatilemetals
in general lead to the formation of submicron fly ash particles, which are more
difficulttoprecipitateindustfilters,andhencecausehealthproblems[8].
Calcium (Ca) and Magnesium (Mg) have relatively high melting point, which
helps increase the melting temperature of ashes and reduces ash sintering on the
grateorinthefurnace.
Silicon(Si)isoneofthemainashformingelements.ItscombinationwithKand
Na can lead to the formation of alkali silicates in fly ash particles, which melts at
lowtemperaturesandresultsindepositionproblem.
Chlorine (Cl) is almost completely vaporized, forming HCl, Cl2 and alkali
problematic issues including emissions (dioxins, acid rain, and aerosol formation)
and operation problems (fouling and corrosion). However, chlorine is not solely
responsible for these issues. Together with the presence of alkali metals, it forms
alkalichlorideswhichreducetheoverallashmeltingtemperatureto700800Cor
even lower for high alkali content biomass such as straw. This causes deposition
and corrosion problems for the combustion system. Generally, chlorine content
higherthan0.1wt%(db)isproblematic.
Heavymetals(Hg,Sb,As,Cd,Cr,Co,Pb,Ni,andSe)arepresentintracelevels
inbiomass,buttheyaretoxicandcauseriskstohumanhealth[10].Ashtreatment
ordustprecipitationcanbeappliedtoreducetheemissionsofthesemetals.
12
II.1.2.5 Grindability
Priortoconversionprocesses,biomassneedstobepulverizedtoobtainamore
homogeneous feedstock as well as to improve the heat and mass transfer during
theprocessesandthecombustionstability.Grindabilitypresentsqualitativelyhow
easy a biomass sample can be pulverized. Generally, fuel with good grindability
consumes less energy to comminute, and vice versa. However, raw biomass
possessesverypoorgrindabilityduetoitsfibrousstructurecomparedtocoal,and
thereforeconsumesmuchmoreenergythancoalinthepulverizationstep.
In the literature, there are two methods that can be adopted for evaluation the
comparing it with that of standard coals [11, 12]. This assessment is somehow
Althoughthismethodcanshowhowfinethefuelparticlesare,itdoesnotexplicitly
showthegrindingenergy.Inthesecondmethod,thepowerconsumptionofamill
topulverizeanamountofbiomasssampleisrecordedandregardedasthespecific
grinding energy (SGE) [13, 14]. This method gives information on the energy
requirement, but not the particle size distribution of the samples. Therefore, the
particlesizedistributionshouldbeanalyzedinaseparatestep.
II.1.2.6 Hydrophobicity
Hydrophobicity is the water repellant property of biomass fuel. Biomass
which are likely to form hydrogen bonds with free water. This gives biomass a
hygroscopic nature, i.e. it has poor hydrophobicity. During storage, biomass fuel
tendstoabsorbwaterevenifitisalreadydried,untilequilibriumisreachedwith
thehumidityinthesurroundingatmosphere.Thepresenceofwaterinbiomassis
13
undesired, as mentioned in section II.1.2.2. Therefore, poor hydrophobicity is a
drawbackofbiomassfuelcomparedtocoal.
biomass fuel so far. Researchers have had to develop or adopt methods on their
ownforsuchinvestigations.However,itcanbefoundintheliteraturetwogroups
of methods for evaluation the hydrophobicity of biomass fuel. In the first group,
biomassbulksamplesorpelletswereimmersedinwaterforsomehoursandthen
the amount of absorbed water was recorded and compared [1517]. In the other
assessments,themoistureuptakeratesofbiomasspowderweremeasuredusinga
controlled humidity cabinet [1821]. Methods in the second group are preferable
because it can minimize the interferences of water trapped in pores, and more
importantly,itgivestheinformationoftheequilibriummoisturecontent(EMC)of
thefuelaswellashowlongtimeneededtoreachthislevel.
II.1.2.7 Bulkdensityandenergydensity
Bulkdensity(kg/m3)andenergydensity(GJ/m3)aredefinedrespectivelyasthe
mass and energy per unit volume of biomass. Compared to coal, these two
densities of biomass is much lower. For example in [22], bulk density of raw
biomassis350680kg/m3versus11001350kg/m3forcoal,whereasenergydensity
values are about 5.8 for raw biomass and 3040 GJ/m3 for coal, respectively. The
low bulk and energy densities limit the use of biomass for heat and power
production,aswellasincreasethecostofbiomasslogisticsandstorage.
II.1.2.8 Pelletability
Pelletizationisamechanicalprocessthatconvertsbulkysolidbiomassfuelsinto
pelletswithbothincreasedbulkandenergydensities.Inaddition,biomasspellets
have more homogeneous shape and structure than bulky biomass, which is
14
qualitative indicator, which can be evaluated via some factors such as pelleting
Generally, biomass with good pelletability requires low pelleting pressure and
temperaturetoproducehighdurablepellets.
II.2 Thermochemicalconversionsofbiomass
frombiomassfuels.Theyincludepyrolysis,gasificationandcombustion,ofwhich
themainproductsandapplicationsaresummarizedinFigureII2.Moredetailsfor
eachprocesswillbeintroducedinthenextsubsections.
FigureII2.Thermochemcialconversionroutesforbiomassfuels(adoptedfrom[24]).
II.2.1 Pyrolysis
Pyrolysisisthethermaldegradationofbiomassatelevatedtemperaturesandin
theabsenceofoxygen.Theprocessinvolvessimultaneousandsuccessivereactions
whenbiomassisheatedinaninertatmosphere.Themainoperatingparametersin
15
pyrolysis are temperature, residence time, heating rate, pressure, reactor
composition,ashcontentandcomposition,particlesize,moisturecontent,etc.also
play an important role in a pyrolysis process [25]. The products from biomass
pyrolysis include a solid (biochar), a viscous liquid mixture (biooils) and some
operating parameters [24]. Low temperatures and long residence times favor the
productionofbiochar.Hightemperaturesandlongresidencetimesincreasethegas
yield.Moderatetemperaturesandshortvaporresidencetimespromotethebiooil
production.
Generally,pyrolysisisdividedintothreecategoriesbasedontheheatingrateof
theprocess:slow(orconventional),fast,andflashpyrolysis.Slowpyrolysistends
toproducemorebiocharthanfastandflashpyrolysis,whilethetwolattersaimat
pyrolysis are presented in Table II1. On the other hand, pyrolysis is also first in
twoconsecutivestepsinbothgasificationandcombustionprocesses.
TableII1.Mainoperatingparametersfordifferentpyrolysisprocesses(adoptedfrom[26]).
whichbiomassisheatedwithalowheatingratetoafinaltemperature.Ittakesup
tohourstocompleteandresultsinbiocharasthemainproduct.
16
Fastpyrolysisemploysmuchfasterheatingrates(about10200C/s)andyields
more than 60% of biooil. Typically, fast pyrolysis can produce 6075 wt% of bio
oil,1525wt%ofbiochar,and1020wt%ofgases.
heated up extremely fast (> 1000 C/s), and the residence time is only part of
second. Up to 80% biooil can be obtained via this technology. Due to very high
heating rates and short reaction times, fine particles are required to minimize the
heatandmasstransferlimitationinflashpyrolysis.
While the charcoal production technologies are mature, the biooil production
technologies are still being developed. Moreover, for fuel application, biooil has
some drawbacks, compared to petroleum oil, which include: high viscosity, high
upgrading and/or refining step is required before pyrolysis biooil can be used
directlyorblendedwithotherpetroleumbasedfuels.
II.2.2 Gasification
waterandothertracecomponents).Productgasiseasierandmoreversatiletouse
thantheoriginalbiomass,e.g.itcanbeusedtopowergasenginesandgasturbines,
[27].Toaccomplishgasification,itisalwaysnecessarytopassthroughapyrolysis
stage first [28]. In other words, pyrolysis is the first step in biomass gasification.
However,agasificationprocessisnormallycarriedoutathighertemperaturesthan
apyrolysisprocess[28].
Duetoincompleteoxidation,thechemistryofagasificationprocessiscomplex
andinvolvesanumberofreactions.Themainreactionsduringbiomassgasification
17
is summarized in Table II2, classified into homogenous gasphasereactions and
heterogeneousreactions[29].
TableII2.Mainreactionsduringbiomassgasification.
Homogenousgasphasereactions
H2+O2H2O Hydrogencombustion/oxidation
CO+O2CO2 Carbonmonoxidecombustion/oxidation
CH4+O2CO+2H2 Methanecombustion/oxidation
CH4+CO22CO+2H2 Dryreformingreaction
CH4+H2OCO+3H2 Steamreformingmethanisation
CO+H2OCO2+H2 Watergasshiftreaction
Heterogeneousreactions
C+O2CO2 Carboncombustion/oxidation
C+O2CO Carbonpartialcombustion/oxidation
C+CO22CO Boudouardreaction
C+H2OCO+H2 Watergasreaction(steamreforming)
C+2H2CH4 Methanisationreaction
II.2.3 Combustion
Combustionmaybedefinedasfastoxidationofbiomass,producingheatathigh
temperatures.Itisaproventechnologyforheatandpowerproduction[30],andis
currently the most important energy application of solid biomass fuel. Biomass
[8].Biomasscombustionsystemsareavailableinaverybroadsizerangefromvery
combustionofbiomassincoalfiredpowerplantsisalsointerestingbecauseofthe
18
andheterogeneousreactions,butoveralltheycanberepresentedbythefollowing
global equation, in which minor elements with small and trace elements are
neglected:
becalculatedfromelementalbalances,asfollows:
1
, 1 1 , 0.79 4 2
2 4 2 0.21
the ratio between the available and the theoretically needed (stoichiometric)
temperature and residence time, the excess air ratio strongly affects the
composition and quality of the combustion products such as NOx emissions and
otherunburntpollutants.
II.3 Biomasscombustiontechnologies
A combustion system should supply fuel and combustion air with an optimal
mixinganddistributioninordertoburnthefuelwithmaximumheatreleaseand
mostlythesameasforcoal,whichincludefixedbed,fluidizedbedandpulverized
fuel combustion. They are demonstrated in Figure II3 and briefly introduced in
thissection.
19
FigureII3.Commonsystemsforbiomasscombustion(adoptedfrom[8]).
II.3.1 Fixedbedcombustion
holes in the grate, is the main technology in this category. It includes fixed grate,
moving grate, travelling grate, rotating grate and vibrating grate. The grate
furnaces have some advantages such as low investment cost (for plants with
capacitylessthan20MWth)aswellaslowoperatingcost.Theyarealsocapableof
working with heterogeneous fuels, large particles sizes and high moisture
feedstock.Inaddition,gratefiringfurnaceshavegoodburnoutofcarboninflyash
particles and low dust load in the flue gas. Another advantage of gratefiring
systems is that they are less sensitivity to slagging than fluidizedbed furnaces.
fluidizedbedfurnace.Inaddition,itisdifficulttomixwoodyandherbaceousfuels
ingratefiring.Also,theenergyefficiencyofgratefiringsystemsislowerthanfor
fluidizedbedsduetoahigheramountofexcessair.
20
II.3.2 Fluidizedbedcombustion
mixedwithamedium(typicallysand)andkeptsuspendedinthismixbyincoming
high velocity air. The technology is classified into two subgroups: bubbling
combustioniscurrentlyconsideredthebesttechnologytoburnbiomass[32].
II.3.3 Pulverizedfuelcombustion
Thepulverizedfuel(PF)technologyisusedforlargescalecombustionsystems
whichwerepreviouslylargelycoalfired.Itrequiresthatbiomassisfinelyground
to reach a particle size less than 1 mm [32] prior to feeding to the combustion
chamber. Also, the moisture content of the fuel should not exceed 20 wt%. The
then become problems, especially for biomass fuel with high ash content. Apart
from the above difficulties, PF combustion requires low excess air and thus
increasesthethermalefficiency.Goodcombustioncontrolandversatileloadcanbe
emissionwithaninstallationofcycloneorvortexburner,i.e.lowNOxburners.
II.3.4 Cocombustion
Cocombustionorcofiringbiomasswithcoalinexistingcoalfiredpowerplants
increasingtheshareofrenewableenergysourcesandtoreduceCO2emissions[33].
Cocombustionconceptscanbedistinguishedas[8]:
Directcocombustion:directfeedingofbiomasstothecoalfiringsystems.
fuelgaswithcoalinthesameplant.
21
Parallelcocombustion:involvesthecombustionofbiomassinaseparate
combustor and boiler producing steam, which is used within the coal
firedpowerplant.
boilers,therestincludes24%withBFBboilers,19%withCFBboilers,and9%with
gratefired boilers [33]. These figures indicate among others the importance of
improvingthegrindabilityofbiomassfuelsforcocombustion.
II.4 Challengesandpretreatmentneeds
Combustion and cocombustion are the main technologies as they account for
more than 90% of the global bioenergy deployment [8]. However, utilization of
thisfeedstock.Forexample,dryingandgrindingpriortofeedingintocombustion
biomassmaterialarealsocostly.Themainchallengescoupledwiththedrawbacks
ofbiomassarelistedinTableII3.
Inordertoovercomethesechallenges,biomassnormallyrequiresapretreatment
biomasscanbeachieved:(1)increasedheatingvalueduetoareductionintheO/C
ratio; (2) intrinsic transformation from hygroscopic into hydrophobic nature; (3)
better grindability coupled with less energy requirement for size reduction of the
fuel.Inthenextsection,anoverviewoftorrefactiontechnologiesispresented.
22
TableII3.Disadvantagesofrawbiomassmaterialsutilizedforthermochemicalconversions.
Biomassdrawbacks Mainchallenges
Highmoisturecontent Reducetheheatingvalue
Requireenergyintensivedryingstep
Reducetheefficiencyoftheconversionprocesses
Increasestorageandtransportationcosts
Increaserisksofbiologicaldegradation
Increasecorrosionbecauseofcondensationofwater
influegas
Lowbulkandenergydensity Increasestorageandtransportationcosts
Requirehighfeedingcapacity
Poorgrindability Increasegrindingenergy
Hygroscopicnature Uptakemoistureduringstorage
Increaserisksofbiologicaldegradation
Highoxygencontent ReducethenumberofCHbonds
Reducetheheatingvalueandenergydensity
Reducethethermalstability
Highalkalimetalcontent Causeashrelatedproblems
Heterogeneity Widevariationinproperties
23
II.5 Biomasspretreatmentviatorrefaction
II.5.1 Drytorrefactionanditschallenges
Dryorconventionaltorrefactionisdefinedasthermaltreatmentofbiomassin
aninertenvironmentatatmosphericpressureandtemperatureswithintherangeof
200300C[3436].Recently,thedefinitionhasbeenextendedtoincluderesearches
ondrytorrefaction(DT)inthepresenceofoxygenandcarbondioxide[3740],and
underelevatedpressures[41,42].
During the last decade, research and development activities on DT for energy
active [11, 16, 34, 35, 4351]. It has been reported that, during combustion, dry
torrefiedbiomassbehavesmorecoallikewithmorestableburningcharacteristics,
compared with untreated biomass [11, 47]. The gasification efficiency and the
syngas quality are improved by DT [46, 48, 49]. Moreover, for fastpyrolysis, DT
appearstodecreasetheyieldofbyproductsandtoimprovethequalityofbiooil
[50,51].
The DT technology has been developed rapidly and is ready for market
introductionandcommercialoperation[52].However,ithasbeenclaimedthatno
clearwinnerinthisareacanbeidentifiedsofar[52].Thissituationisduetoboth
content not higher than 510 wt% [53], i.e. an energy intensive predrying step is
neededtodrybiomasspriortoaDTprocess.AnotherproblemassociatedwithDT
is that the relative ash content in drytorrefied biomass is higher than native
biomass,becauseofthevolatilesmasslossduringthetorrefactionprocess.Thiscan
biomasscomparedwithrawbiomass.Inaddition,drytorrefiedbiomassisverydry
and brittle, which makes this kind of material more difficult to pelletize than
24
untreatedbiomass[5456].Ithasbeenreportedthatnopelletcouldbemadefrom
biomass.
Fromaneconomicpointofview,currentDTtechnologiesareusingwoodchips
fromstemwood,afeedstockofrelativelyhighqualityandthuscost.Utilizationof
other biomass waste sources may help reducing the total cost of biomass
has other technical issues related to emissions from the process, product quality
controlandflexibility,heatintegrationandfeedstockpropertiesvariations[52,57].
promising alternative to DT. The WT process and its advantages over DT will be
discussedinnextsection.
II.5.2 Wettorrefaction
Wettorrefaction(WT)maybedefinedastreatmentofbiomassinhydrothermal
mediaorhotcompressedwaterattemperatureswithin180260C[18,19,5860].
ComparedtoDT,WToffersseveraladvantages:
WTemployswaterinsubcriticalconditionsasreactionmedia,andtheenergy
residuesandotherbiomasswastes,whichareavailableatalowcost.Itshould
beremindedthatthesehighmoisturefeedstocksareproblematicforDT.
temperature and shorter holding time than DT [18]. In addition, the fuel
25
properties of the solid produced by WT are better than DT, e.g. increased
HHV,bettergrindability,andimprovedhydrophobicity.
produce cleaner solid biomass fuels via WT, with regard to the inorganic
impurities.
producedfromhydrochar(fromWT)arebetterthanthoseproducedfromthe
torrefied biomass does not require water addition in order to improve the
pelletabilityandbindingcapacityasisthecaseforDT[64,65].
After WT, the wet hydrochar can be effectively made dry by mechanical
dramaticallyreducingtheenergyrequirementforthepostdryingstep.
sugars, organic acids, furans, and furfurals [59, 66, 67] can be recovered from the
aqueousphaseproductsofWTinordertoimprovetheeconomyoftheWTprocess.
Thereareanumberofconceptsintheliterature,whichmaybefoundsimilarto
those,HTChassometimesbeenusedtorefertoWT.However,itshouldbenoted
thattherearesignificantdifferencesbetweenWTandHTC.
even though small fractions of cellulose and lignin are also degraded, at
becausehemicelluloseisdegradedinsubcriticalwaterconditionsattemperatures
26
below250C[73].ThemainproductofWTishydrochar,anupgradedsolidbiofuel
withhighercarboncontentthanthatoftheuntreatedbiomass.
Ontheotherhand,HTCrequiresfurtherdegradationsofthetwootherbiomass
carbonandremainingash.Duetothisrequirement,HTCiscarriedoutathigher
above 300 C [73, 8890]. However, HTC can also be carried out at temperatures
below 300 C, but with catalyst addition [91]. The temperature ranges of the two
processesinatemperaturepressurephasediagramaredemonstratedinFigureII4.
400
Hydrothermal carbonization
Wet torrefaction
300
supercritical fluid
Pressure (bar)
200
100 liquid
vapor
Saturated line
0
100 200 300 400 500 600 700
Temperature (C)
FigureII4.Wettorrefactionandhydrothermalcarbonizationregionsinatemperature
pressurephasediagramofwater.
More importantly, while hydrochar produced via WT is used only for energy
producedviaHTCcanbeusednotonlyasfuelbutalsoassoilenhancer,fertilizer,
27
activatedcarbon,andevencarbonmaterialforsynthesizingcarbonnanotubes[87,
92, 93]. Due to these differences, it is obvious that the energy efficiency of the
processandthefuelpropertiesofsolidproductsaremorecriticalforWTthanfor
HTC,whereasphysicalandchemicalpropertiesofhydrothermalcharcoal maybe
ofgreaterimportancewhenotherutilizationsthanasfuelareconsidered.Themain
differencesbetweenWTandHTCaresummarizedinTableII4.
TableII4.MaindifferencesbetweenWTandHTC.
Hydrothermal
Wettorrefaction
carbonization
Workingtemperature 180260C >300C
Solidyield >60% 3560%
Mainproduct Upgradedsolidfuel Charcoal,activated
carbon
Applications Heatandpower Heatandpower,
generation absorbent,soilenhancer,
fertilizer,etc
condition
Hotcompressedwater(HCW)isdefinedassubandsupercriticalwaterabove
200 C and at sufficient high pressure [94]. At high temperature and pressure
whenapproachingthecriticalpoint(T=374C,p=220.6bar, =320kg/m3).Some
criticalwater,whichisthemediaformosthydrothermalconversionsofbiomass,is
presented.
28
FigureII5.Changesinphysicochemicalpropertiesofwaterat30MPaasafunctionof
temperature(adoptedfrom[97]).
II.5.3.1 Dielectricconstant
Thedielectricconstant()ofasolventisameasureofitspolarity,i.e.higher
meansmorepolarity.Waterisoneofthemostpolarsolvents,ofwhichitsdielectric
(=36.7), or acetone (=20.7); thus, HCW behaves like an organic solvent which is
suitableformanychemicalreactions.Inaddition,asaprotonicsolvent,HCWcan
donateprotonsandbecomesanaturalacidcatalyst.
II.5.3.2 Ionproducts
A unique property of HCW is that it may behave like a nonpolar solvent, but
the single molecules are still polar, hence it possesses very unusual properties for
new reactions [98]. As can be seen in Figure II4, the ion products of water (Kw)
29
increasefrom1014at25Ctoabout1011intherangebetween200275C.These
ionsmayactasacidorbasecatalystsandthusHCWcanplaytheroleofaproton
donatororacceptor.Therefore,noadditionofcatalystisrequiredinWTsinceitis
carriedoutinHCW.
II.5.3.3 Transportproperty
Both density and viscosity of HCW are decreased to lower values, which
increase its diffusion rate, compared with normal water [95]. A high diffusion
ratehelpsavoidmasstransferlimitations.ThetransportpropertiesofHCW(high
diffusion rate, low viscosity) can enhance the rate of chemical reactions, making
HCWanexcellentreactionmedia[98].
II.5.4 Degradationofbiomassinsubcriticalwaterconditions
Inhydrothermalmedia,hydrolysisisthekeymechanismforthedecomposition
ofthethreemaincomponentsofplantbiomass.ForWT,whichnormallyemploys
However,asHCWcandonateprotonsandbecomeanacidcatalyst,acidhydrolysis
mayalsotakepartinthedecompositionofbiomassconstituents.
SimilartoDT,WTaimsatdecomposinghemicellulosefrombiomassinorderto
destroyitsfibrousstructure.Infact,hemicelluloseispoorlyresistanttohydrolysis
andiseasilydissolvedinwaterfromapproximately180C.Manyresearchers[19,
monosaccharides and other substances are complex, and what kinds of organic
compoundsthatarepresentinthehydrolysisproductarenotclearlyenumerated.
productsinhydrolysisissubjecttoxylose,adepolymerizationproductofitsxylan
30
backbone.Theothersareglucose,arabinose,fucose,galactose,glucuronicacidand
galacturonicacid[98].Asimplepathwayforhydrothermolysisofhemicellulosecan
beshownasfollows[100]:
Inhydrothermalcondition,celluloseismorestablethanhemicelluloseandstart
decomposingattemperatureshigherthan200C.Themaindegradedproductfrom
cellulosehydrolysisisglucose,whichresultsfromthebreakageofglycosidicbonds
inthecellulosemacromolecule.Mostcellulosehydrolysismechanismsarebasedon
thatdevelopedbySaeman[101]:
some studies have found that the crystallinity of cellulose increased after
hydrothermaltreatment[102104],whichmaybesubjecttotherepolymerizationof
degradedproducts.
FigureII6.Hydrothermaldegradationofcottoncelluloseasafunctionofreactiontimeand
temperature(adoptedfrom[105]).
31
The main part of lignin is thermally stable and requires relatively high
temperature as well as enough time for complete degradation. Dinjus et al. [106]
reported that the temperature range of 180 to 250 C is too low for a strong
suchtemperatures.Lietal.[107]alsoagreedthatonlyalimitedamountofligninis
canprecititateandbindthecelluloseirreversibly.
32
ChapterIII
III. METHODOLOGY
III.1 Hydrocharproduction
III.1.1 Materials
Stem woods from Norway spruce (softwood) and birch (hardwood) were used
asfeedstockinthethreefirstpapersinthisthesis.Thewoodsampleswereobtained
fromalocalsupplierinTrondheim,Norwayinformof1cmand3cmcubes.The
woodcubeswereusedforWTasreceived,withonlyanadditionaldryingstep(at
1032Cfor48h).
In the other papers, Norway spruce and birch branches were selected to
from a local forest in Trondheim, Norway. The bark was then removed from the
impurities,contaminantsandcompositiondifferences.Thebarkfreebrancheswere
thencutinto34mmthickslicesandwashedwithwater.Thecleanedsliceswere
maintainthemoisturecontentofthebranches.Thesamplespreparedthiswayare
33
samples were dried at 103 2 C in an oven for 48 h to obtain dry or oven
driedfeedstock.
III.1.2 Experimentalsetup
WT experiments were carried out in a 250 ml Parr reactor model 4651 (Figure
III1), which is made of stainless steel (T316SS) and equipped with a benchtop
ceramicheater(4923EE),atemperaturecontroller(4838EE),apressuregauge,and
two valves as shown in Figure III2. A thermocouple for monitoring the reaction
temperature(temperatureofwaterinthereactor)isconnectedtothecontrollerby
introducedintothereactorviaathermowell,whichiscastinthereactorhead.In
wellinordertokeepthewoodcubesanddriedbranchesentirelysubmergedinthe
waterasshownintheFigureIII2.However,theglassplateisnotneededinWTof
cylinderviaValve1.
Distilledwaterwasusedasthereactionmedia.Theratioofdryfeedstockover
waterwas1:5byweight.Inaddition,forstudyingtheeffectofpressure,aratioof
1:10 was employed with the feedstock prepared in powder form of 0.51 mm to
minimizeheatandmasstransferlimitationsduringthetorrefactionprocess.Allthe
experiments were duplicated, from which data were collected and processed to
generateaveragevaluesforrelevantassessments.
34
FigureIII1.TheParr4651reactor(adoptedfromparrinst.com).
III.1.3 Wettorrefactionprocedure
Before every torrefaction run, the furnace (the heater) without the reactor was
heatedfor30mintoapresettemperature.Atthesametime,thereactorwasloaded,
closed, sealed, and purged with compressed nitrogen gas for 10 min. Then the
reactorwaspressurizedandplacedinthepreheatedfurnacewhichwassettothe
time was counted from the time at which the reactor temperature reached the
preset temperature to the end point when the reactor was taken out from the
furnaceandsubmergedinanicebathforcooling.Whenthereactorcooledtoroom
temperature, the pressure was gradually released and the reactor was opened for
productscollection.
35
FiigureIII2.Schematicd
diagramofttheWTreactorandtheeexperimenntalsetup.
III.1.4 Producttsseparation
Duettopracticaaldifficulty
yinhandliingthegases,onlyp
productsin
nthesolid
dand
liquidphaseswereecollected
dinthisstu
udy.They weresepa
aratedfrom
meachotheerby
collected
d solid (hy
ydrochar) was dried
d at 103 2 C for 48 h and then balan
nced.
Reading
gs from thee balance were tabu he mass of solid prooduct from
ulated as th m the
WT.Theedriedsollidwastheenstoredin
nadesicca
atorfilledwithsilicaagelforfu
urther
studies.
36
III.2 Hydrocharcharacterization
III.2.1 Proximateandultimateanalyses
ProximateanalysesofallthefeedstockwereperformedaccordingtotheASTM
standards: E781, E872 and D1102 for moisture content, volatile matter and ash
content,respectively.Ultimateanalysesofthefuelsondrybasisweredetermined
byanEA1108CHNSOelementalanalyzer(CarloErbaInstruments).
III.2.2 Higherheatingvaluecalculation
The higher heating value of raw biomass and hydrochar were calculated
accordingtoacorrelationproposedbyChanniwalaandParikh[108],showninEq.
(III1)
oxygen, nitrogen, and sulfur in the biomass fuel, respectively. The elemental
compositionwasobtainedfromanultimateanalysis.
III.2.3 Specificgrindingenergy
Forthisassessment,anIKAMF10cuttingmill(IKAWerkeGmbH&Co.KG)
equippedwitha1mmbottomsievewasused.AnanalogcurrentinputmoduleNI
electrical current during grinding. A LabView program was used for the data
acquisition and the calculation of the energy consumption which was logged to a
fileevery2seconds.Thepowerofthemillundernoloadconditionswasmeasured
and subtracted from the power of grinding the biomass samples. The grinding
energywasdeterminedbyintegratingthepowercurveduringthegrindingperiod.
37
Finally, the data was normalized to the initial sample weight, expressed in
kWh/ton.
III.2.4 Moistureuptaketest
ThegroundbiomasssampleobtainedfromtheSGEassessmentwasusedinthis
test. It is screened through a sieve (Fritsch Analysette 3 Pro) to obtain the sample
particles smaller than 250 m. The powder is then dried at 103 2 C for 24 h to
removeanywateruptakenduringgrinding.Next,anamountofapproximately2
grams of dried powder is spread on a glass Petri dish, which is then placed in a
timeduethemoistureuptakeofthetestedmaterialarerecordedevery24hforthe
total test period of one week. The moisture content of the tested material is then
calculatedaccordingtoEq.(III2):
% 100%, 1, , 7 (III2)
themassofthesamplebeforethetestandmeasuredontheithday,respectively.
III.2.5 Morphologyandstructurestudy
The morphology and structure of raw and wettorrefied biomass were studied
bymeansofatabletopSEMHitachiTM3000.Thetestedsamplewasattachedona
holder and loaded into a vacuum chamber for the morphology observation, in
whichanacceleratingvoltageof15kVwasapplied.
38
III.22.6 Pelleetability
III.22.6.1 Pelleetization
Th
he pelletizzation wass carried o
out using a
a single pe
ellet press [54], pressented in
Figu
ureIII3,w
whichallow
wsprecise controlan
ndadjustm
mentofcom
mpressing pressure
diam
meter) and
d a tungsteen carbidee pressing rod. The press is h
heated by a jacket
heatter(450W))ofwhichthetempeeraturewasscontrolledbyaPID
D.Thecom
mpressing
forceeisapplied
dtotherod
dusingan
nInstron10
00kNtextu
ureanalyzzer.
FiggureIII3.S
Singlepelleetpressunitt:a)pictureeoftheequipment.Draawingoftheesingle
pelleetunit:(b) topview,(cc)sectionviiewAA.
Th
he steel cylinder
c was
w first h
heated to a
a preset temperatur
t re. After a
a steady
temp
perature was
w reacheed, the chaannel was filled witth biomasss material and the
leng
gthatdifferentpressu
ures,theaamountof materialw
wasvaried
d.Theleng
gthofthe
betw
ween the bottom and
d top part of the pellet (density
y gradientt). After teempering
for33minutes,thebiomassmateriaalwascompressedatarateof22mm/minuntilthe
pressetpressureewasreached.Afterrwards,theepressurewasreleassed,thebottomrod
remo
ovedandtthepelletw
waspresseedoutfrom
mthechann
nel.Thediischargingspeedof
39
the rod was set to 15 mm/min. The total retention time of the material in the
channel was 810 min. The obtained pellets were stored in sealed plastic bags at
roomtemperatureandhumidity(25C;30%)untilfurthertesting.
III.2.6.2 Pelletdensity
The pellet density was calculated by dividing the weight by the volume of the
pellets.Thelengthanddiameterofthepelletsweremeasuredbymeansofadigital
caliper.
III.2.6.3 Compressingtest
Thecompressingtestswerecarriedoutat48hafterthepelletswereproduced.A
Instruments,England)wasemployedforthistest.Thecompressionspeedwasset
automatically.Thepelletstrengthwasexpressedasthemaximumforceperlength
ofthepellet(N/mm).
III.2.7 Thermogravimetricanalysis
atmosphere[109].TGAiscommonlyusedtodeterminethemasslosscharacteristics
evenatpressurizedconditions.ThemostimportantapplicationofTGAistostudy
estimationoftheproximateandchemical(throughkineticmodelling)compositions
inbiomassfuel.
40
TheoutputdatafromTGAarenormallyusedtoconstructathermogravimetric
(TG) curve, from which the mass losses versus temperature or time can be
observed. In order to know the conversion rate of biomass during the thermal
(DTG)data.
biomassfuels
combustors).Becauseofthis,thepyrolysisandcombustionkineticstudiesforsolid
biomass fuels have been extensively studied for many decades [25, 110113]. A
difficultyinkineticanalysisforcombustionatfullindustrialscalesisthatitisnot
usingasufficiently small sample mass in fine powder form and employing a low
heatingrate,aregimecontrolledbychemicalkineticsisestablishedandthusheat
and mass transport limitations can be neglected [25]. In order to meet these
conversions of biomass in the kinetic regime [25, 110117]. In the next sections,
meansofTGAtechniquewillbepresented.
41
III.3.1 Kineticmodels
III.3.1.1 Pyrolysis
Besides being a method for production of biochar and biooil, pyrolysis or
aftercooling.Asinglereactionoronestepmodelisbasedonthesimpleideaofthe
formation of char and volatiles from initial solid biomass fuel. In a more detailed
kinetic model, the decomposition of biomass fuel includes both primary and
secondaryreactions.Thelattermodelisknownastwosteporconsecutivereaction
model.
AsmentionedaboveinsectionII.1.1,biomassfueliscomposedofhemicellulose,
celluloseandlignin.Thethermalbehaviorsofthesecomponentsaredifferent[22].
Duringpyrolysis,hemicellulosedegradesfirstinthetemperaturerangeof200300
Canditsdegradationisassociatedwithasocalledshoulderfoundontheleftside
ofthepyrolysispeakinaDTGcurve.Thedecompositionofcelluloseoccursat325
375Candcoupleswiththemainpyrolysispeakwhilelignindegradationoccursin
a very broad temperature range from 250500 C [22, 118]. A model with three
parallelreactionsisthusproposedtolookatthepyrolysisbehaviorofeachbiomass
eachcomponentbecausethedegradationofonemayovershadowtheothers[118].
reactionmechanismsforcommonmodelsarepresentedhereafter.
42
III.3.1.1.1 Singlereactionmodel
Single reaction model, also known as onestep model, is the simplest model in
pyrolysismodelling.Inthismodel,solidfuel( )isdecomposedwithareactionrate
toproducechar( )andvolatiles( ):
(III3)
usingonlyonereactiontodescribebiomasspyrolysis,thefitqualityofthemodelis
poor.Especially,forsolidfuelhavinghighhemicellulosecontent(e.g.hardwood),
thefitqualitycanbedramaticallyreducedduetotheappearanceofthementioned
shoulderintheDTGcurve.Inordertoimprovethefitqualityofthesinglereaction
model,eitheratwosteporathreepseudocomponentmodelcanbeusedinstead.
III.3.1.1.2 Twostepmodel
Atwostepmodelorconsecutivereactionmodelassumesthatsolidfuel isfirst
converted to an intermediate solid and volatiles in a primary reaction. The
intermediate solid reacts afterwards to form the final char and the additional
volatiles in secondary step. The rate constants of the primary and secondary
(III4)
(III5)
This model was first applied for studying the pyrolysis of cellulose [119] and
then extended to biomass materials [112, 120]. Recently, the model has also been
employedforkineticmodellingofdrytorrefaction[121124].
III.3.1.1.3 Threepseudocomponentmodel
Solid biomass fuel consists of three main components with different thermal
43
represent all the components during the pyrolysis process. A threepseudo
component model can overcome this limitation. The model has three parallel
reactions,asshownbelow:
(III6)
(III7)
(III8)
reactionrateofeachpseudocomponent.
threemaincomponentsofbiomass,thusthefitqualityincreasessignificantly[125].
In addition, this model can describe well the possible overlapped reactions of the
lumped components in biomass [114, 126, 127]. Moreover, some researchers have
modifiedthismodelbyincludingadditionalstepsinordertofurtherimprovethe
fitquality.Then,themodifiedmodelmaycontainuptofiveorsixparallelreactions
[128, 129]. However, the model with three pseudocomponents is the most
commonlyused.
III.3.1.2 Combustion
Combustion of solid biomass fuel generally consists of two main steps:
devolatilization(orpyrolysis)andcharcombustion(orcharburnoff).Thereaction
mechanisms for combustion are based on those for pyrolysis because the thermal
similar [126, 130, 131]. In the first step, all pyrolysis kinetic models introduced in
additionalreactionforchar( )combustion,releasingcombustionproduct( :
44
(III9)
III.3.2 Mathematicalmodelling
processingoftheexperimentaldatatoformulatetheselectedreactionmechanisms
andtoestimatethekineticparametersisalsoanimportantpartinthekineticstudy.
Inmostkineticformulationsofbiomassdecomposition,theconversionrate( )
ofareactionvirtuallyobeysthefundamentalArrheniusexpression:
. . (III10)
constant, istheabsolutetemperature.Theconversiondegree()isdefinedasthe
massfractionofdecomposedsolidorreleasedvolatiles:
(III11)
any time; is the total mass of released volatiles and is the mass of released
volatiles at any time. The function in Eq. (III10) depends on the reaction
mechanism.
section.Moreover,itisworthnotingthatacomplexmathematicalmodelmayoffer
excellent fit between calculated and experimental data, but also requires more
powerfulcomputerrecourses.Inactualengineeringcontextsandforkineticstudy,
asimplermodelwithareasonablygoodfitismorefavorablethanacomplexone
whichgivesonlyaslightlybetterfit[132,133].
45
III.3.2.1 Modelfreemethod
Modelfree method is employed to determine approximately the activation
energy and preexponential factor from TG data at any conversion rate without
knowledgeaboutthereactionmechanism,viaalineartransformationofEq.(III10).
methodisshownbelow.
Fornonisothermalexperimentswithalinearheatingrate Eq.(III10)can
berewrittento:
. (III12)
IntegratingbothsidesoftheEq.(III12)leadstothefollowingequation:
(III13)
where and
areindependentof .Withtheseassumptions,Eq.(III13)canbeintegratedtogive
alogarithmicform:
(III14)
Then,Eq.(III14)isrewrittenas:
46
Ataconstantconversionrate( ),theplotof versus shouldbeastraight
line, whose slope can be used for calculation of the activation energy ( ).
Furthermore,thepreexponentialfactor( )canbedeterminedviatheordinate.
The advantages of the modelfree methods include: (1) kinetic data can be
the applicability of these models is limited to only a single process [135]. More
seriously, some problems with data manipulation may occur during the use of
simulatedcurve,andifcoupledwithasinglereactionmechanism,theobtainedfit
qualityispoor.
III.3.2.2 Globalkineticmodel
Aglobalkineticmodel(GKM)caneasilyovercomethelimitationofthemodel
freemethodbyproducingacalculatedcurvethatcanbeusedtocomparewiththe
experimentalcurvetoevaluatethefitquality.Inthismodel,Eq.(III10)isrewritten
asEq.(III16),inwhich representsthereactionorder.
. 1 (III16)
It generally assumes that the reactions in the pyrolysis stage are first order,
althoughnthreactionordercanalsobeused[129,136].Ontheotherhand,apower
law(nthorder)expressionisappliedforthecharcombustion,forwhichtheratelaw
isgenerallyrelatedtothepartialpressureofoxygenthroughanempiricalexponent
andthecharporosity.Duetoarelativelysmallamountofsampletestedinanair
flow in a TGA, it is reasonable to assume that the oxygen mass fraction remains
constantduringthereactionprocess.
Generally, the GKM consists of three 1st order reactions when it is applied for
pyrolysis modelling. On the order hand, for combustion kinetic study, GKM
47
requires three 1st order reactions for the devolatilization of the three biomass
componentsandonenthorderreactionforthecharcombustion.Inaddition,many
variations of GKM can be found in the literature. For a simpler calculation, the
numberofreactionscanbereduced.Inordertoimprovethefitquality,eitherthe
numberofpseudocomponentscanbeincreasedorpyrolysisreactionsareforcedto
benthorder.
The disadvantages of this model include [135]: (1) more kinetic constants
the best fit; and (2) more than one differential equation must be integrated at the
nowadays,astandardcommercialcomputercansolvethosealgorithmssmoothly.
III.3.2.3 Distributedactivationenergymodel
The above models assume that the activation energy is constant during the
involve a large number of different reacting species and the reactivity differences
aredescribedbydifferentactivationenergyvalues[137].Thesedifferencescanbe
takenintoaccountbyemployingthedistributedactivationenergymodel(DAEM)
was first proposed by Pitt [138] to study the kinetics of volatiles released during
coaldevolatilization.IntheDAEM,acomplexreactioncanbedescribedbyaseries
of firstorder reaction. The parallel first order reactions have different activation
developedbyBraunetal.[139].TheDAEMwasfirstappliedforbiomassligninby
Avni et al. [140]. Recently, this model was employed for kinetic study of various
biomassmaterials[116,137,141,142].AgeneralequationfortheDAEMisshown
below:
48
1 (III17)
where and are the volatile released at any time and in total, is the
distributionfunctionscanbeusedfor ,whichincludeGaussian,Weibull,and
modelling the pyrolysis and combustion of various biomass materials [116, 137,
142].Eq.(III18)showsacommonGaussianfunctionwithameanactivationvalue
( )andastandarddeviation( ):
1
(III18)
2 2
The DEAM offers an excellent fit between calculated and experimental data.
However, it requires testing the fuels with TGA at different heating programs,
which include linear, stepwise, modulated and constant reaction rate profiles. In
biomassisthat the model hasa doublelayer integral and a variable ( ) that goes
from zero to infinite, and cannot be calculated directly. Therefore, the data
recourses.It is reported that data processing for DAEM may take upto 10h on a
desktopcomputerequippedwitha3.4GHzIntelCorei7processorunderWindows
environment [137]. Such long processing time may limit the use of DAEM in
practicalsituations.
III.3.3 Thermogravimetricdatacollection
ThesolidbiomassfuelswerefirstgroundusinganIKAMF10cuttingmill.Then
the particles passing through a 125 m sieve (Fritsch Analysette 3 Pro) were
collected for the kinetic study to ensure the experiments to be in the chemical
49
reactionkineticregime[144,145].AMettlerToledoTGA/SDTA851ewasemployed
forthethermogravimetricstudy.ForeachTGArun,asampleamountofabout0.5
mg(forcombustionstudyinsyntheticairconsistingof21vol%oxygenand79vol%
nitrogen)or2mg(forpyrolysisstudyinnitrogen)wasspreadina150lalumina
pan located inside the TGA. It is worth noting that the buoyancy effect plays a
significantroleforsuchasmallsampleweight.Therefore,itismandatorytoruna
blank TG curve first. The weight change of the blank experiment was subtracted
from the experimental curves automatically. The experiment started from room
temperature,thefuelsamplewasheatedto105Candheldatthistemperaturefor
1 h for drying. Thereafter, the sample was heated to 700 C at a constant heating
rate of 10 C/min. A gas flow rate of 80 ml/min was applied for all experiments.
Moreover,threerepetitionswererunforeachfuelsample,andtheaveragekinetic
valuesarereported.
III.3.4 Dataprocessing
III.3.4.1 Modelselection
Asmentionedabove,biomassisacomplexmaterialandthebiomassconversion
combustion kinetics have indicated that, while some researchers tried extreme
simplifications,othersusedelaboratemechanismstoexplainverydetailed[25,110,
111].However,inkineticmodellingandsimulation,itisessentialtoselectakinetic
[133].Itisoflittleusetodevelopamodelwhichverycloselymirrorsrealitybutis
supported by a recent study [125], which has evaluated various pyrolysis kinetic
50
modelsforstumpbiomassfuelincludingthemodelfreemethod,onestepmodel,
models, DAEM offers the best fit quality but GKM is the optimal choice when
considering both fit quality and complexity. Based on the results and
recommendations from previous works, GKM with three and four pseudo
componentswereselectedforpyrolysisandcombustionmodelling,respectively,in
the kinetic study. It is because, among others, GKM offers reasonable fit quality,
andrequireslesscomputerresourcesthanDAEM.
III.3.4.2 Kineticevaluation
DatacollectedfromtheTGexperimentsshowtherelationshipbetweenmassloss
and temperature. They were first differentiated to obtain the DTG data, and
model corresponding to the selected physical model was then employed for
simulation and comparison with the experimental DTG data. The optimization of
the predicted DTG curves was based on the nonlinear least squares method
(NLSM), which minimize the sum of the square differences between the
experimental and calculated data. A protocol by Kemmer and Keller [146] and
MATLABcodeswereusedforthecurvefittingprocess.
shows the difference between the actual value and the value predicted by the
model.
(III19)
rates,respectively;andNisthenumberofexperimentalpoints.
51
Thefunctionneedstobeminimizedinordertoobtainthebestfit.Tovalidatethe
optimization or the curve fitting process, the fit quality between actual and
modelleddataiscalculatedaccordingtoEq.(III20)[130,131]:
% 1 . 100% (III20)
Theactualsimulationwasrununtilthemaximumfitvaluewasfound,atwhich
the convergence criteria of the optimization process are achieved. The extracted
kineticparametersare:theactivationenergies( ),thepreexponentialfactors( ),
combustion study, there are 12 kinetic parameters for the 1st order model and 16
parameters for the nth order model. In a pyrolysis study, there are only 9 kinetic
parametersforthe1stordermodeland12parametersforthenthordermodel.
52
ChapterIV
IV. CONCLUDINGSUMMARY
IV.1 Concludingsummary
IV.1.1 PaperIWettorrefactionofstemwoods
Inthiswork,WTofNorwayspruceandbirchwoodwasstudiedandcompared
withDT.Effectsofprocessparameters(temperature175225C,holdingtime:10
90min;pressure:15250bar;andfeedstockparticlesize:13cm)ontheyieldand
fuelpropertiesofsolidproductswereinvestigated.
EffecttrendssimilartothatofDThavebeenobserved.Theyieldofsolidproduct
is reduced with decreasing feedstock particle size. Both reaction temperature and
holdingtimehavesignificanteffectsonsolidproductyield,energyyield,andfuel
propertiesofwettorrefiedbiomass.Whentorrefactiontemperatureorholdingtime
isincreased,theproductandenergyyieldsofthetorrefiedsolidfuelsdecreasebut
the improvements in fuel properties of the solid products increase, which include
increasedfixedcarboncontents,greaterheatingvalues,betterhydrophobicityand
improved grindability. In addition, the consistent lower ash contents of the fuels
after WT suggest that WT can be employed to reduce the ash content of biomass
fuels.
53
Ontheotherhand,itappearsthatbirchwoodismorereactiveandproducesless
solid product than spruce wood, in the same WT conditions. Heating values of
birchwoodincreasefasterthansprucewoodwhentheseverityofWTisincreased.
pressureshigherthanthesaturatedvaporpressureofwateratagiventemperature.
control can avoid the energy penalty due to water vaporization. However,
pressuresthataretoohigharenotrecommended.
numerical predictions has shown that WT can produce solid fuels with a greater
HHV, higher energy yield, and better hydrophobicity at much lower temperature
and holding reaction time. The morphology study of the fuels produced by both
torrefaction methods were investigated and the wettorrefied fuel exhibits less
pronouncedchangesintheirstructurecomparedwiththedrytorrefiedfuel.
IV.1.2 PaperIICombustionreactivityofhydrochar
hydrochar produced from wood via WT, by looking at the effects of WT on the
combustion kinetics of woods. The woods, Norway spruce and birch, and
hydrocharproductsfromPaperIwerestudiedbymeansofaTGAoperatedinthe
order were adopted for the kinetic analysis. The models include three pseudo
components for the three main biomass components (hemicellulose, cellulose and
lignin) and one pseudocomponent for char produced during the devolatilization
stage.Thefollowingconclusionsweredrawnfromthisstudy:
woods.
54
WTtemperatureandholdingtimehavesimilareffectsonthecombustion
makes the woods more reactive in the devolatilization stage, but less
reactiveinthecharcombustionstage.However,toosevereWTconditions
(from 225C and 30min) make the trends reversed due to the
charcombustionstage.
n1showsthattheactivationenergyofhemicelluloseandcharisreduced,butthat
ofcelluloseisincreasedbyWT.Theactivationenergyofhemicellulosewasreduced
from103.8to44.8kJ/molforthesprucewood,andfrom144.7to41.3kJ/molforthe
birchwood.Thatofcharwasreducedfrom183.1to109.4kJ/molforthespruceand
from222.0to132.3kJ/molforthebirch.Theactivationenergyofthecellulosewas
increasedfrom221.5to239.0kJ/molforthespruce,andfrom204.7to236.7kJ/mol
forthebirch.ThemassfractionofhemicellulosewasreducedbyWT(from0.15to
0.05 for the spruce and from 0.23 to 0.06 for the birch), while that for char was
increasedgradually(from0.20to0.40forspruceandfrom0.14to0.34forbirch).
IV.1.3 PaperIIIPyrolysisreactivityofhydrochar
SimilartotheworkpresentedinPaperII,thisworkwascarriedoutinorderto
evaluate the pyrolysis reactivity of hydrochar produced from wood via WT, by
lookingattheeffectsofWTonthepyrolysiskineticsofwoods.Thewoods,Norway
spruceandbirch,andhydrocharproductsfromPaperIwerestudiedbymeansofa
withnthorderwasadoptedforthekineticanalysis.Inaddition,akineticevaluation
fordifferentmodelvariantsbyassumingcommonparameterswasalsoperformed
55
to identify possibilities for describing the thermal decomposition of different
biomassmaterialsbyacommonmodel.
Thestudyshowsthatwettorrefactionresultedinhigherpyrolysispeaksforthe
woods,butlessmassofvolatileswasreleasedduringpyrolysis.Theeffectsofwet
activationenergyofhemicellulosewassignificantlyreduced,from95.67kJ/molto
26.63 kJ/mol and 106.80 kJ/mol to 34.18 kJ/mol for the spruce and birch,
that for cellulose was slightly increased from 188.27 kJ/mol to 193.17 kJ/mol and
189.47 kJ/mol to 194.54 kJ/mol for the spruce and birch, respectively. The average
activation energy of lignin was also affected by wet torrefaction, being increased
from40.22kJ/molto48.09kJ/molforthespruceandfrom38.95to40.69kJ/molfor
thebirch.
performed.Theresultsconfirmthatsomekineticparameterscanbeassumedtobe
commonforpyrolysiskineticmodellingofdifferentbiomasseswithoutsubstantial
reductionsinthefitquality.Wettorrefactionhaspositiveeffectsonthepossibilities
forbiomasspyrolysiskineticmodelingwithassumptionofcommonparameters.
IV.1.4 PaperIVWettorrefactionofforestresidues
stemwoodsfromthePaperI.Theeffectsoftorrefactiontemperature(175,200,225
C) and holding time (10, 30, 60 min) on the yield and fuel properties of the
or holding time decreases the solid yield but enhances the fuel properties of the
56
grinding energy up to 16.0 times for the branches by WT are observed. The ash
contents in the hydrochars are lower than those in the untreated forest residues.
BirchbranchesaremorereactivethansprucebranchesinidenticalWTconditions.
Thecomparison onWT of thebranch and the stem woods show that the effect
trendsofWTontheyieldandfuelpropertiesofthehydrocharsfrombranchesand
stemsweresimilar.However,branchwoodsaremorereactivethanstemwoodsin
stemwoodsforspruce,butthatforbirchissomehowinconsistent.Improvements
inhydrophobicityofthebranchesaremorepronouncedthanthatofthestems.This
branchescomparedtostemwoods.
IV.1.5 PaperVEffectsofcarbondioxideonwettorrefaction
ThisstudyaimedtoidentifyopportunitiesandgainknowledgeforWTprocess
integration,consideringthathotfluegasfromthermalpowerplantscanbeutilized
for WT continuous processes at industrial scales to reduce the cost. The problem
however is that, apart from N2, flue gas contains other gases, of which CO2 is the
main species and may have important effects on the WT process and the fuel
propertiesofthesolidproduct.Forthispurpose,WTofforestresiduesindifferent
conditions (temperature: 175, 200, 225 C; holding time: 10, 30, 60 min) and two
atmospheres(N2andCO2)wereexperimentallyinvestigated.
The results show that WT in CO2 produced 4.66.0% less solid product with
decreasedheatingvaluebutimprovedhydrophobicityandbettergrindabilitythan
thatinN2.Anincreaseofupto1.4%inEMCandareductionof6.5kWh/tinSGE
wereobservedforthesolidproductobtainedfromWTinCO2,comparedwiththat
in N2, in an identical condition of 200 C and for 30 min. The proximate analyses
show higher fixed carbon and lower volatile matter contents for the hydrochars
57
obtained from WT in CO2. Additionally, the ash content of these products is
capable ofremoving even more ash elements in the solid biomass fuel, compared
withWTinN2.
IV.1.6 PaperVIPelletabilityandpelletpropertiesofhydrochar
Finally,pelletabilityandpelletpropertiesofthehydrocharfromforestresidues
werestudiedandpresentedinthispaper.Thepelletizationwasperformedusinga
single pellet press for both raw and wettorrefied forest residues. The pellet
strengthwastheninvestigatedviadiametriccompressiontests,employinga60mm
diameterprobeconnectedtoaLloydLR5Ktextureanalyzer.
The results show that the pellets made from wettorrefied forest residues are
more compressible and mechanically stronger than the pellets made from raw
behaviors of lignin below and above its glass transition temperature. In identical
condition,birchpelletsaredenserthansprucepelletsandtheeffectoftorrefaction
temperatureismorepronouncedforbirchthanspruce.Increasesindensityforthe
hydrocharpelletscomparedwiththepelletsmadefromrawmaterialsisupto159
kg/m3forspruceand213kg/m3forbirch.Improvementsinthestrengthoftorrefied
pellet compared with raw pellet are up to 3.4 and 2.7 times for spruce and birch,
strength of the pellets. Moreover, compression strength and density of the pellets
arecorrelatedfollowingapowerlawtrend.Belowthedensityof1000kg/m3,large
increases in density results in only small increases in the strength. However, this
relationshipwasreversedwhenthedensitywashigherthan1000kg/m3.
58
IV.2 Recommendationforfurtherworks
WTofagriculturalwastesandaquaticenergycropssuchasalgalbiomass.
DetailedstudiesonaqueousandgaseousproductsfromWT.
DetailedstudiesonremovalofashelementsofbiomassduringWT.
GasificationreactivityandkineticsofhydrocharobtainedfromWT.
pelletsindroptubefurnaces.
ContinuousprocessesforWT,processoptimizationandintegration.
AcomparativestudyonthetechnoeconomicsofWTandDTprocesses.
59
60
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72
CollectionofPapers
73
PaperI
Comparativeassessmentofwettorrefaction
QuangVuBach,KhanhQuangTran,RogerA.Khalil,yvindSkreiberg,and
GulaimSeisenbaeva.
Energy&Fuels2013,27,67436753.
Article
pubs.acs.org/EF
Department of Energy and Process Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim,
Norway
ABSTRACT: Wet torrefaction of typical Norwegian biomass fuels was studied within the temperature window of 175225 C,
using a benchtop autoclave reactor of 250 mL in volume from Parr Instrument. Two types of local biomass fuels were employed
as feedstock, Norway spruce (softwood) and birch (hardwood). Eects of process parameters including pressure, reaction
temperature, holding time, and feedstock particle size on the yield and properties of the solid products were investigated. It
appears that birch wood is more reactive and produces less solid products than spruce wood in the same wet torrefaction
conditions. Increasing pressure above the saturated vapor pressure of water enhances the torrefaction rate. Both reaction
temperature and holding time have signicant eects on solid product yield and fuel properties of wet torreed biomass. The
yield of solid products is slightly reduced with decreasing feedstock particle size. The ash content of biomass fuel is signicantly
reduced by wet torrefaction. In addition, a comparison between wet and dry torrefaction supported by regression analyses and
numerical predictions shows that wet torrefaction can produce solid fuels with greater heating values at much lower temperatures
and shorter holding times.
2013 American Chemical Society 6743 dx.doi.org/10.1021/ef401295w | Energy Fuels 2013, 27, 67436753
Energy & Fuels Article
Table 1. Proximate and Ultimate Analyses for the Feedstock (Dry Basis)
proximate analysis ultimate analysis
type of biomass asha VMa xed Ca Ca Ha Oa Na Sa HHVb
Norway spruce 0.23 86.50 13.27 50.31 6.24 43.38 0.07 <0.02 19.94
Norway birch 0.28 89.46 10.26 48.94 6.35 44.60 0.11 <0.02 20.42
a
wt %. bMJ/kg, ash free.
therefore likely that the rst commercial torrefaction plant will which may increase the investment cost. However, several
be designed for relatively high quality biomass sources. studies for a process similar to WT can be found in the
Torrefaction of agricultural residues and biomass wastes, literature under the terminology of hydrothermal carbon-
especially wet biomass, will be more complicated due to the ization (HTC).4547 These studies can be benecial and
technical challenges related to the air emissions from the complementary to further research and development in WT of
process, product quality and exibility, product quality control, biomass for energy applications. Nevertheless, it should be
heat integration, and feedstock properties variations.34,35 mentioned that, although the terminologies of WT and HTC
WT of biomass has also been studied for the energy have been sometimes used interchangeably, there is a signicant
applications (combustion, gasication, and pyrolysis) with a dierence between them. While WT processes aim at
focus on using biomass wastes as feedstock, which include producing upgraded solid fuels for energy applications only,
sewage sludge36 and wet agricultural wastes such as cow and HTC processes are employed mainly for producing charcoal,
swine manure.37,38 Due to the fact that WT processes employ with a high carbon content, which can be used not only as fuel
water in subcritical conditions as reaction media, the energy but also as activated carbon, soil enhancer, fertilizer, etc.
intensive predrying for the feedstock is eliminated. After WT, Clearly, energy eciency is more critical for the WT process
similar to DT, a hydrophobic solid fuel is also obtained and can than for the HTC, and thus the former tends to be performed
be eectively made dry by mechanical and/or natural at relatively lower temperatures than the latter.
dewatering, an attractive option capable of dramatically In this present work, WT of Norwegian biomass fuels was
reducing the energy requirement for the postdrying step.39 experimentally studied. Eects of process parameters such as
Other potential advantages of WT include the ease of pressure, temperature, holding time, and particle size of the
pelletization, where wet torreed biomass does not require feedstock on the products yield and fuel properties of the solid
water addition in order to improve the pelletability and binding product were investigated. Two types of woody biomass,
capacity as in the case for DT.40,41 The yield and the fuel Norway spruce (softwood) and birch (hardwood), were
quality of solid products obtained from WT are reported to be selected as feedstock. In addition, numerical analyses using a
even better than that from DT.19 At 200 C, for example, WT regression approach were employed to support a comparison
of loblolly pine can give a mass yield as high as 88.7%, and 95% between wet and dry torrefaction.
for the energy yield, compared to 83.8% and 89.7% respectively
for DT at 250 C with the same feedstock type and holding 2. MATERIALS AND METHODS
time.19 Furthermore, apart from the solid fuel product, some 2.1. Materials. Stem wood from Norway spruce (softwood) and
water, CO2, small amounts of CO, H2, some hydrocarbons, and birch (hardwood) were selected as feedstock for the present study
dissolved organic and inorganic compounds are released from since they are the main wood species in Norwegian forests. The
biomass during WT.39 The fact that WT is capable of dissolving selection aims among others to utilize the results from a previous study
and thus washing out the inorganic components from solid of DT,26 recently published by our research group, for a comparison
between wet and dry torrefaction. The wood samples were obtained
biomass fuels is an additional advantage of WT over DT since it from a local supplier in Trondheim, Norway. Proximate analyses of the
produces cleaner solid fuels, with respect to inorganic feedstock were performed according to ASTM standards: ASTM
content, which are more suitable for combustion and E871, ASTM E872, and ASTM D1102 for moisture content, volatile
gasication processes. On the other hand, many valuable matter, and ash content, respectively. Ultimate analyses of the fuels on
organic compounds, including acetic acid, formic acid, lactic dry basis were determined by an EA 1108 CHNS-O elemental
acid, glycolic acid, levulinic acid, phenol, furfural, HMF, and analyzer (Carlo Erba Instruments). In addition, the higher heating
sugars are found in the aqueous phase products of WT, making value (HHV) was calculated according to a unied correlation
up approximately 10% by mass of the feedstock.19,20 The proposed by Channiwala et al.11 Results from the ultimate, proximate
potential use of these water-soluble organic fractions for analyses and the HHVs of the feedstocks are given in Table 1.
2.2. Experimental Setup and Procedure. In this study, WT
production of valuable products may contribute to further experiments were carried out in a 250 mL Parr reactor model 4651,
improving the economy of the WT process. which is made of stainless steel (T316SS) and equipped with a
Despite the various advantages of WT over DT, only a few benchtop ceramic heater (4923EE), a temperature controller
studies on WT have been reported.19,20 This may be due to the (4838EE), a pressure gauge, and two valves. A thermocouple for
inherent disadvantages of WT, as a method for biofuel monitoring the reaction temperature (temperature of water in the
processing in hydrothermal media,4244 which include the reactor) is connected to the controller by which the electrical duty of
engineering challenges of reactor material corrosion, precip- the heater is controlled. The thermocouple is introduced into the
itation and deposition of inorganic salts released during WT reactor via a thermo-well, which is cast in the reactor head. In addition,
process of biomass, and handling of aqueous residues produced a self-made detachable perforated glass plate is mounted to the
thermo-well in order to keep the feedstock entirely submerged in the
from WT. As WT is operated at elevated pressures, continuous water. The reactor is connected to a nitrogen (99.99% purity) cylinder
production could be an additional challenge, e.g., a high via a valve.
pressure feeding system is required. Corrosion resistant Distilled water was used as the reaction media. The ratio of dry
material capable of standing at elevated pressures and feedstock over water was 1:5 by weight. However, for studying the
temperatures must be used for building the WT reactor eect of pressure, a ratio of 1:10 was employed with the feedstock
prepared in powder form of 0.51 mm to minimize the eects of heat adopt and answer this question for WT. In one method, the power
and mass transfer limitations during torrefaction process. For studying consumption of the mill during operation is recorded and regarded as
the eects of feedstock particle size on the process and products, the the energy required for grinding of the biomass fuel. The grinding
feedstock was cut into cubes with 1 and 3 cm sides (hereafter called 1 energy of native and torreed biomass fuels are normalized to their
and 3 cm cube, respectively). All of the experiments were duplicated, total ground mass, and then compared.9,10 This method gives a
from which data were collected and processed to generate average comparative measurement of the energy requirement, with no control
values for relevant assessments. over the particle size distribution of the samples. Therefore, the
Before every torrefaction run, the furnace (the heater) without the particle size distribution should be analyzed in a separate step. The
reactor was heated for 30 min to a preset temperature. At the same second method estimates the grindability by measuring the portion of
time, the reactor was loaded, closed, sealed, and purged with materials passing through a 75 m sieve and comparing it with that of
compressed nitrogen gas for 10 min. Then the reactor was pressurized standard coals.29,49 This method can show how ne the fuel particles
and placed in the preheated furnace which was set to the maximum are, but it does not explicitly show the grinding energy. More recently,
power, giving a heating rate of approximately 12 C/min. The holding a multistage assessment similar to the second method has been
time was counted from the time at which the reactor temperature reported by Tran et al.50 In this study, the quantity of comparison is
reached the preset temperature to the end point when the reactor was the total grinding time summed up from the grinding times recorded
replaced from the furnace and submerged in a water bath lled with from multiple stages of grindings and sieving of the same mass for
tap water for cooling. When the reactor cooled to room temperature, dierent materials until the whole mass goes through a 1.4 mm sieve.
the pressure was gradually released and the reactor was opened for It appears that the aforementioned methods have their pros and
products collection. cons. However, there is no better method for this purpose so far. For
In this study, only products in the solid and liquid phases were this present study, the rst method has been adopted for a quantitative
collected. They were separated from each other by ltration using a estimation of the specic grinding energy for raw and wet torreed
lter paper with a pore size of 512 m. After separation the collected biomass. An IKA MF 10 cutting mill (from IKA-Werke GmbH & Co.
solids were dried at 105 C for 48 h and then balanced. Readings from KG) equipped with a 1 mm bottom sieve was used. An analog current
the balance were tabulated as the mass of solid product from the WT. input module NI 9203 (from National Instruments Corporation) was
The dried solids were then stored in a desiccator lled with silica gel employed to record the electrical current during grinding. Samples of 1
for further studies. cm cubes were used for the assessment. A LabView program was used
2.3. Assessment Methods. 2.3.1. Method for Assessment of for the data acquisition and the calculation of the energy consumption
Hydrophobicity. To our present knowledge, there exists no standard which was logged to a le every 2 s. The power of the mill under no-
method for assessment the hydrophobicity of torreed biomass fuels. load conditions was measured and subtracted from the power of
Researchers have had to develop or adopt methods on their own for grinding the biomass samples. The grinding energy was determined by
such investigations. Pimchuai et al.4 and Tapasvi et al.26 immersed the integrating the power curve during the grinding period. Finally, the
fuel samples in water for 2 h, while Bergman et al.5 soaked torreed data was normalized to the initial sample weight.
pellets in water for up to 15 h and then compared the dierences in 2.3.3. Numerical Approach for Comparison between Wet and
water uptake level. Yan et al.19 measured the equilibrium moisture Dry Torrefaction. Due to the dierences in working pressure, it is not
content (EMC) of the fuels in various conditions diering in relative straightforward to directly compare wet and dry torrefaction of
humidity. Li et al.6 and Lam et al.48 measured the moisture absorption biomass. Multiple regression analysis method was therefore employed
rates of the fuels using a controlled humidity chamber. to numerically assess and establish relevant mathematical models
It is important to highlight that solid biomass fuels, especially based on the data collected from the WT experiments. The models
biochar obtained from woody biomass torrefaction, are porous were then used to predict the operation points for WT comparable
materials. The porosity of tested materials may signicantly interfere with DT, on the basis of a common solid product yield, for a
with the hydrophobicity test results, considering the fact the water may comparison of the heating value, grindability, and hydrophobicity. The
be up-taken by the pores as well. Therefore, size reduction for the solid product yield (Ysolid) is dened and determined according to eq 2
materials to be tested is necessary in order to minimize the mtorrefied solid product
interference. For this reason the method of exposing tested materials Ysolid(%) = 100%
in the powder form to water vapor in a climatic chamber, similar to the m initial dry biomass (2)
method employed by Li et al.,6 has been adopted for this present
study. For each test, an amount of approximately 2 g of the material to where the term of mtorrefied solid product means the mass of solid product
be tested is rst ground manually in an agate mortar and screened and the mass of initial dry biomass is for the term of minitial dry biomass.
through a sieve (Fritsch Analysette 3 Pro) to obtain the sample Multiple regression analysis is a useful tool for simulating
powder with particles smaller than 250 m. The powder is then dried experimental data. It was successfully applied and reported for both
at 105 C for 24 h. Next, the dried powder is spread on a glass Petri DT24 and hydrothermal treatment51 of biomass. The general form of
dish, which is then placed in a climatic chamber (series VC3 0100 of the multiple regression model adopted for the present work is given in
Votsch Industrietechnik) operated under the controlled conditions of eq 3
20 C and 90% relative humidity. The mass changes by time due the Y = 0 + 1X1 + 2X 2 + ... + pX p + (3)
moisture up-take of the tested material are recorded every 24 h for the
total test period of 1 week. The moisture content of the tested material where Y is the dependent variable; X1, X2, ..., Xp are the process or
is then calculated according to eq 1 independent variables; 0, 1, 2, ..., p are constants to be determined
mi m0 from experimental data; and is the noise or error observed in the
MCi(%) = 100%, i = 1, 2, ..., 7 variable Y.
m0 (1)
where MCi is the moisture content of the tested material on the ith 3. RESULTS AND DISCUSSION
day; m0 and mi are the mass of the sample before the test and 3.1. Eects of Process Parameters on Solid Product
measured on the ith day, respectively. Yield. 3.1.1. Eects of Pressure. For this investigation only the
2.3.2. Quantitative Assessment of Grinding Energy Saving Due spruce sample was used as feedstock, with a biomass/water
to Grindability Improvement by Torrefaction. It is widely recognized
that torrefaction improves the grindability of biomass fuels, which ratio of 1:10 by weight. In order to minimize possible eects of
consequently helps reduce energy requirement for the fuel heat and mass transfer limitations in this investigation,
communition. However, a practical question of how much grinding feedstock in powder form with particle size of 0.51 mm was
energy that can be saved has not been suciently addressed. There are used. The experiments were performed in the common
two methods reported in the literature, which can be considered to conditions of 200 C as torrefaction temperature and 10 min
6745 dx.doi.org/10.1021/ef401295w | Energy Fuels 2013, 27, 67436753
Energy & Fuels Article
as holding time. Four dierent pressures were investigated, reaction rate, as well as to reduce the energy loss in the form of
including 15.54 (the saturated vapor pressure of water at 200 latent vaporization heat. The slightly longer heating time
C), 70, 160, and 250 bar. Results from this investigation are (reduced heat transfer) at 250 bar compared to that at 70160
shown in Figure 1. bar might be due to experimental and measurement
uncertainty.
More interestingly, it is also observed from Figure 1 that the
reduction in solid yield or the increase in reaction rate in other
words becomes less pronounced at pressures higher than 160
bar. This indicates that the observed reaction rate enhance-
ments in subcritical water conditions upon increasing pressure
have probably been caused mainly by the increase of the water
portion present in the liquid phase, rather than by the improved
thermal conductivity of the system. Nevertheless, the improved
thermal conductivity does help shorten the heating time and
thus reduce the energy requirement of the process.
By considering the energy requirement for vaporization of
water at a temperature within the WT temperature window
(180260 C approximately), in combination with the
observations from this investigation, it is suggested that WT
of biomass for energy application should be carried out at
pressures higher than the saturated vapor pressures. In such
conditions, the potential energy penalty by phase trans-
Figure 1. Eects of pressure on solid product yield for WT of spruce formation of water in the form of latent heat can be minimized
at 200 C for 10 min.
and the reaction rate can be enhanced. However, it is not
advisable to perform WT at pressures much higher than the
As can be seen from Figure 1, pressure has a weak eect on saturated vapor pressures of water, since further increases in
the solid yield of WT. When pressure increases from 15.54 to reaction rate are less signicant. In addition, the higher the
250 bar the yield decreases from 76.4% to 73.1%. This indicates pressure, the more energy and more investment for the reactor
that the reaction rate increases with increasing pressure. In the are required. For these reasons, the pressure of 70 bar has been
rst instance, this eect can be due to the increase in thermal selected for other investigations in this present work.
conductivity of water with increasing pressure.52 Another 3.1.2. Eects of Torrefaction Temperature and Holding
possible reason for this reduction in solid yield may be related Time. For the experiments reported in this section feedstock of
to the acidity change of subcritical water with increasing 1 cm3 cubes as particle size were used. The eects of
pressure due to the acid hydrolysis of hemicellulose and torrefaction temperature on solid yield was investigated for
cellulose.21,53 In addition, this can also be attributed to the fact the constant holding time of 30 min, whereas a reaction
that in subcritical conditions water exists in both liquid and gas temperature of 200 C was kept unchanged for the
phases. However, more water would remain in the liquid phase investigation of holding time. Figure 2 presents the eects of
at pressures higher than the saturated vapor pressure, torrefaction temperature (Figure 2A) and holding time (Figure
considering Le Chateliers principle. Since the feedstock is 2B) on the yield of solid products from WT of the spruce and
solid biomass immerged in the liquid, water in the gas phase is birch wood samples.
not in direct contact with the feedstock and thus more liquid As can be seen from Figure 2, similar trends are observed for
water would improve the reaction rate as well. This is also in the eects of torrefaction temperature and holding time on the
agreement with observations reported in the literature showing solid product yield. When reaction temperature or holding time
that the reaction rate increases with decreasing ratios of increases, the yield decreases. However, the eect of temper-
feedstock over water.5456 Furthermore, the thermal con- ature is more pronounced than that of holding time within the
ductivity of water in the liquid phase is obviously higher than in tested conditions. When temperature is increased from 175 to
the gas phase, which in turn would result in better heat transfer 225 C the solid product yield decreases from 88.3 to 69.7%
in the reactor and thus higher reaction rates. The improved and from 79.5 to 58.0% for spruce and birch, respectively.
heat transfer in the system can also be observed from the Similarly, when holding time is increased from 10 to 60 min the
heating time dened as time needed for heating the reactants solid product yield decreases from 82.5 to 73.3% for spruce and
(water and biomass) from 25 to 200 C, which is also from 66.4 to 63.1% for birch.
presented in Figure 1. It appears that the heating time decreases The dierence in eect of temperature and holding time on
dramatically from 18.5 to 10.9 min when pressure increases the solid product yield can be explained by the theory of
from the saturated vapor pressure of water at 200 C (15.54 chemical reaction kinetics. In general, for a thermal
bar) to 18 and then 70 bar. However, no signicant change in decomposition reaction of reactant C, the rate law can be
heating time is observed when pressure is increased further. At written as dC/dt = k[C], where [C] is concentration of the
250 bar the heating time even turns up to 11.4 min, being reactant and k is the reaction rate constant. The rate constant k
slightly longer than that at 70 and 160 bar. From these virtually obeys Arrhenius law k = AeE/(RT), where A is a pre-
observations, it is reasonable to believe that in the conditions of exponential factor, E is the activation energy, R is the gas
200 C and 70 bar most of the water in the reactor is in the constant, and T is the absolute temperature. This Arrhenius
liquid phase. From this point, further increases in pressure is equation indicates that the rate constant, and thus the reaction
not useful with respect to preventing water from vaporization, rate, is exponentially proportional to the reaction temperature.
which aims to improve the heat transfer in the system and the On the other hand, the reaction rate is just directly proportional
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Energy & Fuels Article
Figure 2. Eects of temperature (A) and holding time (B) on the solid Table 2. Proximate Analysis of Torreed Spruce and Birch
product yield. Wood
to the reaction (holding) time. That is the reason why spruce wood birch wood
temperature has more signicant eects on solid yield than torrefaction
holding time. condition asha VMa xed Ca asha VMa xed Ca
Figure 2 also indicates that birch wood is more reactive than raw 0.23 86.50 13.27 0.28 89.46 10.26
spruce wood, which can be attributed to the fact that birch is a 1 cm, 175 C, 0.11 85.72 14.17 0.09 88.57 11.34
hardwood generally containing more hemicellulose than 30 min
1 cm, 175 C, 0.09 85.42 14.49 0.08 87.75 12.17
softwood.57 It is known that, during hydrothermal treatment, 60 min
hemicellulose starts to degrade rst among the three main 1 cm, 175 C, 0.10 84.82 15.08 0.07 87.22 12.71
components of lignocellulosic materials.21,58 Moreover, hemi- 90 min
celluloses of hardwood contains even more xylan than that of 1 cm, 200 C, 0.14 84.64 15.22 0.08 87.97 11.94
softwood, 15 which is the most reactive hemicellulosic 10 min
compound within the torrefaction temperature window. 1 cm, 200 C, 0.12 83.92 15.95 0.09 85.15 14.76
30 min
3.1.3. Eects of Feedstock Particle Size. The eect of
1 cm, 200 C, 0.09 81.87 18.03 0.10 82.64 17.27
feedstock particle size on the yield of solid products from WT 60 min
for the spruce sample was studied in the conditions of 225 C 1 cm, 225 C, 0.14 78.58 21.28 0.09 80.32 19.59
as torrefaction temperature, and 10 or 30 min as holding time, 10 min
using feedstock of 1 and 3 cm cubes. Results from these 1 cm, 225 C, 0.14 74.74 25.12 0.13 73.78 26.09
experiments are presented in Figure 3, showing that the yield of 30 min
solid products slightly decreases with decreasing feedstock 3 cm, 225 C, 0.20 77.56 22.25 0.13 77.71 22.16
10 min
particle size. In addition, the solid yield reduction caused by 3 cm, 225 C, 0.20 72.66 27.14 0.15 72.34 27.50
decreasing feedstock particle size becomes less pronounced 30 min
when the holding time is increased from 10 to 30 min. This
a
indicates that the eects of feedstock particle size can basically wt %, dry basis.
3.2.3. Eects of Process Parameters on the Heating Value. from WT, Yenergy(%), dened in the same way as for DT was
HHVs of wet torreed biomass were calculated on the basis of determined according to eqs 4 and 5:
the ultimate analysis data presented in Table 3. Figure 5 shows
Yenergy(%) = YsolidDenergy (4)
HHVtorrefied solid product
Denergy =
HHVinitial dry biomass (5)
where the term of HHVtorrefied solid product denotes the HHV of
the solid product, the HHV of initial dry biomass is the term of
HHVinitial dry biamass, and Ysolid has been dened earlier in section
2.3.3.
Figure 6 demonstrates the eects of torrefaction temperature
and holding time on the energy yield of the solids obtained
eect of holding time on the energy yield is not as pronounced increasing torrefaction temperature or holding time. The
as the eect of temperature. The energy yield decreases reduction in moisture uptake or the increase in hydrophobicity
observed when temperature is increased from 175 to 225 C of torreed biomass is the result from the breakdown and
are signicant, being from 89.1 to 80.0% and from 81.1 to removal of hydroxyl groups in the wood cell wall components
59.1% for spruce and birch, respectively. When holding time is during the pretreatment.59 The devastation strongly depends
increased from 10 to 60 min the energy yield decreases from on the severity of the torrefaction condition, therefore, the
85.1 to 78.7% for spruce, and from 67.7 to 64.3% for birch. In hydrophobicity of the torreed fuel increases or the moisture
addition, it can be observed from Figure 6A that when uptake decreases with increasing of treatment temperature and
temperature is increased from 175 to 225 C the dierences in holding time. The results are in good agreement with other
energy yield between spruce and birch are enlarging from 8.0% studies.4,5,19 However, the eect of feedstock particles size on
to 20.8%. This is similar to the observation of the temperature- the hydrophobicity of torreed fuels is not pronounced. Similar
sensitive dierences in solid product yield discussed in section trends were also observed in the case of birch wood.
3.1.2. 3.2.6. Eects of Process Parameters on the Grindability. As
3.2.5. Eects of Process Parameters on the Hydro- presented earlier in section 2.3.2, a quantitative assessment of
phobicity. Figure 7 represents results from the tests of grinding energy savings due to improvement in grindability of
biomass fuel via torrefaction was performed for this present
study through a measurement campaign of the specic grinding
energy (SGE) required for fuel communition. Results from this
campaign are presented in Figure 8, which show the inuences
of reaction temperature (Figure 8A) and holding time (Figure
8B) on the SGE of wet torreed spruce and birch in dierent
conditions.
By examining qualitatively the data in Figure 8, panels A and 220, 216, and 210 C, respectively. From these two sets of
B, one can observe that the grindability of both spruce and torrefaction temperature and corresponding holding time, the
birch is improved when either torrefaction temperature or HHV of the solid products can be predicted using the HHV
holding time increases. Also, torrefaction temperature has model (eq 7). Results from these predictions are summarized in
stronger eects on the grindability than holding time. In Table 5, which indicate that in all cases the HHV of solid fuels
addition, temperature appears to have stronger eects on the
grindability of birch than spruce. Table 5. Predicted Results for WT of Norway Spruce with a
The most signicant reduction in SGE is observed for the Solid Yield of 74%
samples torreed at 225 C for 30 min, being the most severe
tempa holding timeb increase in HHVc energy yieldc
torrefaction among the tested conditions. The reduction is by a
factor of 18.3 for spruce and 25.6 for birch, compared with the 222 5 9.4 80.96
raw materials. However, the biomass torreed at 175 and 200 220 10 9.3 80.88
C shows only a small decrease in specic grinding energy 216 20 8.9 80.59
consumption. 210 30 8.5 80.29
a
Units in C. bUnits in min. cUnits in %.
4. COMPARISON WITH DRY TORREFACTION
As discussed in section 2.3.3, a regression model has been obtained from WT is always higher than that from DT. The
adopted to support a comparison between wet and dry dierences are signicant, varying from 9 to 21% of the increase
torrefaction. By implementing a regression analysis in MS in HHV compared with the case of DT (7.8%). Having greater
Excel, using the general model (eq 3) and the experimental data increases in HHV for the same product yield, the predicted
obtained from the WT experiments of the present work, three cases of WT obviously have higher energy yields than the DT.
second-order polynomial models were generated for two In addition, the torrefaction temperature is much lower, and the
dependent variables (temperature and holding time): the holding time is much shorter for WT than DT.
solid yield Ysolid (eq 6), the higher heating value HHV (eq 7), Two extra WT experiments, 222 C for 5 min and 210 C for
and the specic grinding energy SGE (eq 8). 30 min, were carried out to validate the predictions and thus
the comparison. Results from these experiments are presented
Ysolid(%) = 205.83 0.70T 0.99t + 0.01T 2 in Table 6, which includes the data of the DT experiment used
+ 3.36 103Tt + 2.44 103t 2 (6) for the comparison. From Table 6 it can be seen that the actual
solid yields, increases in HHV, and energy yields are in good
3 2 agreement with the predictions.
HHV(MJ/kg) = 38.54 0.24T 0.04t + 0.73 10 T
To compare the eects of two dierent torrefaction methods
6.24 105Tt 1.69 104t 2 (7) on the structure of the fuels, the morphology of raw spruce,
both wet and dry torreed spruce samples having the same
SGE(kWh /t ) = 1038.19 + 14.55T + 2.43t 0.04T 2 solid yield, was examined by means of a Hitachi TM-1000
0.02Tt + 0.01t 2 (8) scanning electron microscopy (SEM) equipped with an energy
dispersive X-ray spectroscopy (EDX). The EDX was employed
where, T and t represent torrefaction temperature and holding for the elemental analysis of the surface layer with 1 m depth.
time, respectively. The quality of the regression analysis (with a The SEM images (not shown) indicate that the openings and
condence interval of 95%) and the standard deviations () of long fractures occur on the surface of the torreed particles,
these models are summarized in Table 4. which is not the case for the raw material. These changes in
structure are believably caused by the release of gaseous
Table 4. Quality of the Regression Analysis (Condence products during the torrefaction. However, the changes for the
Interval = 0.95) dry torreed sample appear more pronounced than for the wet
summary model of eq 6 model of eq 7 model of eq 8 torreed sample. This observation is reasonable, considering
statistics Ysolid HHV SGE that, for the same solid yield, the DT was carried out at a higher
R2 0.994 0.998 0.962 temperature (275 C) than the WT experiments (at 225 C).
R2 adjusted 0.986 0.996 0.866 In addition, results from the EDX analysis presented in Figure 9
standard 1.541 0.208 22.249 conrm that the content of potassium and calcium in wet
deviation torreed fuel are signicantly lower than that in raw and dry
torreed fuels. It should be noted that the normalized data are
For the comparison, selected data from a previous study26 on showing relative amounts of the elements in the quite low
DT of Norway spruce wood (from the same source as for this content of inorganic constituents in the wood. Changes in
present study) was utilized, being a solid yield of 74% and an content of other elements are not pronounced. These results
increase in HHV of 7.8% (compared with the untreated conrm the possibility to reduce the ash content of fuel by WT.
sample). These data were obtained from the DT conditions of However, further studies focusing on this direction are needed.
275 C and for 60 min. The use of the HHV data in increasing In addition, the SGE for the spruce samples torreed by
percent for the comparison aims to eliminate possible either method, WT or DT, is compared to each other on the
interferences which may be caused by the slight dierences in basis of the same solid product yield. For this comparison, the
fuel characterization of the two studies, though the samples SGE of the dry torreed fuel is extracted from the previous
were from the same source. Using the solid yield model (eq 6) work,26 and those for the wet torreed fuels are calculated using
to search for torrefaction temperatures, at which WT of the eq 8. The obtained SGE data are summarized in Table 6.
spruce sample can produce the same solid yield of 74% with a Interestingly, despite having the same solid yield and greater
holding time of 5, 10, 20, and 30 min give the results of 222, heating values, wet torreed fuels exhibit slightly higher SGE
6751 dx.doi.org/10.1021/ef401295w | Energy Fuels 2013, 27, 67436753
Energy & Fuels Article
wet torreed fuels uptake less water than the dry torreed fuel,
despite the fact that the dry torreed sample was treated at a
much higher temperature and for a longer residence time.
5. CONCLUSIONS
Wet torrefaction of Norway spruce and birch wood has been
studied and compared with dry torrefaction. Eects of process
parameters on the yield and fuel properties of solid products
have been investigated. Eect trends similar to that of DT have
been observed. The yield of solid product is reduced with
decreasing feedstock particle size. Both reaction temperature
and holding time have signicant eects on solid product yield,
energy yield, and fuel properties of wet torreed biomass.
When torrefaction temperature or holding time is increased, the
product and energy yields of the torreed solid fuels decrease
but the improvements in fuel properties of the solid products
increase, which include increased xed carbon contents, greater
heating values, better hydrophobicity and improved grind-
Figure 9. X-ray elemental analysis for main elements in spruce
torreed by DT and WT.
ability. In addition, the consistent lower ash contents of the
fuels after WT suggest that WT can be employed to reduce ash
content of biomass fuels.
values compared with the dry torreed fuel. Table 6 indicates On the other hand, it appears that birch wood is more
that temperature is a major parameter in reduction of SGE for reactive and produces less solid products than spruce wood, in
torreed fuel, i.e., higher torrefaction temperature reduces the same WT conditions. Heating values of birch wood increase
grinding energy. However, it should be kept in mind that the faster than spruce wood when the severity of WT is increased.
DT conditions (275 C and 30 min) may require more energy The investigation of pressure eects suggests that WT should
than the WT conditions (210 C and 30 min or 222 C and 5 be carried out at pressures higher than the saturated vapor
min). pressure of water at a given temperature. It is because the rate
Furthermore, the moisture uptake of the wet torreed of WT is enhanced by pressure. In addition, this pressure
biomass was also tested using the same method adopted in this control can help avoid the energy penalty due to water
present study for a comparison with WT. Data collected from vaporization. However, pressures that are too high are not
the test are presented in Figure 10, which clearly show that the recommended.
The comparison between WT and DT supported by
regression analyses and numerical predictions has shown that
WT can produce solid fuels with a greater HHV, higher energy
yield, and better hydrophobicity at much lower temperature
and holding reaction time. The morphology analyses of the
fuels produced by both torrefaction methods were investigated
and the wet torreed fuel exhibits less pronounced changes in
their structure compared with the dry torreed fuel.
AUTHOR INFORMATION
Corresponding Author
*E-mail: quang.vu.bach@ntnu.no. Tel.: +47 73591645. Fax:
+47 73593580.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This work is nancially supported by the Research Council of
Norway and industry partners through the KMB project STOP
Figure 10. Moisture uptake behavior of spruce biomass torreed by (STable OPerating conditions for biomass combustion plants),
dierent methods. which is gratefully acknowledged.
6752 dx.doi.org/10.1021/ef401295w | Energy Fuels 2013, 27, 67436753
Energy & Fuels
Article
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2008, 87, 844856. 4A was updated. The revised paper was reposted on November
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PaperII
Effectsofwettorrefactiononreactivityandkineticsofwood
inaircombustion
QuangVuBach,KhanhQuangTran,yvindSkreiberg,RogerA.Khalil,and
AnhN.Phan.
Fuel2014,137,375383.
Fuel 137 (2014) 375383
Fuel
journal homepage: www.elsevier.com/locate/fuel
h i g h l i g h t s
Torrefaction temperature and holding time signicantly inuence the combustion reactivity and kinetics of woody biomass.
The effect of torrefaction pressure is insignicant.
Mass fraction and activation energy of hemicellulose are reduced by wet torrefaction.
Activation energy of cellulose is increased by wet torrefaction.
a r t i c l e i n f o a b s t r a c t
Article history: This work continues our assessment of wet torrefaction for energy applications, looking at effects of the
Received 24 March 2014 process parameters (temperature, holding time and pressure) on the reactivity and intrinsic kinetics of
Received in revised form 18 June 2014 wood under air combustion conditions. Woody materials, Norway spruce and birch, were wet torreed
Accepted 5 August 2014
in various conditions (temperature: 175, 200, 225 C; holding time: 10, 30, 60 min; and pressure:
Available online 19 August 2014
15.54, 70, 160 bar). The reactivity of the treated and untreated woods was thermogravimetrically exam-
ined under a synthetic air environment (21% O2 and 79% N2 in volume). A four-pseudo-component model
Keywords:
with different reaction orders was adopted for kinetic modelling and extracting the kinetic parameters.
Wet torrefaction
Wood reactivity
The results showed that when increasing either torrefaction temperature or holding time, the torreed
Combustion kinetics woods behaved more char-like than the raw fuels. However, pressure did not show signicant effect
Kinetic modelling on the reactivity. Relatively longer char combustion stages and higher conversion rates (up to
Biofuel pretreatment 0.5 103 s1) were observed for the woods after torrefaction. The activation energy was decreased
for hemicellulose and char, but increased for cellulose after torrefaction, whereas the trend for lignin
is not clear. In addition, the hemicellulose mass fraction decreased after torrefaction (from 0.15 to 0.05
for spruce and from 0.23 to 0.06 for birch). The amount of char in the torreed woods increased gradually
with increasing torrefaction temperature or holding time (from 0.24 to 0.40 for spruce, and from 0.18 to
0.34 for birch).
2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2014.08.011
0016-2361/ 2014 Elsevier Ltd. All rights reserved.
376 Q.-V. Bach et al. / Fuel 137 (2014) 375383
Like dry torrefaction (DT), which may be dened as thermal Nevertheless, the model was based on an empirical method which
treatment of biomass in an inert environment at atmospheric pres- was not validated because the model itself could not either repro-
sure and temperatures within the range of 200300 C [2628], duce simulated curves or give any information about the t quality
WT results in the following main improvements in the fuel proper- between the predicted and experimental data. Recently, studies on
ties of biomass: (1) increased heating value due to a reduction in the combustion kinetics of dry torreed woody biomass materials
the O/C ratio; (2) intrinsic transformation from hygroscopic into using multi pseudo-component models have been reported by
hydrophobic nature of biomass; (3) better grindability coupling Brostrm et al. [42] and Tapasvi et al. [43]. The former employed
with less energy requirement for size reduction of the fuel. After a global kinetic model and the latter employed a distributed activa-
WT, the wet hydrophobic solid product can be effectively made tion energy model (DAEM). The results from the two approaches
dry by mechanical and/or natural dewatering, which is an showed that DT had little effect on the kinetic parameters of the
attractive option capable of dramatically reducing the energy torreed biomass regardless of the treatment conditions. Brostrm
requirement for the post-drying step. In addition to the solid fuel et al. [42] reported that the activation energy values of hemicellu-
product, many valuable organic compounds including acetic acid, lose, cellulose and lignin were constant at 100.6, 213.1, and
formic acid, lactic acid, glycolic acid, levulinic acid, phenol, furfural, 121.3 kJ/mol, respectively for both raw and dry-torreed spruce.
HMF, and sugars are found in the aqueous phase products of WT, Tapasvi et al. [43] found that the activation energy values for cellu-
making up approximately 10 wt% of the feedstock [4,6]. The poten- lose, non-cellulosic part and char remained at 135, 160 and 153 kJ/
tial use of these water-soluble organic fractions for production of mol, respectively for different types of feedstock and DT conditions.
valuable products may contribute to further improving the econ- This present study is a follow-up of our rst assessment of WT
omy of the WT process. for energy applications [1], which has been published as men-
Recently, an assessment of WT for energy applications (com- tioned earlier. The objective of the present work was to assess
bustion, gasication, and pyrolysis) in comparison with DT has the effects of WT conditions (temperature, holding time and pres-
been reported by our research group [1]. The assessment includes sure) on the combustion reactivity and kinetics of biomass solid
a literature review of past studies relevant to WT, which will not be fuels. Thermogravimetric analysis (TGA) was employed for this
repeated in this present work. A core theme of the assessment was work as it is a proven method for studying devolatilization and
to investigate the effects of process parameters including pressure, combustion of biomass in the kinetic regime [44,45].
reaction temperature, holding time, and feedstock particle size on
the yield and fuel properties of the solid product. For reaction tem- 2. Materials and methods
perature and holding time, positive trends of their effects on the
yield and fuel properties of the solid products were observed, 2.1. Materials
which are similar to those for DT. However, pressure and feedstock
particle size only have minor effects. More interestingly, the ash As mentioned in the introduction, the present work is a follow-
content of biomass fuel is signicantly reduced by WT. This sug- up of our rst report on comparative assessment of WT for energy
gests that WT can be employed to produce cleaner biomass solid applications. The biomass materials used for this work were
fuels as well, with respect to inorganic elements. In addition, a obtained from the previous work, in which the full details about
comparison between WT and DT supported by regression analyses materials and experimental methods were presented and can be
and numerical prediction showed that WT can produce solid fuel found elsewhere [1]. For a convenience, a brief extraction is
with greater heating value, higher energy yield, and better hydro- imported in this present work.
phobicity at much lower temperatures and holding times than DT Stem wood from Norway spruce (softwood) and birch (hard-
[1]. wood) were selected as feedstock for the study since they are the
Despite various advantages of WT over DT, only a few studies on main wood species in Norwegian forests. The samples were cut
WT have been reported [15] compared to a sharply increasing into 1 cm cubes for WT in hot compressed water, using a 250 ml
number of studies on DT during the last few years [2634]. In addi- Parr reactor series 4650 (Parr Instrument, USA) at different tem-
tion, most WT studies focused on the effects of process parameters peratures (175, 200, 225 C), pressures (15.54, 70, 160 bar) and
on the yield and fuel properties of the solid product. To our knowl- holding times (10, 30, 60 min). The corresponding vapour pres-
edge, no study of using solid fuel obtained from WT for energy sures of water at 175, 200, and 225 C are 8.93, 15.54, and
applications has been reported so far. Combustion is currently 25.50 bar, respectively. However, in order to keep more water in
the most important energy application of biomass solid fuel, con- the liquid phase, the pressure of 70 bar was used for all of the
sidering its contribution to more than 90% of the global bioenergy WT experiments, except for the investigation of the pressure effect
deployment [3539]. It is therefore important and necessary to at 200 C [1]. For this investigation, the pressures of 15.54, 70 and
investigate into the effects of WT on combustion reactivity and 160 bar were employed. Distilled water was used as the reaction
kinetics of biomass solid fuels. media. The ratio of dry feedstock over water was 1:5 by weight.
Several studies on combustion of dry torreed biomass have After WT, the wet solid products were dried at 105 C for 48 h
been reported [30,4043], which would be benecial for studying and then stored in a desiccator for further analyses. The proximate
combustion behavior of wet torreed biomass fuel. Pimchuai and ultimate analyses of the samples used for this work are pre-
et al. [40] and Bridgeman et al. [30], for example, studied the com- sented in Table 1. The proximate analyses were performed accord-
bustion of biochars obtained from DT of different biomass materi- ing to ASTM standards: ASTM E871, ASTM E872 and ASTM D1102
als. They found that the combustion of dry torreed husks and for moisture content, volatile matter and ash content, respectively.
herbaceous biomass released more heat than that of the raw mate- The ultimate analyses were determined (on a dry basis) by means
rials due to the higher xed carbon content of the biochars. How- of an EA 1108 CHNS-O elemental analyzer (Carlo Erba Instru-
ever, no kinetic data was reported from these studies. Arias et al. ments). The higher heating values (HHVs) were calculated on dry
[41] applied a simple rst-order kinetic model to estimate the acti- and ash free basis, according to Channiwala and Parikh [46].
vation energy and pre-exponential factor of raw and dry-torreed
eucalyptus samples in a two-stage combustion process (devolatil- 2.2. Thermogravimetric analysis method and procedure
ization followed by combustion). The results showed that both
kinetics parameters (the activation energy and pre-exponential A thermogravimetric analyzer (Mettler Toledo TGA/SDTA851e)
factor) increased in stage 1 and decreased in stage 2 after DT. was employed for this study. The biomass solid fuels were rst
Q.-V. Bach et al. / Fuel 137 (2014) 375383 377
Table 1
Proximate and ultimate analyses of raw and wet torreed fuels (dry and ash free).
VM: volatile matter, FC: xed carbon, HHV: higher heating value.
a
wt%.
b
MJ/kg.
ground using an IKA MF 10 cutting mill. Then the particles passing where Av, Bv, Cv and Dv are the pseudo-components; and Vi (i = 1, 2,
through a 125 lm sieve (Fritsch Analysette 3 Pro) were collected 3, 4) is the lumped volatiles and/or gases released from the thermal
for the kinetic study to ensure the experiments to be in the chem- degradation of the respective pseudo-component. The three rst
ical reaction kinetic regime [47,48]. For each TGA run, an amount reactions (Eqs. (1)(3)) are associated with the devolatilization of
of about 0.5 mg sample was spread in a 150 ll alumina pan located the three main components of biomass including hemicellulose,
inside the TGA reactor. It is worth noting that the buoyancy effect cellulose and lignin, respectively. The rates of these reactions can
plays a signicant role for such a small sample weight. Therefore, it be presented by the general power law (nth-order) expression,
is mandatory to run a blank TG (mass loss versus temperature) although n = 1 is usually used [42,49,51,52]. The last reaction (Eq.
curve rst. The weight change of the blank experiment was sub- (4)) represents the char combustion, for which the rate law is gen-
tracted from the experimental curves automatically. The experi- erally related to the partial pressure of oxygen through an empirical
ment started from room temperature, the fuel sample was exponent and the char porosity. Due to a relatively small amount of
heated to 105 C and held at this temperature for 1 h for drying. the sample tested in an air ow, it is reasonable to assume that the
Thereafter, the sample was heated to 700 C at a constant heating oxygen mass fraction remains constant during the reaction process.
rate of 10 C/min. A synthetic air ow rate of 80 ml/min was Consequently, the general power law (nth-order) expression can
applied for all experiments. Moreover, three repetitions were run also be applied to represent the char combustion. Overall, the
for each fuel sample, and the average kinetic values are reported. conversion rate of these four reactions can be described by the
following Arrhenius expression:
2.3. Kinetic model selection
dai Ei
Ai exp 1 ai ni ; i 1; . . . ; 4 5
Branca and Di Blasi [49] proposed and examined two different
dt RT
models to describe the combustion of biomass fuel. They are ser- where A is the pre-exponential factor, E is the activation energy of
ies- and parallel-reaction models, of which each model consists the reaction, R is the universal gas constant, T is the absolute
of four reactions (3 reactions for the devolatilization of the three temperature, n is the reaction order, and i is for the ith pseudo-
main components of lignocellulosic biomass, and 1 reaction for component. The conversion degree (a) is dened as the mass frac-
the char burn-off). It was concluded that both models gave similar tion of decomposed solid or released volatiles:
results for the estimated kinetic parameters. However, the parallel-
reaction mechanism, or the pseudo-component model, is favorable
m0 m v
a 6
and widely used [42,50,51] because it can describe the possible m0 mf v f
overlapped reactions of the lumped components in biomass. where m0 and mf are the initial and nal masses of solid, m is the
According to this model, the biomass sample is regarded as a mass of solid at any time; vf is the total mass of released volatiles
sum of four pseudo-components, and the activation energies were and v is the mass of released volatiles at any time.
assumed to be constant during the reactions to simplify the simu- The overall conversion rate is the sum of the partial conver-
lation process. sions, where ci indicates the mass fraction of each pseudo-compo-
For the present study, the parallel-reaction model proposed by nent in the following equation:
Branca and Di Blasi [49] was adopted. The four parallel reactions
applied for the model are as follows: da X 4
dai
ci 7
O2 dt i1
dt
Av ! V 1 1
O2
Bv ! V 2 2 2.4. Numerical method
simulation and comparison with the experimental DTG data. The (softwood) [54]. Also, hemicellulose of hardwood usually contains
optimization of the predicted DTG curves was based on the non- more xylan than softwood, which is the most reactive compound
linear least squares method, which minimized the sum of the in the temperature range of the devolatilization (200350 C) [54].
square differences between the experimental and calculated data. In the char combustion stage, the birch wood char exhibits
The objective function is given in Eq. (8): lower reactivity than that of spruce wood char. The char combus-
" tion rate peak is only 0.38 103 s1 for the birch, but
XN #2
daj daj 0.53 103 s1 for the spruce.
S 8
j1
dt exp dt cal
da da 3.2. Effects of torrefaction conditions on reactivity of wood in air
where dtj exp and dtj cal represent the experimental and calculated
combustion
conversion rates, respectively; and N is the number of experimental
points.
3.2.1. The effect of torrefaction temperature
In order to validate the optimization or the curve tting process
The woods torreed at three different temperatures (175, 200,
in other words, the t quality between actual and modelled data is
and 225 C), in the common conditions of 30 min as holding time
calculated according to Eq. (9) [49,53]:
and 70 bar as pressure were used for this test. The test results
q 0 1
are presented in Fig. 2, which includes the data collected for the
S
B N C raw woods for comparison. Fig. 2A is for the spruce wood and
Fit % B
@1 da
C 100%
A 9 Fig. 2B for the birch wood. As can be seen, the torreed woods start
j
dt
exp max decomposing at temperatures around 150 C, somehow lower than
those for the raw woods (around 180 C). However, the conversion
The actual simulation was run until the maximum t value was rates in this early stage are very low, approximately being less than
found, at which the convergence criteria of the optimization pro- 0.2 103 s1 in all cases. A slightly higher reactivity of the torr-
cess are achieved. The extracted kinetic parameters are: the activa- eed woods than their origins in the early decomposition stage
tion energies (E1E4), the pre-exponential factors (A1A4), the mass may be due to the higher reactivity of a small amount of remaining
fractions (c1c4), and the reaction orders (n1n4) for each pseudo- organic compounds, with low molecular weights, produced from
component. Totally, there are 12 kinetic parameters for the 1st the degradation of hemicellulose during the WT processes
order model and 16 parameters for the nth order model. [55,56]. Most of these organic compounds were washed out and
collected in the water-soluble product portion, but some of them
3. Results and discussions
3.5
3.1. Thermogravimetric analysis of spruce and birch wood in air Raw
(A) - Spruce
175C
Conversion rate, d/dt103 (s-1)
3.0
Fig. 1 shows the TG and DTG curves, representing the thermal 200C
225C
behavior of the raw spruce and birch woods in the temperature 2.5
range of 100600 C. The standard deviation of the conversion rate
data for the tested samples was 1.38 105 s1. For both types of 2.0
feedstock, the decomposition starts at around 180 C with a low
conversion rate. Then the decomposition rate increases rapidly 1.5
from around 250 C to the devolatilization peaks (2.3 103 s1)
at 321324 C, from which the rate decreases quickly, down to 1.0
0.30 103 s1 for the spruce wood and 0.25 103 s1 for the
birch wood at around 350 C. This marks the end of the devolatil- 0.5
ization and the beginning of the char combustion, which has much
lower rates than the devolatilization. In addition, a clear shoulder 0.0
100 200 300 400 500 600
in the devolatilization stage is observed for the raw birch wood,
but not for the raw spruce. This is because the hemicelluloses con- Temperature (C)
tent of birch (hardwood) is normally higher than that of spruce
3.5
(B) - Birch Raw
175C
Conversion rate, d/dt103 (s-1)
3.0
2.5 200C
Raw spruce 225C
Conversion rate, d/dt103 (s-1)
100
Raw birch 2.5
2.0
80 2.0
Weight (%)
1.5
60 1.5
1.0 1.0
40
0.5 0.5
20
0.0
0.0 0 100 200 300 400 500 600
100 200 300 400 500 600 Temperature (C)
Temperature (C)
Fig. 2. DTG analyses in air for spruce (A) and birch (B) woods torreed at 70 bar for
Fig. 1. TGA and DTG curves in air for raw spruce and birch woods. 30 min.
Q.-V. Bach et al. / Fuel 137 (2014) 375383 379
may have been trapped in the pores and/or adsorbed on the surface 3.5
of the torreed biomass. At temperatures from 250 C up to 310 C, (A) - Spruce Raw
Fig. 4. DTG curves in air for spruce torreed in the condition of 200 C, 10 min at
3.2.3. The effect of torrefaction pressure different pressures.
Table 2
Combustion kinetic data for spruce fuels.
70 bar (at different temperatures and with different holding times) during WT the hemicellulose component of the wood was decom-
were selected for the kinetic analysis. The selection of this pressure posed and cracked into smaller molecules such as polysaccharides
was based on the recommendation discussed in our previous study [55,56], which remained in the solid products.
[1]. In total, 12 experimental data sets were analyzed kinetically, of However, the effect trend of WT on the activation energy of lig-
which 6 were for the spruce wood and 6 for the birch wood. The nin is not clear. Similar observations were described by Biswas
kinetic data extracted from this analysis are presented in Tables et al. [61], which reported that the thermal reactivity of woody lig-
2 and 3 for the spruce and birch, respectively. The quality of the nin may either increase or decrease due to hydrothermal pretreat-
t between the experimental and predicted data is also included ment, depending on the severity of the pretreatment conditions
in the tables. In addition, for a graphical demonstration of the t which may result in condensation and re-polymerization reactions.
quality, curves ttings for the raw woods and the woods torreed In contrast to hemicellulose, the activation energy of cellulose is
at 200 C for 30 min (at 70 bar) are presented in Figs. 5 and 6, increased by WT. This is presumably due to the increased crystal-
respectively. In these gures, the actual conversion rates from linity of cellulose caused by hydrothermal treatment [6264]. It is
the experiments are presented by the black dotted curves. The because that during thermal degradation, crystalline cellulose was
red solid curves denote the predicted rates. The other four curves reported to have much higher activation energy than non-crystal-
are presenting the conversion rates of the three main components line cellulose due to the increased cross linking [65].
of wood (hemicellulose, cellulose, and lignin) and the char formed Similar to hemicellulose, the activation energy of char combus-
from the devolatilization step. The gures show good ts between tion is decreased by WT (from 183.09 kJ/mol for the raw spruce to
the experimental and modelled results. The t quality numerically 109.38 kJ/mol for spruce torreed at 225 C and 30 min; from
presented in Tables 2 and 3 is within 9899% in all cases. 222.00 kJ/mol for raw birch to 132.26 kJ/mol for birch torreed at
Tables 2 and 3 show that the modelling with different reaction 225 C for 30 min). This is presumably due to the changes in ash con-
orders generated quite similar kinetic data. The data of the activa- tent of the woods after WT since it was reported in the literatures
tion energy and pre-exponential factor are comparable with those [6669] that the ash content and ash composition of char from bio-
reported in the literature [45,49,53,59,60]. In addition, most of the mass would both enhance or inhibit the char reactivity. It is because
calculated n values are close to 1. However, the nth order model both mass transfer limitations and catalytic effects of the ash.
still exhibits somehow better t and gives more information about The mass fraction of hemicellulose is reduced by WT. In addi-
the reaction order. Therefore, the kinetic data obtained from the tion, the mass fraction is decreased gradually with increasing WT
nth order model are chosen for further assessments hereafter. severity, from 0.15 for the raw spruce to 0.05 for the spruce torr-
It can be seen that, while there is no clear trend for the effect of eed at 225 C and 30 min; and from 0.23 for the raw birch to
WT on the pre-exponential factor, the activation energy of hemi- 0.06 for the birch torreed at 225 C and 30 min. From the condi-
cellulose is reduced dramatically by WT, e.g. decreases from tions of 200 C and 30 min to more severe conditions (higher tem-
103.76 to 44.82 kJ/mol and from 144.68 to 41.29 kJ/mol for the peratures or longer holding times), the hemicellulose mass fraction
spruce and birch, respectively, by WT at 225 C (and 70 bar) for of the torreed fuel is small, less than 10% of the total mass. With
30 min. This effect can also be observed from the hemicellulose the reduction of hemicellulose fraction, the mass fraction of the
curves in Figs. 5 and 6, which show clearly that WT caused a shift other component fractions in the torreed biomass fuels (cellulose,
of the hemicellulose curves to a lower temperature range. This is in lignin, and char) are relatively increased compared with the raw
agreement with the literature [61] and can be explained by that materials, as presented in Tables 2 and 3.
Q.-V. Bach et al. / Fuel 137 (2014) 375383 381
Table 3
Combustion kinetic data for birch fuels.
(A) Raw spruce, n=1 (C) Torrefied spruce, 200C, 30 min, n=1
2.5 3.0
Exp. Data Exp. Data
Conversion rate, d/dt103 (s-1)
0.5
0.5
0.0 0.0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature (C) Temperature (C)
0.5
0.5
0.0 0.0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature (C) Temperature (C)
The mass fraction of cellulose in the torreed fuels from both decreased with either increasing temperature or holding time.
feedstocks increased to a maximum value, 0.47 and 0.56 for The contribution of cellulose fractions is in good agreement with
spruce and birch torreed at 200 C and 30 min, and then the heights of the devolatilization peaks shown in Figs. 2 and 3.
382 Q.-V. Bach et al. / Fuel 137 (2014) 375383
(A) Raw birch, n=1 (C) Torrefied birch, 200C, 30 min, n=1
2.5 3.5
Exp. Data Exp. Data
Conversion rate, d/dt103 (s-1)
1.0 1.5
1.0
0.5
0.5
0.0 0.0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature (C) Temperature (C)
1.0 1.5
1.0
0.5
0.5
0.0 0.0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature (C) Temperature (C)
The higher cellulose fraction is, the higher devolatilization peak is of cellulose in the devolatilization stage and the competition
observed. This helps conrm the suspicion and explain the incon- between catalyzing and inhibiting effects of char ash on the
sistent trend in the effects of WT temperature or holding time on char combustion stage.
the devolatilization peaks height as observed and discussed earlier
in this paper. In addition, the kinetic analysis using the four-pseudo-compo-
The mass fraction of lignin varies in a narrow range (0.170.23 nent model with n 1 showed that the activation energy of hemi-
for torreed spruce and 0.150.25 for torreed birch) because the cellulose and char was reduced, but that of cellulose was increased
hydrothermal media within the WT conditions has little effects on by WT. The activation energy of hemicellulose was reduced from
the overall degradation of lignin [22]. On the other hand, the mass 103.8 to 44.8 kJ/mol for the spruce wood, and from 144.7 to
fraction of char is increased gradually (from 0.20 and 0.14 for raw 41.3 kJ/mol for the birch wood. That of char was from 183.1 to
spruce and birch to 0.40 and 0.34 for spruce and birch torreed at 109.4 kJ/mol for the spruce and from 222.0 to 132.3 kJ/mol for
225 C and 30 min, respectively) with torrefaction temperature the birch. The activation energy of the cellulose was increased from
and holding time. 221.5 to 239.0 kJ/mol for the spruce, and from 204.7 to 236.7 kJ/
mol for the birch. The mass fraction of hemicellulose was reduced
4. Conclusions by WT (from 0.15 to 0.05 for the spruce and from 0.23 to 0.06 for
the birch), but that for char was increased gradually (0.200.40 for
The effects of WT on the reactivity and kinetics of woods under spruce and 0.140.34 for birch).
air combustion conditions were investigated using thermogravi-
metric method and kinetic modelling. Two types of woody bio- Acknowledgements
mass, Norway spruce and birch woods were used as feedstock.
The following conclusions can be drawn from this study: This work is nancially supported by the Research Council of
Norway and industry partners through the KMB project STOP
WT pressure had insignicant effects on the combustion reac- (STable OPerating conditions for biomass combustion plants),
tivity of the woods. which is gratefully acknowledged.
WT temperature and holding time had similar effects on the
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[28] Chew JJ, Doshi V. Recent advances in biomass pretreatment torrefaction [65] Gaur S, Reed TB. Thermal data for natural and synthetic fuels. CRC Press; 1998.
fundamentals and technology. Renew Sustain Energy Rev 2011;15:421222. [66] Spiro CL, McKee DW, Kosky PG, Lamby EJ. Catalytic CO2-gasication of
[29] Chen W-H, Hsu H-C, Lu K-M, Lee W-J, Lin T-C. Thermal pretreatment of wood graphite versus coal char. Fuel 1983;62:1804.
(Lauan) block by torrefaction and its inuence on the properties of the [67] Kannan MP, Richards GN. Gasication of biomass chars in carbon dioxide:
biomass. Energy 2011;36:301221. dependence of gasication rate on the indigenous metal content. Fuel
[30] Bridgeman TG, Jones JM, Shield I, Williams PT. Torrefaction of reed canary 1990;69:74753.
grass, wheat straw and willow to enhance solid fuel qualities and combustion [68] Moilanen A, Thermogravimetric characterisations of biomass and waste for
properties. Fuel 2008;87:84456. gasication processes. Doctoral Dotoral Thesis, bo Akademi University,
[31] Medic D, Darr M, Shah A, Potter B, Zimmerman J. Effects of torrefaction process Turku, Finland; 2006.
parameters on biomass feedstock upgrading. Fuel 2012;91:14754. [69] Lane DJ, Ashman PJ, Zevenhoven M, Hupa M, van Eyk PJ, de Nys R, et al.
[32] Phanphanich M, Mani S. Impact of torrefaction on the grindability and fuel Combustion behavior of algal biomass: carbon release, nitrogen release, and
characteristics of forest biomass. Bioresour Technol 2011;102:124653. char reactivity. Energy Fuels 2013;28:4151.
[33] Tapasvi D, Khalil R, Skreiberg , Tran K-Q, Grnli M. Torrefaction of Norwegian
birch and spruce: an experimental study using macro-TGA. Energy Fuels
2012;26:523240.
PaperIII
Effectsofwettorrefactiononpyrolysisofwoodybiomassfuels
QuangVuBach,KhanhQuangTran,andyvindSkreiberg.
SubmittedtoEnergy.
Elsevier Editorial System(tm) for Energy
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Manuscript Number:
Keywords: Wet torrefaction; Biomass fuel; Hydrochar; Pyrolysis kinetics; Kinetic modelling
Order of Authors: Quang-Vu Bach; Khanh-Quang Tran; yvind Skreiberg ; Thuat T Trinh
Abstract: The pyrolysis of Norway spruce and birch woods under nitrogen atmosphere was studied by
means of a thermogravimetric analyzer operated in the non-isothermal mode, followed by a kinetic
analysis employing a three-pseudo-component model with nth-order reactions. Raw woods and the
woods treated via wet torrefaction in the conditions of various temperatures (175, 200, 225 C) and
holding times (10, 30, 60 min) were included in this work. The study showed that wet torrefaction
resulted in higher pyrolysis peaks for the woods, but less mass of volatiles was released during
pyrolysis. The effects of wet torrefaction on pyrolysis of the lignocellulosic components are different.
The activation energy of hemicellulose was significantly reduced by wet torrefaction. However, those
for cellulose and lignin were slightly increased by wet torrefaction. In addition, a kinetic evaluation
with assumption of common parameters was performed. The results confirmed that some kinetic
parameters can be assumed to be common for pyrolysis kinetic modelling of different biomasses
without substantial reductions in the fit quality. Wet torrefaction has positive effects on the
possibilities for biomass pyrolysis kinetic modeling with assumption of common parameters.
Highlights (for review)
Highlights
Torrefaction temperature and holding time significantly influence the pyrolysis reactivity
Mass fraction and activation energy of hemicellulose are significantly reduced by wet
torrefaction.
Activation energies for cellulose and lignin are slightly increased by wet torrefaction.
Some kinetic parameters could be assumed common without substantial reductions in the
fit quality.
*Manuscript
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Effects of Wet Torrefaction on Pyrolysis of Woody
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18 Quang-Vu Bach a,*, Khanh-Quang Tran b, yvind Skreiberg b and Thuat T. Trinh c
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21 Department of Energy and Process Engineering, Norwegian University of Science and
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23 Technology, NO-7491, Trondheim, Norway
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Department of Thermal Energy, SINTEF Energy Research, NO-7465, Trondheim, Norway
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Department of Chemistry, Norwegian University of Science and Technology, NO-7491,
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32 Trondheim, Norway
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38 Corresponding author E-mail: quang.vu.bach@ntnu.no; qvbach@gmail.com
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41 Tel.: +47 73591645
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44 Fax: +47 73593580
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4 Abstract
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7 The pyrolysis of Norway spruce and birch woods under nitrogen atmosphere was studied by
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10 means of a thermogravimetric analyzer operated in the non-isothermal mode, followed by a
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12 kinetic analysis employing a three-pseudo-component model with nth-order reactions. Raw woods
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15 and the woods treated via wet torrefaction in the conditions of various temperatures (175, 200,
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17 225 C) and holding times (10, 30, 60 min) were included in this work. The study showed that
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19 wet torrefaction resulted in higher pyrolysis peaks for the woods, but less mass of volatiles was
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22 released during pyrolysis. The effects of wet torrefaction on pyrolysis of the lignocellulosic
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24 components are different. The activation energy of hemicellulose was significantly reduced by
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27 wet torrefaction. However, those for cellulose and lignin were slightly increased by wet
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29 torrefaction.
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32 In addition, a kinetic evaluation with assumption of common parameters was performed. The
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35 results confirmed that some kinetic parameters can be assumed to be common for pyrolysis
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37 kinetic modelling of different biomasses without substantial reductions in the fit quality. Wet
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torrefaction has positive effects on the possibilities for biomass pyrolysis kinetic modeling with
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42 assumption of common parameters.
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48 Keywords: Wet torrefaction, Biomass fuel, Hydrochar, Pyrolysis kinetics, Kinetic modelling
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4 1 Introduction
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7 Wet torrefaction (WT) is a promising method for biomass pretreatment and production of
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9 advanced solid biofuels. It may be defined as processing of lignocellulosic materials in
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12 hydrothermal media (HM) or hot compressed water (HCW) at temperatures between 180-260 C
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14 [1-6]. The main product of the WT is hydrochar (hydrothermal biochar), a hydrophobic solid
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17 fuel with much better grindability, lower moisture content and higher calorific value compared
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19 with the untreated biomass [1-6]. In addition to hydrochar, WT also produces various water-
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22 soluble byproducts including acetic acid, formic acid, lactic acid, glycolic acid, levulinic acid,
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24 phenol, furfural, hydroxymethylfurfural (HMF), and sugars, which account altogether for
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approximately 10 wt% of the dry feedstock [4-6]. Separation and utilization of these organic
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29 fractions may contribute to an economic improvement of the WT process at industrial scales.
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32 Recently, a study on WT of biomass for energy applications has been reported by our research
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34 group [1]. The study also included a comparison with dry torrefaction (DT), which may be
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37 defined as mild pyrolysis of biomass within the temperature range of 200-300 C [7-9]. The
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39 results showed that WT can produce solid fuels with greater heating values, higher energy yields,
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42 and better hydrophobicity at significantly lower temperatures and shorter holding times than DT.
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44 In addition, WT is capable of removing parts of the ash components and hence produces cleaner
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solid fuels, with respect to inorganic elements.
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At present, combustion is the most important energy application of solid biomass fuel,
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52 considering its contribution to more than 90% of the global bioenergy deployment [10-14].
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54 Pyrolysis (devolatilization) is the first step, after drying, in the combustion process of solid
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57 biomass fuel. In addition, pyrolysis can be used as a standalone process for further treatments of
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59 biomass fuels [15]. Therefore, it is important to understand the thermal behavior and kinetics of
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4 biomass pyrolysis for the design, modification or optimization of the thermal conversion units.
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7 For these reasons, past research in the field was very active. For example, Brostrm et al. [16]
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9 employed a multi pseudo-component kinetic model to study effect of DT on the pyrolysis of
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12 Norway spruce. The model described closely the actual pyrolysis, assuming first order reactions.
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14 Later, Tapasvi et al. [17] established an even more detailed and more complex model, mainly
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based on the distributed activation energy model (DAEM), to describe better the pyrolysis and
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19 combustion kinetics of biomass. On the other hand, Many et al. [18] and Conesa and Domene
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21 [19] found that the pseudo-component kinetic model with nth order described the biomass
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24 pyrolysis kinetics better than the model with first order reactions. More recently, a comparative
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26 kinetic evaluation on pyrolysis of dry-torrefied stump biomass has been reported [20]. The results
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29 showed the differences in fit quality of the three-pseudo-component model with first order, the
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31 three-pseudo-component model with nth order, and DAEM were insignificant. In addition, the
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three-pseudo-component model with nth order was recommended for a pyrolysis kinetic study of
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36 solid biomass fuel.
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39 Despite the advantages of WT over DT and the importance of understanding the thermal
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41 behavior and kinetics of biomass pyrolyis, only few studies on WT [1-6] can be found in the
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44 literature, of which the focus was on the effects of process parameters on the yield and fuel
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46 properties of the solid product. To our knowledge, there is no open literature available for
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49 pyrolysis of hydrochar, except for the one reported by Yan et al. [21]. In that study, the pyrolysis
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51 of solid obtained from HTC of loblolly pine was thermogravimetrically analyzed and compared
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with that of the untreated pine. Two simple kinetic models, Kissinger's and Ozawas methods,
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56 were employed for a kinetic study of the pyrolysis. However, the kinetic information obtained by
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58 these methods is limited and does not closely represent the reality, considering the complexity in
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4 the chemical composition of lignocellulosic biomass materials. It is therefore crucial for WT
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7 technology to carry out more relevant studies on thermal behavior and kinetics of hydrochar
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9 pyrolysis.
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12 In addition, Trnini et al. [22] indicated that, in kinetic modelling for thermal decomposition of
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15 biomass, it is possible to have common kinetic parameters for various types of lignocellulosic
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17 biomass fuels, considering the similarities and differences between the fuels. Also, Tapasvi et al.
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19 [17] suggested that if some of the kinetic parameters are assumed to be common, the following
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22 benefits can be achieved: (1) the common parameters indicate the similarities in the kinetic
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24 behavior of different samples; (2) a given parameter value is based on more experimental data, it
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27 is therefore less dependent on the experiment uncertainties. For this purpose, a first
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29 approximation of similarities for lignocellulosic biomass materials can be made based on the fact
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32 that their main organic components are hemicellulose, cellulose, and lignin [17, 22]. If the
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34 approximation is good enough, then only the contribution factors for the pseudo-components
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need to be varied from biomass to biomass.
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In this present work, the pyrolysis kinetics of hydrochars produced from woods via WT in
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42 different conditions was studied by means of thermogravimetric analysis (TGA) and compared
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44 with the untreated materials. The three-pseudo-component model with nth order was adopted for
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47 the kinetic analysis, including a kinetic evaluation for different model variants by assuming
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4 2 Materials and methods
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The raw and torrefied woods used in this work were obtained from our previous work [1]. A
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13 brief description of the materials preparation is given here. Norway spruce and birch wood cubes
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15 with sides of 1 cm were used as feedstock. The dry feedstock and distilled water (with a ratio of
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18 1:5 by weight) were placed in a 250 ml Parr reactor series 4650 (Parr Instrument, USA) for WT
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20 at a constant pressure of 70 bar but different temperatures (175, 200, 225 C) and holding times
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23 (10, 30, 60 min). After WT, the wet solid products were dried in an oven at 105 C for 48 h and
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25 then stored in a desiccator for further analyses. The proximate and ultimate analyses of the raw
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and wet torrefied samples used for the TGA in this work are listed in Table 1. The higher heating
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30 values (HHVs) were calculated on dry and ash free basis, according to Channiwala and Parikh
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32 [23].
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36 2.2 Thermogravimetric experiments
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39 TGA is a proven method for studying the pyrolysis of biomass [24-27]. In the present work, a
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41 Mettler Toledo TGA/SDTA851e was employed and operated in a non-isothermal mode. The fuel
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samples were first ground by an IKA MF 10 cutting mill, and particles less than 125 m (sieved
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46 by a Fritsch Analysette 3 Pro vibrator) were collected for the pyrolysis/devolatilization study to
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48 ensure that the experiments were in the kinetic control regime [28-30]. A sample of 2 mg was put
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51 in a 150 l alumina pan for the TGA in a Mettler Toledo TGA/SDTA851e reactor. It should be
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53 noted that the buoyancy effect plays a significant role for such a small sample weight. Therefore,
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56 running a blank curve is mandatory, and the weight change of the blank experiment was
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58 subtracted from the experimental curves automatically. The experiment started from room
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4 temperature, the fuel sample was heated to 105 C and held at this temperature for 1 h for drying.
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7 Thereafter, the sample was heated up to 700 C at a constant heating rate of 10 C per minute. A
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9 nitrogen flow rate of 100 ml/min was applied for all experiments.
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13 2.3 Kinetic modeling
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15 In this study, a global kinetic model with three parallel reactions adopted from Branca et al.
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18 [28] was employed for modelling pyrolysis kinetics. One advantage of this model is that it does
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20 not require testing the fuel at different heating rates. It is because the heating rate within the range
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23 from 3 to 108 C/min does not affect the activation energy, pre-exponential factor and reaction
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25 order. Moreover, the model can well describe the separate decompositions of the three main
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components of lignocellulosic biomass including hemicellulose, cellulose, and lignin [16-19, 28,
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30 31, 32]. The three independent parallel reactions used in this work are shown below:
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(1)
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(2)
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(3)
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40 where Av, Bv, and Cv are the pseudo-components; and Vi (i = 1, 2, 3) is the total volatiles released
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45 The conversion rates of all reactions follow the Arrhenius expression:
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exp (1 ) ! , # 1, 2, 3 (4)
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52 where A is the pre-exponential factor, E is the activation energy of the reaction, R is the universal
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54 gas constant, T is the absolute temperature, n is the reaction order, and i is for the ith pseudo-
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57 component. The conversion degree () is defined as the mass fraction of decomposed solid or
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%& % (
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%& %' ('
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8 where m0 and mf are the initial and final masses of solid, m is the mass of solid at any time; vf is
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13 The overall conversion rate is the sum of the partial conversion rates, where ci indicates the
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16 contribution factor or the volatile fraction produced from each component in the following
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* + (6)
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26 Curves fitting were based on the non-linear least squares method, in which the objective
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:
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. * /0 2 0 2 9 (7)
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1,
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G.
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F H N
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I J
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D K74 L
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52 The curve fitting process was run until a best fit between the simulated data and the
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experimental results was obtained. Then, kinetic parameters can be extracted, including: the
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4 (c1, c3, c3), and the reaction orders (n1, n2, n3). Conventionally, the names of pseudo-component 1,
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10 3 Results and discussion
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14 3.1 Thermal decomposition behavior of spruce and birch woods
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16 Figure 1 shows the TG and DTG curves, respectively representing the mass loss and the
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19 conversion rate of the raw spruce and birch woods in the temperature range of 100-600 C. The
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21 TG curves indicate that both woods started decomposing at around 200 C and most of the mass
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24 losses were taking place within 200-380 C. The mass losses were more significant for birch
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26 wood than for spruce. This difference can be attributed to the difference in the volatile matter
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29 content of birch and spruce, as presented in Table 1.
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32 The DTG curves give additional information about the pyrolysis of the woods. Indeed, they
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34 show that the decomposition of both feedstocks actually started at around 180 C and became
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36 significant from 200 C. At temperatures higher than 400 C the decompositions were less
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39 significant. More importantly, the DTG curves reveal locations of the decomposition rate peaks,
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41 which were at about 362 C for spruce and 364 C for birch. It appears that the peak locations of
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44 the woods were very close to each other, but the peak heights were different. The height for the
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46 birch (1.7510-3 s-1) was higher than that for the spruce (1.5510-3 s-1). In addition, a clear
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49 shoulder was observed for the DTG curve of the raw birch, but not for the raw spruce. This
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51 difference is due to the fact that birch (hardwood) has higher hemicelluloses contents than spruce
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(softwood) [33].
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4 3.2 Effects of wet torrefaction on pyrolysis of spruce and birch woods
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7 3.2.1 The effect of torrefaction temperature
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10 Figure 2 presents the DTG curves for spruce and birch wood torrefied at different temperatures
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12 (175, 200, and 225 C) under the common conditions of 30 min and 70 bar. The curves for the
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15 untreated woods are also included in the figures for comparison. The figures show that the
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17 torrefied woods started decomposing at temperatures, around 150 C, i.e. lower than those for the
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20 raw woods (around 180 C), and with slightly higher conversion rates. The higher reactivity of
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22 the torrefied woods, compared to the raw woods, in the early stage of the decomposition may be
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25 due to the presence of a small amount of remaining organic compounds, with low molecular
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27 weights and thus high reactivity, produced from the degradation of hemicellulose during the WT
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process [34, 35].
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32 At temperatures from 250 C up to 350 C, the torrefied woods were less reactive than the raw
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35 woods. This is due to the fact that within this temperature window the degradation of
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37 hemicellulose is the most dominant compared to other components, and the torrefied woods have
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40 less or no hemicellulose compared with the original feedstock [2]. On the other hand, the DTG
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42 peak locations were slightly affected by WT. For the birch, the DTG peak locations were slightly
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45 shifted towards higher temperatures, indicating an increase in the activation energy. However, an
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47 unclear trend was observed for the spruce. Similar observations can be noted for the DTG peak
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heights. Indeed, when increasing the torrefaction temperature from 175 C to 200 C, the peak
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52 height increased (from 1.9010-3 s-1 to 2.0410-3 s-1 for spruce and from 2.2010-3 s-1 to 2.4310-3
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54 s-1 for birch). However, further increasing the torrefaction temperature to 225 C decreased the
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57 peak height. The peak height for spruce torrefied at 225 C was even lower than that for the raw
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59 spruce. This observation will be discussed further in combination with a kinetic analysis.
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4 3.2.2 The effect of torrefaction time
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7 The effects of torrefaction time on pyrolysis of the woods are presented in Figure 3, which
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10 includes DTG data for the woods torrefied for 10, 30 and 60 min under the common conditions of
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12 200 C and 70 bar, and the raw woods. It can be seen from the figures that the effect of holding
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15 time was more pronounced for the birch wood (Figure 3B) than for the spruce wood (Figure 3A).
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17 The trends in shifting the DTG peak location and height by torrefaction time were similar to
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19 those by torrefaction temperature. When torrefaction time was increased from 10 to 30 min, the
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22 peak height of torrefied spruce and birch increased. Further increased torrefaction time to 60 min
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24 resulted in almost no further change for the birch, but caused a decrease for the spruce, with
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27 respect to the peak height. However, the peak height for the spruce torrefied for 60 min was still
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29 higher than that of the raw spruce (not the case for the effect of torrefaction temperature, Figure
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32 2B). This observation will also be discussed later in combination with a kinetic analysis.
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35 3.3 Kinetic evaluation by assuming three-pseudo-component model with nth-order
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38 A kinetic analysis employing the three-pseudo-component model with nth-order was performed
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40 for a quantitative evaluation of the effects of WT on the pyrolysis reactivity of wood. In total, 12
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43 experimental data sets were analyzed kinetically, of which 6 were for the spruce wood and 6 for
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45 the birch wood. The kinetic data extracted from this analysis are presented in Table 2 and Table 3
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48 for the spruce and birch, respectively. The quality of the fit between the experimental and
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50 predicted data is also included in the tables. In addition, for a graphical demonstration of the fit
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52 quality, curves fittings for the raw woods and the woods torrefied at 200 C for 30 min (at 70 bar)
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55 are presented in Figure 4 and Figure 5, respectively. In these figures, the actual conversion rates
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57 from the experiments are represented by the black dotted curves. The red solid curves denote the
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60 predicted rates. The other three curves are presenting the conversion rates of the three main
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4 components of wood (hemicellulose, cellulose, and lignin). The figures show good fits between
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7 the experimental and modelled results. The fit quality numerically presented in Table 2 and Table
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9 3 is within 98-99% in all cases. In addition, most of the calculated n values are close to 1.
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12 It can be seen that both the activation energy and pre-exponential factor of hemicellulose are
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15 reduced dramatically by WT. The activation energy of hemicellulose decreases respectively from
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17 95.67 to 26.63 kJ/mol and from 106.80 to 34.18 kJ/mol for the spruce and birch; and pre-
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19 exponential factor decreases respectively from 1.63106 s-1 to 1.60 s-1 and from 3.34107 s-1 to
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22 1.98101 s-1 for the spruce and birch, by WT at 225 C (and 70 bar) for 30 min. This effect can
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24 also be observed from the hemicellulose curves in Figure 4 and Figure 5, which show clearly that
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27 WT caused a shift of the hemicellulose curves to a lower temperature range. This is in agreement
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29 with the literature [36] and can be explained by the decomposition and cracking of hemicellulose
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32 into smaller molecules [34, 35], which remained in the solid products.
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35 In contrast to hemicellulose, the activation energy and pre-exponential of cellulose is increased
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37 by WT. It can be seen from the tables that the average activation energy values of cellulose for
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the torrefied spruce and birch are respectively 194.54 0.76 kJ/mol and 193.17 0.75 kJ/mol. In
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42 addition, the pre-exponential factors of cellulose vary in a very narrow range of 6.87-6.921013 s-
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for both torrefied spruce and birch, compared to the values of 188.27 kJ/mol and 2.561013 s-1
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47 for raw spruce and 189.47 kJ/mol and 3.171013 s-1 for raw birch. This is presumably due to the
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49 increased crystallinity of cellulose caused by hydrothermal treatment [37-39]. It is reported that
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52 crystalline cellulose has higher activation energy during thermal degradation than non-crystalline
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54 cellulose due to increased cross-linking [40].
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57 The effects of WT temperature and holding time on the activation energy and pre-exponential
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of lignin are not clear, although these values are increased by WT. In detail, the activation energy
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4 is increased respectively from 40.22 kJ/mol and 38.95 kJ/mol for the raw spruce and birch to an
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7 average value of 48.09 0.58 kJ/mol and 40.69 0.71 kJ/mol for the torrefied spruce and birch,
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9 respectively. In addition, the pre-exponential factor of lignin is increased from 2.05 s-1 for raw
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12 spruce to 1.06-1.11101 s-1 for torrefied spruce, and from 1.26 s-1 for raw birch to 4.23-4.28 s-1
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14 for torrefied birch. Similar observations were described by Biwas et al. [36], who reported that
15
16
the thermal reactivity of woody lignin may either increase or decrease due to hydrothermal
17
18
19 pretreatment, depending on the severity of the pretreatment conditions which may result in
20
21 condensation and re-polymerization reactions.
22
23
24 The contribution factor of hemicellulose is reduced by WT. In addition, the reduction is
25
26
27 decreased gradually with increasing WT severity, from 0.29 for the raw spruce to 0.05 for the
28
29 spruce torrefied at 225 C and 30 min; and from 0.36 for the raw birch to 0.03 for the birch
30
31
32 torrefied at 225 C and 30 min. From the conditions of 200 C and 30 min to more severe
33
34 conditions (higher temperatures or longer holding times), the hemicellulose mass fraction of the
35
36
37
torrefied fuel is small, less than 15% of the total mass. With the reduction of hemicellulose
38
39 fraction, the mass fraction of the other component fractions in the torrefied biomass fuels
40
41 (cellulose, lignin, and char) are increased proportionately compared with the raw materials, as
42
43
44 presented in Table 2 and Table 3.
45
46
47 The contribution factor of cellulose in the torrefied fuels from both feedstocks increased to a
48
49 maximum value, 0.53 for spruce torrefied at 200 C, 60 min and 0.62 for birch torrefied at 200
50
51
52 C, 30 min, and then decreased with either increasing temperature or holding time. The
53
54 contribution of cellulose fractions is in good agreement with the heights of the pyrolysis peaks
55
56
57
shown in Figure 2 and Figure 3. The higher the cellulose fraction is, the higher pyrolysis peak is
58
59
60
61
62 13
63
64
65
1
2
3
4 observed. This explain the inconsistent trend in the effects of WT temperature or holding time on
5
6
7 the pyrolysis peaks height as observed and discussed earlier in this paper.
8
9
10 The contribution factor of spruce lignin is almost unchanged (0.16 to 0.15) when torrefaction
11
12 temperature is increased from 175 to 200 C, but then it is increased from 0.15 to 0.27 when the
13
14
15 torrefaction temperature is increased from 200 to 225 C. In addition, the factor is increased from
16
17 0.12 to 0.18 when holding time is prolonged from 10 to 60 min. On the other hand, when
18
19 torrefaction temperature is increased (from 175 to 225 C), contribution factor of birch lignin is
20
21
22 increased (from 0.11 to 0.32). However, the effect of holding time on the contribution factor of
23
24 birch lignin is not clear, e.g. it decreases from 0.29 to 0.19 when holding time is increased from
25
26
27 10 to 30 min but then it increased to 0.35 when holding time was further increased to 60 min. The
28
29 variation in the observed contribution factors may be due to various reasons, which include the
30
31
32 condensation or re-polymerization between decomposition products of hemicellulose and lignin
33
34 [36], the increasing fraction of acid soluble lignin [41], or the softening, melting and
35
36
37
carbonization of lignin [42].
38
39
Moreover, it should be noted that the sum of the contribution factors is not equal to 1 because
40
41
42 these factors indicate the mass fraction of the volatiles released from the dry biomass components
43
44 (hemicellulose, cellulose and lignin), i.e. the solid residue is accounting for the difference [26,
45
46
47 43]. It can be seen that the sum of c values of woods are gradually reduced with increasing the
48
49 WT severity. The decreasing trend of the sum of c values is similar to that of the volatile matter
50
51
52 in the proximate analyses. Moreover, the sum of c values are only 1.2-3.6% lower than the
53
54 volatiles fraction presented in Table 1, showing good agreement in volatile content between the
55
56
57
proximate analysis and the values calculated from the modeling results.
58
59
60
61
62 14
63
64
65
1
2
3
4 3.4 Evaluation with assumption of common parameters
5
6
7 As discussed earlier in the introduction, an evaluation with assumption of common kinetic
8
9 parameters was attempted and reported in this section to identify possibilities for describing the
10
11
12 thermal decomposition of different biomass materials by a common model. For this purpose, data
13
14 collected from the TG experiments for the raw woods were evaluated first. A similar evaluation
15
16
17 was then performed for the woods torrefied under the same conditions (200 C, 30 min and 70
18
19 bar). The evaluation identifications and results are presented in Table 4 and Table 5 for the
20
21
22 original and torrefied woods, respectively. In these tables, the kinetic analysis presented in the
23
24 preceding section (3.3) was employed to serve as the base case (Evaluation 1, Model Variant III),
25
26
27
for which none of the kinetic parameters was assumed common.
28
29
Let us now examine the component curves of the base case, presented in Figure 4A and Figure
30
31
32 5A for the native woods. It is observed that the pink curves of the third pseudo-component
33
34 (lignin) are wide and flat compared to those of cellulose and hemicellulose, the second and first
35
36
37 pseudo-components. A major part of the pink curves overlaps with the temperature domains of
38
39 the curves for the second and first pseudo-components. A change of the pink curves in these
40
41
42 domains can be compensated by relatively small changes by pseudo-components 1 and 2 without
43
44 significant worsening of the overall fit quality. Accordingly, the kinetic parameters for lignin
45
46
47
(activation energy E3 and pre-exponential factor A3) of both native woods can be forced to be
48
49 identical in value [17] and were assumed common in Evaluation 2 (Table 4).
50
51
52 It can also be observed from Table 2 and Table 3 that the kinetic parameters of cellulose (E2
53
54 and A2) for both native woods are similar. Consequently, these parameters could also be forced to
55
56
57 have common values [17] in Evaluation 3 (Table 4). Finally, all of the kinetic parameters for the
58
59
60
61
62 15
63
64
65
1
2
3
4 three pseudo-components, including the activation energy values (E1, E2 and E3) and pre-
5
6
7 exponential factors (A1, A2 and A3), were assumed common [17] in Evaluation 4 (Table 4).
8
9
10 For the torrefied woods (Table 5) evaluations similar to those for the native woods (Table 4)
11
12 were postulated and performed to serve the comparison purpose of this work. In addition, as can
13
14
15 see in Figure 4B and Figure 5B, the component (blue) curves for hemicellulose appear flat.
16
17 Therefore, Evaluation 5 with assumption of E1 and A1 as common parameters was performed for
18
19 the torrefied woods and included in Table 5.
20
21
22 In addition to Model Variant III, the evaluations were also tested for two other model variants
23
24
25 (Variant II and Variant I) formulated by partially giving the value of one to the reaction order of
26
27 ith pseudo-component (ni). It is because of the fact that while some believe the decomposition
28
29 17,27-29
30 during pyrolysis of biomass can be described by first reaction order (ni = 1) , others
31
32 reported that reaction orders higher than one gave better description for the pseudo-components
33
34
35 of biomass [17-19]. Partially fixing the value of ni to one would bring about model variants,
36
37 which may produce better fits and thus more closely describe the biomass pyrolysis. Indeed, it is
38
39
observed from Table 2 and Table 3 that, in most of the cases, n2 is close to one, but n3 is far from
40
41
42 1. In addition, n1 varies within the range of 1.01 - 1.49. On the basis of these observations and
43
44 information from the literature [17, 22], three model variants were selected for the evaluations
45
46
47 and presented in Table 4 and Table 5. Variant III is actually from the base case, nth-order, for
48
49 which none of the component reaction orders was fixed to one (ni 1; and i = 1, 2, 3). Variant II
50
51
52 is different from Variant III by fixing n2 to one (n1 1, n2 = 1, n3 1). Finally, Variant I has two
53
54 common reaction orders of unity (n1 = 1, n2 = 1, n3 1).
55
56
57 Results from all of the evaluations with assumptions of common parameters for different model
58
59
variants are tabulated in Table 4 and Table 5 for the raw and torrefied woods, respectively. The
60
61
62 16
63
64
65
1
2
3
4 higher value the fit quality is, the better the model variant represents the biomass decomposition.
5
6
7 In addition, the curve fitting of Evaluations 1, 3 and 4 (Variant III) for the untreated and torrefied
8
9 woods is presented respectively in Figure 6 and Figure 7 for a graphical demonstration of the fit
10
11
12 quality.
13
14
15 As can be seen from the tables, the trends of changes in fit quality for both of the untreated and
16
17 torrefied woods are similar, inversely proportional to the number common parameters assumed.
18
19 These trends are mathematically obvious and in agreement with the literature [17, 22]. Indeed,
20
21
22 the fit quality reduces consistently when moving from Evaluation 1 downward to Evaluation 4,
23
24 for each of the model variants. Similarly, the reduction trend in fit quality is observed for each of
25
26
27 the evaluations, when moving from Variant III toward Variant I.
28
29
30 For the untreated woods (Table 4) the fit qualities of the base case (Evaluation 1, Variant III)
31
32 are 99.25% and 99.21% for spruce and birch, respectively. Further examination of the data in two
33
34
35 columns of Variant III, one for spruce and one for birch, from the top to the bottom give the
36
37 information that the fit qualities in Evaluation 2 slightly reduce to 99.24% and 99.14% for spruce
38
39
and birch, respectively. These insignificant reductions in fit quality confirm that the assumptions
40
41
42 of Evaluation 2 are reasonable. Similar observations and confirmations are also noted for both
43
44 woods in Evaluation 3. However, the fit quality in Evaluation 4 reduces significantly to 94.60%
45
46
47 and 96.85% for spruce and birch, respectively. This suggests that the assumptions of Evaluation 4
48
49 for the untreated woods are not reasonable.
50
51
52 In addition, analyses similar to those applied for different evaluations in one column as above
53
54
55 can also be applied for assessment of different model variants in each of the evaluation rows, by
56
57 examining the data from the right to the left or from Variant III to Variant I. As the results of the
58
59
overall assessment, by column and by row throughout the table, all the cases with insignificant
60
61
62 17
63
64
65
1
2
3
4 reductions in fit quality are summarized by highlighting with red and blue colors for the native
5
6
7 spruce and birch, respectively, in Table 4. Furthermore, all of the analyses presented above for
8
9 the untreated woods can also be applied for the torrefied woods, Table 5, from which the results
10
11
12 are also highlighted in the same way by the same colors for comparison.
13
14
15 Table 4 and Table 5 show that, although the effects of WT on the fit quality in the first three
16
17 evaluations are varied being somewhat positive or negative, the variations are insignificant.
18
19 However, the effects become clear and significant for Evaluation 4, in which all of the kinetic
20
21
22 parameters are forced to be common. These improvements in fit quality of Evaluation 4 are
23
24 presumably due to the normalization of the fuels with particular respect to component 1,
25
26
27 considering the very high fit quality obtained from Evaluation 5 (Table 5) in which E1 and A1 are
28
29 forced common.
30
31
32 Overall, the data in Table 4 and Table 5 indicate that WT has positive effects on the
33
34
35 possibilities for biomass pyrolysis kinetic modeling with assumption of common parameters.
36
37 These can be attributed to the effect of WT on normalizing the composition of different
38
39
biomasses, which is similar to carbonization.
40
41
42
43 4 Conclusions
44
45
46 The effects of WT on the thermal decomposition behavior and pyrolysis kinetics of spruce and
47
48 birch woods were investigated by means of a thermogravimetric analyzer, followed by a kinetic
49
50
51
analysis employing the three-pseudo-component model with nth-order reactions. The torrefaction
52
53 conditions were varied within three different temperatures (175, 200, 225 C) and holding times
54
55 (10, 30, 60 min). It appears that, in most of the cases, WT enhanced the pyrolysis peak height, but
56
57
58 decreased the total volatiles released from the thermal decomposition. Too severe WT conditions
59
60 (e.g. 225 C and 30 min) resulted in decreased pyrolysis rate due to the accelerated
61
62 18
63
64
65
1
2
3
4 decomposition of cellulose. The kinetic parameters of hemicellulose were gradually reduced by
5
6
7 WT. The kinetic parameters of cellulose were all increased due to its crystallization in
8
9 hydrothermal media. In addition, WT increases the activation energy and pre-exponential factor
10
11
12 of lignin, although the effect trends of WT temperature and holding time are not clear.
13
14
15 In addition, a kinetic evaluation with assumption of common parameters was performed. The
16
17 results confirmed that some kinetic parameters can be assumed to be common for pyrolysis
18
19 kinetic modelling of different raw biomasses without substantial reductions in the fit quality.
20
21
22 WT has positive effects on the possibilities for biomass pyrolysis kinetic modeling with
23
24 assumption of common parameters.
25
26
27
28 5 Acknowledgement
29
30
31
This work is financially supported by the Research Council of Norway and industry partners
32
33 through the KMB project STOP (STable OPerating conditions for biomass combustion plants),
34
35 which is gratefully acknowledged.
36
37
38
39 6 References
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18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 23
63
64
65
1
2
3
4 Table 1. Heating values, proximate and ultimate analyses of raw and torrefied woods
5
6
7
8 Solid Proximate analysis Ultimate analysis
Sample HHVb
9 yielda Asha VMa FCa Ca
Ha Na Oa Sa
10
11 Raw 0.23 86.50 13.27 50.31 6.24 0.07 43.38 < 0.02 20.42
12
13 175C, 30min 88.27 0.11 85.72 14.17 51.34 6.18 0.07 42.42 < 0.02 20.81
14
Spruce
15 200C, 10min 82.48 0.14 84.64 15.22 51.21 6.39 0.06 42.35 < 0.02 21.02
16
17
200C, 30min 78.45 0.12 83.92 15.95 52.55 6.15 0.06 41.23 < 0.02 21.33
18 200C, 60min 73.28 0.09 81.87 18.03 53.69 5.89 0.06 40.36 < 0.02 21.51
19
20 225C, 30min 69.74 0.14 74.74 25.12 56.99 5.87 0.07 37.07 < 0.02 22.97
21
22 Raw 0.28 89.46 10.26 48.94 6.35 0.11 44.60 < 0.02 19.94
23
24 175C, 30min 79.53 0.09 88.57 11.34 49.42 6.38 0.12 44.07 < 0.02 20.21
25
200C, 10min 66.42 0.08 87.97 11.94 49.61 6.16 0.13 44.10 < 0.02 20.01
Birch
26
27 200C, 30min 64.64 0.09 85.15 14.76 51.25 6.18 0.11 42.46 < 0.02 20.78
28
29 200C, 60min 63.06 0.10 82.64 17.27 51.34 5.94 0.13 42.59 < 0.02 20.51
30
31 225C, 30min 58.01 0.13 73.78 26.09 56.92 5.86 0.09 37.13 < 0.02 22.93
32 a b
33 wt%, MJ/kg
34 VM: volatile matter, FC: fixed carbon, HHV: higher heating value
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 24
63
64
65
1
2
3
4 Table 2. Pyrolysis kinetic data for spruce woods
5
6
7
8 Torrefaction Kinetics parameters
9
Fit (%)
condition E (kJ/mol) A (s-1) c n
10
11 H 95.67 1.63E+06 0.29 1.01
12
13 C 188.27 2.56E+13 0.38 1.01
14 Raw spruce 99.25
15 L 40.22 2.05E+00 0.19 3.70
16
17 Sum 0.86
18 H 64.39 1.99E+03 0.21 1.03
19
20 C 194.86 6.91E+13 0.47 1.03
21 175C, 30min 98.98
22 L 47.85 1.06E+01 0.16 3.00
23
24 Sum 0.85
25
26
H 37.09 4.95E+00 0.23 1.10
27 C 194.85 6.90E+13 0.48 1.01
28 200C, 10min 98.82
29 L 48.20 1.08E+01 0.12 1.96
30
31 Sum 0.83
32
33 H 32.99 2.55E+00 0.15 1.21
34
C 195.03 6.85E+13 0.51 1.01
35 200C, 30min 99.23
36 L 48.53 1.11E+01 0.15 1.84
37
38 Sum 0.81
39
40 H 30.24 1.05E+00 0.09 1.06
41
42 C 194.76 6.92E+13 0.53 1.04
43
200C, 60min 99.19
L 48.64 1.07E+01 0.18 1.64
44
45 Sum 0.80
46
47 H 26.63 1.60E+00 0.05 1.01
48
49 C 193.19 6.90E+13 0.40 1.05
50 225C, 30min 99.12
51 L 47.22 1.06E+01 0.27 1.62
52 Sum 0.72
53
54 H: hemicellulose, C: cellulose, L: lignin
55
56
57
58
59
60
61
62 25
63
64
65
1
2
3
4 Table 3. Pyrolysis kinetic data for birch woods
5
6
7
8 Torrefaction Kinetics parameters
9
Fit (%)
condition E (kJ/mol) A (s-1) c n
10
11 H 106.80 3.34E+07 0.36 1.55
12
13 C 189.47 3.17E+13 0.44 1.01
14 Raw birch 99.21
15 L 38.95 1.26E+00 0.07 1.33
16
17 Sum 0.87
18 H 56.06 6.06E+02 0.18 1.15
19
20 C 194.00 6.87E+13 0.55 1.01
21 175C, 30min 99.15
22 L 41.18 4.25E+00 0.11 1.18
23
24 Sum 0.85
25
26
H 54.74 3.05E+03 0.06 1.49
27 C 193.79 6.87E+13 0.50 1.01
28 200C, 10min 98.52
29 L 39.79 4.31E+00 0.28 1.45
30
31 Sum 0.84
32
33 H 38.61 2.67E+01 0.03 1.01
34
C 192.67 6.92E+13 0.62 1.05
35 200C, 30min 99.08
36 L 40.08 4.23E+00 0.19 2.10
37
38 Sum 0.84
39
40 H 35.62 1.80E+01 0.03 1.11
41
42 C 193.17 6.91E+13 0.42 1.03
43
200C, 60min 98.34
L 41.40 4.27E+00 0.35 1.91
44
45 Sum 0.80
46
47 H 34.18 1.98E+01 0.03 1.07
48
49 C 192.22 6.92E+13 0.37 1.01
50 225C, 30min 98.89
51 L 41.01 4.26E+00 0.32 1.84
52 Sum 0.71
53
54 H: hemicellulose, C: cellulose, L: lignin
55
56
57
58
59
60
61
62 26
63
64
65
1
2
3
4 Table 4. Fit quality with assumption of common parameters for the native woods
5
6
7 Fit quality, %
8
9
10 Raw spruce Raw birch
11
12 Common Variant Variant Variant Variant Variant Variant
13 Evaluation I II III I II III
parameters
14 n1=1 n11 n11 n1=1 n11 n11
15
16 n2=1 n2=1 n21 n2=1 n2=1 n21
17
18 n31 n31 n31 n31 n31 n31
19
20 1 None 99.24 99.24 99.25 98.97 99.20 99.21
21
22 2 E3 and A3 99.21 99.21 99.24 98.97 99.14 99.14
23
24 E2, E3
3 98.44 98.89 98.89 98.50 98.89 98.90
25 and A2, A3
26
27 E1, E2, E3
28 4 93.17 94.61 94.60 95.61 96.85 96.85
29
and A1, A2, A3
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 27
63
64
65
1
2
3
4 Table 5. Fit quality with assumption of common parameters for the woods torrefied at 200 C
5
6
7 for 30 min.
8
9
10 Fit quality, %
11
12 Torrefied spruce Torrefied birch
13
14 Variant Variant Variant Variant Variant Variant
15
Common
Evaluation I II III I II III
16 parameters
17 n1=1 n11 n11 n1=1 n11 n11
18 n2=1 n2=1 n21 n2=1 n2=1 n21
19
20 n31 n31 n31 n31 n31 n31
21
22 1 None 99.22 99.22 99.23 99.30 99.30 99.32
23
24 2 E3 and A3 98.79 98.86 99.07 99.20 99.20 99.28
25
26 E2, E3
27 3 97.08 97.08 97.71 98.06 98.95 98.96
28 and A2, A3
29
30
E1, E2, E3
4 96.51 96.51 97.71 96.98 96.99 97.04
31 and A1, A2, A3
32
33
5 E1 and A1 99.07 99.21 99.21 99.29 99.29 99.31
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 28
63
64
65
1
2
3
4 1 Figure 1. Thermogravimetric analysis for pyrolysis of the untreated spruce and birch woods
5
6
7
8
9 1.8
10 Raw spruce
100
11 Raw birch
Conversion rate, d/dt103 (s-1)
1.5
12
13
14 1.2 75
15
Weight (%)
16
0.9
17 50
18
19 0.6
20
25
21
0.3
22
23
24 0.0 0
25 100 200 300 400 500 600
26 Temperature (C)
27 2
28
29
30 3
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 29
63
64
65
1
2
3
4 1 Figure 2. DTG data for (A) the native spruce and (B) the birch wood torrefied at different
5
6
7 2 temperatures (175, 200, or 225 C), and common conditions: time = 30 min, pressure = 70 bar
8
9
10
11 2.4
12
13
(A) Raw
2.1
Conversion rate, d /dt103 (s-1)
14 175C
200C
15 1.8 225C
16
17 1.5
18
19 1.2
20
21 0.9
22
23 0.6
24
0.3
25
26
0.0
27 100 200 300 400 500 600
28
29 Temperature (C)
30 3
31
32
33
34 2.7
35 (B) Raw
36 2.4
175C
37
Conversion rate, d /dt103 (s-1)
2.1 200C
38 225C
39 1.8
40
41 1.5
42
1.2
43
44 0.9
45
46 0.6
47
0.3
48
49 0.0
50 100 200 300 400 500 600
51
Temperature (C)
52
53 4
54
55 5
56
57
58
59
60
61
62 30
63
64
65
1
2
3
4 1 Figure 3. DTG data for (A) the native spruce and (B) the birch torrefied for different time (10,
5
6
7 2 30, or 60 min), in common conditions: temperature = 200 C, pressure = 70 bar
8
9
10
11 2.4
12
13
(A) Raw
2.1 10 min
14
Conversion rate, d /dt103 (s-1)
30 min
15 1.8 60 min
16
17 1.5
18
19 1.2
20
21 0.9
22
23 0.6
24
0.3
25
26
0.0
27 100 200 300 400 500 600
28
29 Temperature (C)
30 3
31
32
33
34 2.7
35 (B)
36 2.4 Raw
10 min
37
Conversion rate, d /dt103 (s-1)
2.1 30 min
38 60 min
39 1.8
40
41 1.5
42
1.2
43
44 0.9
45
46 0.6
47
0.3
48
49 0.0
50 100 200 300 400 500 600
51
Temperature (C)
52
53 4
54
55 5
56
57
58 6
59
60
61
62 31
63
64
65
1
2
3
4 1 Figure 4. Curve fitting for (A) the untreated spruce and (B) the spruce torrefied at 200 C and
5
6
7 2 30 min
8
9
10
11 2.4
12 Exp. Data
13 2.1 (A) Cal. Data
Conversion rate, d/dt10 (s )
-1
14 Hemicellulose
3
15 1.8 Cellulose
16 Lignin
17 1.5
18
1.2
19
20 0.9
21
22 0.6
23
24 0.3
25
26 0.0
100 200 300 400 500 600
27
28 Temperature (C)
29 3
30
31
32
33 2.4
34 Exp. Data
35 2.1
(B) Cal. Data
Conversion rate, d/dt10 (s )
-1
36 Hemicellulose
3
37 1.8 Cellulose
Lignin
38
1.5
39
40 1.2
41
42 0.9
43
44 0.6
45
46 0.3
47
48 0.0
100 200 300 400 500 600
49
50 Temperature (C)
51 4
52
53
54
5
55
56
57
58
59
60
61
62 32
63
64
65
1
2
3
4 1 Figure 5. Curve fitting for (A) the untreated birch and (B) the birch torrefied at 200 C and 30
5
6
7 2 min
8
9
10
11 2.7
12 Exp. Data
13 2.4 (A) Cal. Data
Conversion rate, d/dt10 (s )
-1
14 Hemicellulose
2.1
3
15 Cellulose
16 Lignin
1.8
17
18 1.5
19 1.2
20
21 0.9
22
0.6
23
24 0.3
25
26 0.0
100 200 300 400 500 600
27
28 Temperature (C)
29 3
30
31
32
33 2.7
34 Exp. Data
35 2.4 (B) Cal. Data
Conversion rate, d/dt10 (s )
-1
36 2.1
Hemicellulose
3
37 Cellulose
Lignin
38 1.8
39
1.5
40
41 1.2
42
43 0.9
44
0.6
45
46 0.3
47
48 0.0
100 200 300 400 500 600
49
50 Temperature (C)
51 4
52
53
54
5
55
56
57
58
59
60
61
62 33
63
64
65
1
2
3
4 1 Figure 6. Curve fitting for the untreated woods by Evaluation 1, 3, and 4 of Variant III
5
6
7
8
9 2.4 2.4
10 Spruce Birch
2.1 2.1 Exp. Data
11 Cal. Data
Conversion rate, d /dt103 (s-1)
18
19 0.6 0.6
20 0.3 0.3
21
22 0.0
100 200 300 400 500 600
0.0
100 200 300 400 500 600
23
24
2.4 2.4
25
26 2.1 2.1
27
Conversion rate, d /dt103 (s-1)
28 1.8 1.8
29 1.5 1.5
30
31 1.2 Evaluation 3: 1.2
common parameters:
32 E2, A2, E3, A3
33 0.9 0.9
34 0.6 0.6
35
36 0.3 0.3
37
0.0 0.0
38 100 200 300 400 500 600 100 200 300 400 500 600
39
40 2.4 2.4
41
42 2.1 2.1
Conversion rate, d /dt103 (s-1)
43 1.8 1.8
44
45 1.5 1.5
46 Evaluation 4:
1.2 1.2
47 common parameters:
48 0.9
E1, E2, E3, A1, A2, A3
0.9
49
50 0.6 0.6
51 0.3 0.3
52
53 0.0 0.0
100 200 300 400 500 600 100 200 300 400 500 600
54 Temperature (C) Temperature (C)
55
56 2
57
58
59
60
61
62 34
63
64
65
1
2
3
4 1 Figure 7. Curve fitting for the woods torrefied at 200 C and 30 min by Evaluation 1, 3, and 4
5
6
7 2 of Variant III
8
9
10
11 2.5 2.5
12
13 Spruce Birch Exp. Data
Cal. Data
14 2.0 2.0
Conversion rate, d /dt10 (s )
Hemicellulose
3 -1
15 Cellulose
16 Lignin
17
1.5 1.5
18 Evaluation 1:
no common parameter
19 1.0 1.0
20
21
22 0.5 0.5
23
24 0.0 0.0
25 100 200 300 400 500 600 100 200 300 400 500 600
26
27 2.5 2.5
28
29
2.0 2.0
30
Conversion rate, d /dt103 (s-1)
31
32 1.5 1.5
33 Evaluation 3:
34 common parameters:
E2, A2, E3, A3
35 1.0 1.0
36
37 0.5 0.5
38
39
40 0.0
100 200 300 400 500 600
0.0
100 200 300 400 500 600
41
42 2.5 2.5
43
44
45 2.0 2.0
Conversion rate, d /dt103 (s-1)
46
47
48 1.5 1.5
49 Evaluation 4:
common parameters:
50 1.0 E1, E2, E3, A1, A2, A3 1.0
51
52
53 0.5 0.5
54
55
0.0 0.0
56 100 200 300 400 500 600 100 200 300 400 500 600
PaperIV
Torrefactionofforestresiduesinsubcriticalwater
QuangVuBach,KhanhQuangTran,andyvindSkreiberg.
SubmittedtoAppliedEnergy.
Elsevier Editorial System(tm) for Applied Energy
Manuscript Draft
Manuscript Number:
Keywords: Wet torrefaction; Wet feedstock; Forest residue; Biomass pretreatment; Solid biofuel.
Abstract: In this study, effects of temperature (175, 200, 225 C) and holding time (10, 30, 60 min) on
wet torrefaction of branch woods was simultaneously studied and compared with the results from a
previous study on wet torrefaction of stem woods. Similar effect trends were observed between the
studies. Birch branch wood is more reactive than spruce branch wood. Both torrefaction temperature
and holding time have significant effects on the solid yield and the fuel properties of hydrochars.
Branch woods are slightly more reactive than stem woods under identical torrefaction conditions. The
effects of torrefaction temperature on the grindability and hydrophobicity of hydrochar from branch
woods are more significant than those from stem woods. In all cases, the differences in solid and
energy yield between branch and stem woods are within 2.1-6.3% w/w and 1.0-3.0% for spruce and
birch, respectively. The differences in grindability and hydrophobicity between branch and stem
woods are respectively up to 8.1% and 15.7% for spruce, whereas 10.3% and 10.9% for birch.
Highlights (for review)
Wet torrefaction of branch woods was simultaneously studied and compared with that
of stem woods.
Birch branch wood is more reactive than spruce branch wood
Branch woods are slightly more reactive than stem woods under identical torrefaction
conditions
The differences in solid and energy yield between branch and stem woods are within
2.1-6.3% (w/w) and 1.0-3.0% (w/w) for spruce and birch, respectively.
Manuscript
1
3 Department of Energy and Process Engineering, Norwegian University of Science and
2
5 Department of Thermal Energy, SINTEF Energy Research, NO-7465 Trondheim, Norway
*
6 Corresponding author E-mail: quang.vu.bach@ntnu.no
1
1 Abstract
2 In this study, effects of temperature (175, 200, 225 C) and holding time (10, 30, 60 min) on
3 wet torrefaction of branch woods was simultaneously studied and compared with the results from
4 a previous study on wet torrefaction of stem woods. Similar effect trends were observed between
5 the studies. Birch branch wood is more reactive than spruce branch wood. Both torrefaction
6 temperature and holding time have significant effects on the solid yield and the fuel properties of
7 hydrochars. Branch woods are slightly more reactive than stem woods under identical
9 hydrophobicity of hydrochar from branch woods are more significant than those from stem
10 woods. In all cases, the differences in solid and energy yield between branch and stem woods are
11 within 2.1-6.3% (w/w) and 1.0-3.0% (w/w) for spruce and birch, respectively. The differences in
12 grindability and hydrophobicity between branch and stem woods are respectively up to 8.1% and
14
15 Keywords: Wet torrefaction; Wet feedstock; Forest residue; Biomass pretreatment; Solid
16 biofuel.
2
1 1 Introduction
2 The use of solid biomass fuels for heat and power generation has received increasing interest
3 [1-3]. This is because biomass is a renewable and carbon neutral resource, which is considered
4 as an alternative energy source for a sustainable development [4]. However, the use of native
5 biomass for heat and power generation is not straightforward [5, 6]. Compared to coal, biomass
6 fuel has some drawbacks, which include lower bulk density, higher moisture content, inferior
7 heating value, and poorer grindability. Due to these disadvantages, the expenses for handling,
8 transport, and storage of biomass fuels are increased. In order to overcome these drawbacks of
11 solid fuels with much better grindability and increased heating value, compared to the native
12 materials. The technology can be classified into two categories: dry and wet torrefaction. Dry
13 torrefaction (DT) may be defined as thermal treatment of biomass in the absence of oxygen at
14 temperatures within the range of 200-300 C and at atmospheric pressure [4, 11, 12]. Recently,
15 research on DT has been extended to work in the presence of oxygen and carbon dioxide [13-
16 16], and under elevated pressures [17, 18]. Wet torrefaction (WT) may be defined as processing
19 [24-33] and sometimes can be found in the literature under different terms such as hydrothermal
21 sometimes been used interchangeably, it is worth noting that the fuel properties and applications
22 of the solid products from WT and HTC are significantly different from each other. WT aims at
23 upgrading solid biomass fuels and produce hydrochar for energy applications (combustion,
3
1 gasification, and pyrolysis) only. HTC is employed mainly for producing charcoal with much
2 lower volatile matter but higher carbon content than hydrochar. The charcoal can be used not
3 only as fuel but also as activated carbon, soil enhancer, fertilizer, and even more [44-46]. In
5 relatively high yields of hydrochar (more than 60%), whereas HTC are commonly conducted at
6 temperatures higher than 300 C, from which the solid yield may be as low as 35% [36].
8 combustion, gasification, and pyrolysis have been very active during the last decade [4, 7-9, 11,
9 12, 47-59]. The DT technology has been developed rapidly and is ready for market introduction
10 and commercial operation [49]. However, it has been claimed that no clear winner in this area
11 can be identified so far [49]. This situation might partially be due to the fact that current
12 technologies of DT use wood chips from stem wood, a feedstock of relatively high quality and
13 thus cost. Utilization of inexpensive biomass resources such as agricultural residues, forest
14 residues and other biomass waste sources may help reducing the total cost of biomass
15 torrefaction at industrial scale. A problem associated with DT is that this method normally
16 requires the input feedstock to have a moisture content not higher than the critical value of 5-
17 10% by weight [60], which is much lower than that of the low cost biomass resources
19 needed and thus raising up the cost again. To overcome this challenge, WT may be an alternative
20 for DT, because it involves water as reaction medium and thus the energy intensive step of pre-
23 biomass fuels [20, 23], which include the possibility to produce solid fuels with better fuel
4
1 properties at lower temperatures and holding times, compared to DT. In addition, parts of the
2 ash-forming inorganic components are dissolved in the water during WT and thus the hydrochar
3 products have lower ash contents compared with the origin materials [23, 61]. Moreover, the
4 compressibility of hydrochar and the mechanical strength of pellets produced from hydrochar
5 (from WT) are reported to be better than those produced from the native material and the biochar
7 Despite the advantage of WT over DT with respect to the capacity of upgrading wet biomass
8 with no need of pre-drying the feedstock, most of the past studies on WT [20, 23, 62, 63] or HTC
9 [24-33] used dry woods as feedstock. Only a few works [64-66] tested WT for wet sewage
10 sludge. However, no study on WT of fresh forest residues has been reported in the open literature
11 so far. Forest residues refer to branches and tops of trees, usually discarded during wood
12 harvesting in the Nordic forests [67]. In general, chemical compositions of forest residues are
13 significantly different from stem woods. Branches for example contain much more
14 hemicelluloses and extractives than stem woods [68, 69]. The behaviour of branches during
15 torrefaction can therefore be expected to be different from stem woods. Therefore, the study
16 reported in this present paper was carried out, of which the primary objective is to evaluate the
17 process of WT for fresh branches. For this purpose, effects of torrefaction temperature and
18 holding time on the yield and fuel properties of hydrochar produced from branch woods were
19 experimentally investigated and assessed. In addition, results from this study were compared
20 with those from our previous study [23] on WT of stem woods of the same plant species.
5
1 2.1 Materials
2 Norway spruce and birch branches were selected to represent forest residues. Fresh branches of
3 2-2.5 cm in diameter were collected from a local forest in Trondheim, Norway. The bark was
4 then removed from the core wood of the branches in order to avoid possible interferences caused
5 by impurities and contaminants. The bark-removed branches were then cut into 3-4 mm thick
6 slices. The cleaned slices were then stored in a climate cabinet (series VC 0100 of Vtsch
8 Proximate analyses of the feedstocks were performed according to ASTM standards: E871,
9 E872 and D1102 for moisture content, volatile matter and ash content, respectively. Ultimate
10 analyses of the fuels were determined on dry basis by an EA 1108 CHNS-O elemental
11 analyzer (Carlo Erba Instruments). Results from the proximate and ultimate analyses are
12 presented in Table 1, which includes the higher heating values (HHV) calculated according to
15 Figure 1 demonstrates the experimental setup used in the present study, of which the main
16 components include a 250 ml Parr reactor model 4651, a bench-top ceramic heater (4923EE)
17 connected to a temperature controller (4838EE). The reactor is made of stainless steel (T316SS)
18 and equipped with a pressure gauge, a thermo-well, and two valves. A thermocouple, introduced
19 into the reactor via the thermo-well, for monitoring the WT temperature (temperature of water in
20 the reactor), is connected to the controller by which the electrical duty of the heater is controlled.
21 The WT procedure reported in our previous study [23] was adopted for the present work and
22 the torrefaction conditions are summarized in Table 2. Distilled water was used as the reaction
23 media. The ratio of dry feedstock over water was 1:5 by weight. Before every torrefaction run,
6
1 the furnace (the heater) without the reactor was heated for 30 min to a preset temperature. At the
2 same time, the reactor was loaded, closed, sealed, and purged with compressed nitrogen gas
3 (99.99% purity) for 10 minutes. Then the reactor was pressurized and placed in the preheated
4 furnace operating at the maximum power, giving a heating rate of approximately 12 C per
5 minute. The holding time was counted from the time at which the reactor temperature reached
6 the preset temperature to the end point when the reactor was removed from the furnace and
7 submerged in an ice bath for cooling. When the reactor cooled to room temperature, the pressure
8 was gradually released and the reactor was opened for collection of the products in solid and
9 liquid phases. The solid products (hydrochars) were separated from the liquid by filtration using
10 a filter paper with a pore size of 5-12 m. After separation, the collected hydrochars were
11 washed with acetone prior to being dried at 103 2 C for 24 h and then balanced. Readings
12 from the balance were recorded as the mass of dry solid product from the WT ( . The dried
13 hydrochars were then stored in a desiccator filled with silica gel for further analyses.
16 The specific grinding energy (SGE) of the branches before and after torrefaction was
17 determined using an IKA MF 10 cutting mill (from IKA-Werke GmbH & Co. KG) equipped
18 with a 1 mm bottom sieve. The grinder was connected to a current input module NI 9203 (from
19 National Instruments Corporation) to record the electrical current during grinding. A LabView
20 program was used for the data acquisition. The energy consumption was calculated and logged to
21 a file every 2 seconds. The grinding energy was determined by integrating the power curve
22 during the grinding period. The power of the mill under no-load condition was measured and
23 subtracted from the power of grinding the tested samples. Finally, the data was normalized to the
7
1 initial sample weight to obtain the specific grinding energy. More details about this assessment
4 The hydrophobicity assessment method discussed and reported in our previous study [23] were
5 adopted for the present work. The tested branches were ground and sieved through a Fritsch
6 Analysette 3 Pro vibrator to select the particles smaller than 250 m for a moisture up-take test.
7 The remaining fine powder was dried at 103 2 C for 24 h to remove any moisture up-taken
8 during the grinding and sieving periods. Approximately 2 grams of the tested sample was spread
9 on a glass Petri dish. Then the dish loaded with the powder sample was placed in a climate
11 C and 90% relative humidity. The mass changes due to the moisture up-take of the tested
12 material were recorded every 24 h for the total test period of one week. The moisture content of
% 100%, 1, 2, , 7 (1)
14 where MCi is the moisture content of the tested sample on the ith day; m0 and mi is the mass of
15 the initial dry sample and mass recorded on the ith day, respectively
18 In this section, results from studying the effects of the most important process parameters,
19 torrefaction temperature and holding time, on the yield and fuel properties of hydrochar obtained
20 from WT of the fresh branches are reported. For studying the effect of temperature (175, 200,
21 225 C), the holding time was kept constant at 30 min, whereas the temperature was maintained
8
1 at 200 C for studying the effect of holding time (10, 30, 60 min). All of the experiments in this
2 investigation were conducted at a constant pressure of 70 bar, adopted from our previous study
3 [23]. The experiments were duplicated or triplicated, from which data were collected and
6 As discussed earlier in the introduction part, solid yield is a critical indicator for a biomass
8 temperature and holding time on the yield of solid obtained from WT of the wet spruce and birch
9 branches. Figure 2 presents results from this investigation, for which the solid yield ( is
% 100% (2)
11 where and denote the mass of hydrochar and its native biomass, respectively, on a
12 dry basis.
13 As can be seen from Figure 2 the solid yield decreases with either increasing temperature or
14 holding time. When the temperature is increased from 175 to 225 C the solid yield decreases
15 from 82.0 to 67.6% and from 78.5 to 56.9% for the spruce and birch branches, respectively.
16 Also, when the holding time is varied from 10 to 60 min the solid yield decreases from 77.6 to
17 69.5% and from 64.2 to 60.2% for the spruce and birch branches, respectively. However, the
18 effect of holding time is less pronounced than that of temperature, which is similar to earlier
19 observations in comparable studies [23, 24]. In addition, these effects are more significant for the
20 birch than for the spruce, which is due to the fact that birch is a hardwood and contains more
9
1 3.1.2 Effects on energy yield and chemical composition of hydrochar
2 Another important indicator of a biomass torrefaction process is energy yield, YE, which
3 indicates how much energy that remains in the solid after the processing. YE is defined according
% (3)
(4)
5 where and respectively denote the HHV of hydrochar and the native
6 branches, on a dry basis; is the yield of hydrochar defined in Eq. (2).
7 Table 2 presents the calculated values of energy yield for WT of the branches in different
8 conditions. The table includes data from proximate and ultimate analyses and the higher heating
9 values (HHV) for the untreated branches and hydrochars obtained from the WT process. It can
10 also be observed that the energy yield constantly decreases with either increasing torrefaction
11 temperature or holding time. This trend is valid for both softwood and hardwood, being
12 decreased from 86.1 to 76.7% and from 80.4 to 64.3% for the torrefied spruce and birch,
13 respectively. However, the energy yield for spruce is always higher than that of birch in identical
14 WT conditions. This difference is presumably caused by the higher reactivity of birch than
16 In addition, Table 2 also show that the HHV increases with either increasing torrefaction
17 temperature or holding time. The increases in HHV vary from 5.0-13.5% for the torrefied spruce
18 and 2.4-13.0% for the torrefied birch, when temperature is increased from 175 to 225 C. On the
19 other hand, when holding time was prolonged from 10 to 60 min, increases in HHV are 6.2-
20 10.7% and 4.2-9.5% for the torrefied spruce and birch, respectively. It can be seen that the effect
10
1 increasing heating value, the mass energy densification of all torrefied branches increases. More
2 importantly, increases in the severity level of WT conditions result in decreases in hydrogen and
3 oxygen contents, but increases in carbon content of the hydrochar products. Consequently, both
4 H/C and O/C ratios of the hydrochar are reduced compared with their origins, as can be seen in
5 the Van Krevelen diagram presented in Figure 3. A decreasing trend of these ratios with
9 the method of the specific grinding energy (SGE) described earlier. The lower SGE a material
10 exhibits, the better grindability it has. Figure 4 presents the effects of torrefaction temperature
11 (Figure 4A) and holding time (Figure 4B) on the SGE of the torrefied spruce and birch branches
12 in different conditions. The SGE of the torrefied branches is higher than that of the native
13 material, and decreases with increasing torrefaction temperature or holding time. This clearly
14 indicates that the grindability of the branches is improved by WT and the improvement increases
15 with increasing temperature or reaction time. Among the tested conditions, the highest reduction
16 in SGE is 13.3 times for the spruce and 16.0 times for the birch. In addition, the grindability of
17 birch is improved more significantly than for spruce in identical conditions. Moreover, the
18 figures show a huge decrease in SGE of torrefied branches when the temperature increases from
19 200 to 225 C, which may be due to a change in the microstructure of the fuel. This will be
20 discussed in more detail in the next section, which presents a morphology study.
22 Results from the moisture up-take tests for the raw and torrefied spruce branches are shown in
23 Figure 5, of which Figure 5A and Figure 5B present the effects of torrefaction temperature and
11
1 holding time, respectively. Similar to the SGE for grindability, the lower moisture up-take level a
2 material exhibits, the better hydrophobicity it has. It can be seen from the figures that all of the
3 tested samples reached the equilibrium moisture content (EMC) on the second day. More
4 importantly, the hydrophobicity of the forest residue is improved by WT. The EMC decreases
5 with either increasing torrefaction temperature or holding time. Very similar trends were
6 observed for the birch branches, which are therefore not shown.
8 A morphology and structure study for the native spruce branches and branches torrefied at
9 different temperatures (for a constant holding time of 30 min) was carried out by means of a
10 table top scanning electron microscope (SEM) Hitachi TM 3000, with an accelerating voltage of
11 15 kV. SEM images at a magnification of 500 are presented in Figure 10A (for the cross
12 section) and Figure 10B (for the longitudinal section). The images show that WT alters the
13 structure of the branch wood with the occurrence of cracks and openings. The degree of structure
15 increasing temperatures. This suggests a correlation with the significant reduction in SGE of the
18 In this section, the processes of WT for branch woods and stem woods are compared. The
19 compared indicators include solid yield, energy yield, grindability and hydrophobicity. The
20 comparison focuses only on the effect of torrefaction temperature (175, 200, 225 C), i.e. holding
21 time was kept constant at 30 min. Relevant data from our previous study on WT of Norway
22 spruce and birch stem woods [23] are used to serve this comparison.
12
1 3.2.1 Comparison on solid yield
2 The yields of hydrochars obtained from WT of the stem woods and branches are presented in
3 Figure 7. Decreasing trends of the hydrochar yield with increasing WT temperature are observed
4 for all types of feedstocks. More importantly, the yields for branch woods are always lower than
5 those for the stem woods of the same plant species, torrefied in identical conditions. The
6 differences are significant for both soft and hard woods, being 6.3% at 175 C for spruce and
7 3.0% at 200 C for spruce and birch, respectively. These differences can be attributed to the
8 higher hemicelluloses and extractives contents of branch woods compared to stem woods as
9 presented in the introduction. However, while the solid yield difference between spruce branch
10 and stem woods decrease with increasing temperature, no clear trend can be observed in the case
11 of birch.
13 The energy yields for WT of the four feedstocks at different temperatures are presented in
14 Figure 8. Similar to solid yield, decreasing trends of energy yield with increasing WT
15 temperature are observed for all of the feedstocks. In addition, the energy yields for branch
16 woods are always lower than those of the stem woods, torrefied in identical conditions. This
17 similarity can only be attributed to the decreasing trend of solid yield with increasing
18 temperature, considering the relationship between solid yield and energy yield in Eq. (3). It is
19 because of the fact that HHV, embedded in the DE term of Eq. (3), of hydrochar increases with
20 increasing torrefaction temperature (discussed in Section 3.1.2). This indicates that the solid
21 yield decreases faster than the HHV increase with increasing torrefaction temperature. In
22 addition, no clear trend of differences in energy yield between branch and stem woods can be
23 observed.
13
1 3.2.3 Comparison on grindability
2 Figure 9 presents the results from SGE measurements for the stems and branches, untreated
3 and torrefied at different temperatures. The data of the first point (Raw) were calculated on the
4 basis of triplicate measurements, but those of the others were based on single measurements only
5 due to the small reactor volume and thus limited amounts of hydrochar produced in the WT
6 experiments. The triplicate measurements were performed for the untreated woods confirm that
7 while the grindability of untreated spruce branch is better than untreated spruce stem wood, the
8 situation for untreated birch is opposite. In order to understand this observation, different
9 strength measurements are needed which is beyond the scope of the present work. More
10 importantly, differences in grindability between branch and stem woods for spruce are always
11 more significant and consistent than for birch. At 200 C, the grindability of both spruce and
12 birch branches are better than their stem woods. The difference at this point is 8.1% for torrefied
13 spruce and 10.9% for torrefied birch. Thereafter, virtually no significant difference in SGE
14 between branch and stem woods can be observed at point 225 C. Overall, reductions in SGE
15 with increasing torrefaction temperature are observed for all tested woods. In addition, the SGE
16 dramatically decreases when temperature is increased from 200 to 225 C. The highest reduction
19 The EMC data for the stems and branches, untreated and torrefied in various conditions are
20 presented in Figure 10. It appears that untreated branches consistently exhibit higher EMC values
21 than the corresponding stem woods. This is presumably due to the higher hemicelluloses and
14
1 more hydroxyl groups than celluloses and lignin [71]. In addition, extractives may be
2 hydrophilic in nature.
3 At 175 C, WT makes branches more hydrophobic than the corresponding stem woods. This
4 confirms the hydrophilic nature of the extractives. It is because plant biomass extractives have
5 smaller molecular and thus less thermally stable than hemicelluloses. In other words, the
6 extractives should have been decomposed first and responsible for the significant reductions in
7 EMC at point 175 C. In addition, the differences in EMC between branch and stem woods
8 become most significant at 200 C, being 15.7% and 10.3% for spruce and birch, respectively.
11 4 Conclusions
12 WT enhances significantly the fuel properties of Norway spruce and birch branches. The yield
13 of hydrochars produced from branch woods via WT processes decreases with increasing
14 torrefaction temperature and/or holding time. However, the improvements in fuel properties of
15 hydrochar increase with increasing torrefaction temperature and/or holding time. Increases in
16 HHV up to 13.5% and reductions of specific grinding energy up to 16.0 times for the wet
17 branches could be achieved via WT. In addition, birch branches are more reactive than spruce
19 The comparison on WT of the branches and the stem woods show that the effect trends of WT
20 on the yield and fuel properties of the hydrochars from branches and stems were similar.
21 However, branch woods are more reactive than stem woods in identical WT conditions. The
22 trend of reduction in SGE of branches is similar to stem woods for spruce, but that for birch is
15
1 than that of the stems. This may be attributed to the higher hemicellulose and extractives
3 5 Acknowledgements
4 This work is financially supported by the Research Council of Norway and industry partners
5 through the KMB project STOP (STable OPerating conditions for biomass combustion plants),
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31
21
1 Table 1. Fuel characteristics of the feedstocks.
2
Proximate analysisb Ultimate analysisb
Type of Moisture
HHVc
feedstock contenta
Ash VM FC C H O N S
Spruce 49.962.34 0.680.05 85.180.26 14.140.15 51.310.14 6.220.09 42.350.06 0.1220.01 <0.02 20.840.07
Birch 56.311.93 0.640.04 89.740.32 9.630.09 48.550.17 6.190.06 45.090.14 0.1650.03 <0.02 19.630.06
a b c
3 wt %; wt %, dry basis; MJ/kg, dry and ash free basis
4 VM: volatile matter, FC: fixed carbon
5
22
1 Table 2. Torrefaction conditions and fuel characteristics of hydrochars obtained from wet torrefaction of forest residues (dry basis).
Raw 0.68 85.18 14.14 51.31 6.22 0.122 42.35 < 0.02 20.86
175C-30min 0.54 82.40 17.06 54.08 6.06 0.140 39.72 < 0.02 21.91 1.05 86.09
200C-10min 0.58 81.61 17.81 54.73 6.02 0.147 39.10 < 0.02 22.16 1.06 82.48
Spruce
200C-30min 0.52 80.76 18.72 56.86 5.88 0.160 37.09 < 0.02 22.95 1.10 80.98
200C-60min 0.46 76.04 23.50 57.51 5.77 0.148 36.58 < 0.02 23.09 1.11 76.98
225C-30min 0.50 74.82 24.68 59.41 5.55 0.167 34.87 < 0.02 23.67 1.13 76.75
Raw 0.64 89.74 9.63 48.55 6.19 0.165 45.09 < 0.02 19.56
175C-30min 0.56 88.19 11.25 49.84 6.10 0.184 43.88 < 0.02 20.03 1.02 80.44
200C-10min 0.61 86.66 12.73 50.87 6.01 0.228 42.90 < 0.02 20.39 1.04 66.94
Birch
200C-30min 0.55 83.40 16.04 52.48 5.98 0.232 41.31 < 0.02 21.08 1.08 66.98
200C-60min 0.61 81.63 17.76 53.63 5.84 0.206 40.32 < 0.02 21.42 1.09 65.97
225C-30min 0.65 79.67 19.68 55.23 5.80 0.231 38.74 < 0.02 22.10 1.13 64.28
VM = volatile matter: FC = fixed carbon; a: ash free; *: lower than the detection limit.
2
23
1 Figuree 1. Schemaatic diagram
m of the expeerimental seetup and thee reactor.
2
3
24
1 Figure 2. Effects of (A) torrefaction temperature and (B) holding time on the hydrochar yield
2 of spruce and birch branches.
70
60
50
175 200 225
Temperature (C)
3
70
60
50
10 30 60
Holding time (min)
4
25
1 Figure 3. Van Krevelen diagram for the raw and torrefied branches in different conditions.
1.3
1.2
1.1
0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75
Atomic O/C
2
1.3
1.2
1.1
0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75
Atomic O/C
3
26
1 Figure 4. Effects of (A) torrefaction temperature and (B) holding time on specific grinding
2 energy of raw and torrefied branches.
120
80
40
0
Raw 175 200 225
Temperature (C)
3
120
80
40
0
Raw 10 30 60
Holding time (min)
4
27
1 Figure 5. Moisture uptake behavior of raw spruce branches and spruce branches torrefied at
2 different (A) torrefaction temperatures and (B) holding times.
20
15
10
Raw
5 175C
200C
225C
0
0 1 2 3 4 5 6 7
Days
3
20
15
10
Raw
5 10 min
30 min
60 min
0
0 1 2 3 4 5 6 7
Days
4
28
1 Figure 6. SEM images of the raw spruce branches and branches torrefied at different
2 temperatures.
Torrefaction
Cross section Longitudinal section
temperature
Raw sample
175 C
200 C
29
225 C
30
1 Figure 7. Hydrochar yield for branch and stem woods torrefied in subcritical water for 30 min.
Spruce stem
90 Spruce branch
Birch stem
Birch branch
Hydrochar yield (%)
80
70
60
50
175 200 225
Temperature (C)
2
3
31
1 Figure 8. Energy yield for branch and stem woods torrefied in subcritical water for 30 min.
Spruce stem
Spruce branch
90
Birch stem
Birch branch
Energy yield (%)
80
70
60
175 200 225
Temperature (C)
2
32
1 Figure 9. Specific grinding energy (SGE) for branch and stem woods torrefied in subcritical
2 water for 30 min.
160
120
SGE (kWh/t)
80
Spruce stem
40
Spruce branch
Birch stem
Birch branch
0
Raw 175 200 225
Temperature (C)
3
33
1 Figure 10. Equilibrium moisture content (EMC) for branch and stem woods torrefied in
2 subcritical water for 30 min.
25
Spruce stem
Spruce branch
20 Birch stem
Birch branch
EMC (%)
15
10
5
Raw 175 200 225
Temperature (C)
3
34
PaperV
EffectsofCO2onwettorrefactionofbiomass
QuangVuBach,KhanhQuangTran,RogerA.Khalil,andyvindSkreiberg.
EnergyProcedia,accepted.
Available onliine at www.scciencedirect.co
om
Energy Procedia
P 00 (20114) 000000
www.elsevier.com
w m/locate/procediaa
Abstract
Effects of COO2 on the yield and fuel propeerties of the sollid product obtaained from wett torrefaction off biomass weree
experimentallly investigated.. Norwegian forrest residues weere used as feedstock. CO2 an nd N2 were empployed as purgee
gas, separatelly. The results show
s pared with wet torrefaction in N2, the processs in CO2 is takinng place faster,,
that, comp
producing 4.66-6.0% less sollid product witth lower heating
ng value in iden ntical conditionn. A reduction oof 6.5kWh/t in n
SGE and an iincrease of up to t 1.4% in EMC C were observe d for the solid product
p obtaineed from WT in CO2 compared d
with that in N2. In addition, CO
C 2 enhances the
t capacity of wet torrefaction n to remove ashh elements fromm solid biomasss
fuels.
Keywords: Wett torrefaction; Bioomass fuels; Foreest residues; Flue gas utilization.
1. Introducction
Wet torrrefaction (WT) of biomass is a methhod of hydrothermal processing for uppgrading and d
production of solid fuels with impro oved fuel prooperties such as increased heating valuue and betterr
grindability [1, 2]. The prrocess may bee defined as m mild pyrolysiss of biomass in n hot compresssed water, in n
the temperatture range of 180-260C [1 1, 2], and there
refore is very much
m suitablee for wet feeddstocks, whichh
include foreest residues, wet
w agriculturaal wastes, sew wage sludge, and
a aquatic en nergy crops. IIn addition too
the main soolid product, WT also pro oduces liquidd by-products including waater soluble aand insolublee
organic commpounds, whicch can be furth her treated forr the productio
on of biogas, liquid
l fuels annd/or valuablee
chemicals [33, 4].
Recent sstudy in a batch reactor show that W WT exhibits several
s advanntages compaared with dry y
torrefaction (DT), whichh include the capacity of washing out ash elements from biomaass fuels [2]..
However, liike DT, WT requires
r nert atmospherre, for which a large amou
an in unt of nitrogenen for purgingg
and pressurrizing is norrmally used. The nitrogenn requiremen nt will be much
m larger ffor industriall
applicationss and up-scalinng of the tech
hnology, for w which continuo ous processes may also be employed. In n
such a context, the concept of process integration including heat integration should be considered [5, 6].
For this purpose, utilization of hot flue gas from thermal power plants would be a potential option. The
problem however is that, apart from N2, flue gas contains other gases, of which CO2 is the main species
and may have important effects on the WT process and the fuel properties of the solid product. For this
reason, some studies on influences of CO2 addition have been reported [7, 8] for DT of biomass, but not
for WT. In the present work, WT of Norwegian forest residues (FR) was experimentally studied under
different conditions with N2 or CO2 addition. The effect of CO2 addition on the solid product yield and its
fuel properties was investigated.
3. Results
3.1. Effects on the solid yield
(A) - Holding time of 30 min (B) - Torrefaction temperature of 200C
WT in N2 WT in N2
80 80
Solid product yield (%)
WT in CO2 WT in CO2
Solid product yield (%)
60 60
40 40
20 20
0 0
175 200 225 10 30 60
Fig. 1. Solid yield for WT of FR at different temperatures (A) and holding times (B)
Fig. 1 A and B show the yield of solid products obtained from the WT in N2 or CO2 atmosphere with
varying temperature or holding time, respectively. The figures indicate no difference in the trend of the
effects of these two process parameters on the solid yield for the two different cases with regards to the
gas atmosphere. The solid yield for both cases decreases with either increasing torrefaction temperature or
holding time. However, at the same hydrothermal conditions less solid is produced in the case of CO2
addition than that of N2 addition. This indicates that CO2 has a positive effect on the reaction rate of
biomass WT, compared to N2. In addition, this effect seems more significant at higher temperatures and
longer holding times. The yield difference is within 4.6-6.0% and 3.8-5.7% for temperatures of 175-
225C and holding times of 10-60 min, respectively.
3.2. Effects on fuel properties of the solid product
Fig. 2 A and B present the heating value of solid products obtained from the WT in N2 or CO2
atmosphere with varying temperature or holding time, respectively. In all cases, the heating value of the
solid product obtained from the WT with CO2 addition is slightly lower than that of N2 addition.
Q. V. Bach et al./ Energy Procedia 00 (2014) 000000 3
Moreover, the difference in HHV of solid from the WT in CO2 and N2 becomes less significantly when
either increasing WT temperature or holding time.
(A) - Holding time of 30 min (B) - Torrefaction temperature of 200C
WT in N2 WT in N2
20 20
15 15
10 10
175 200 225 10 30 60
Temperature (C) Holding time (min)
Fig. 2. Heating values of solids from WT of FR at different temperatures (A) and holding times (B)
Proximate analysis data for the solid obtained from the WT in different gas atmospheres are presented
in Table 1, and indicates that increased reaction temperature or holding time results in increased fixed-
carbon (FC) content but decreased volatile matter (VM) content of the solid product. More interestingly,
the ash content of the FR torrefied in CO2 is significantly lower than that in N2.
WT in N2 WT in CO2
Torrefaction condition
Ash (%) VM (%) FC (%) Ash (%) VM (%) FC (%)
175C30min 0.54 82.40 17.06 0.35 82.29 17.36
200C10min 0.58 81.61 17.81 0.34 81.18 18.49
200C30min 0.52 80.76 18.72 0.21 78.79 21.00
200C60min 0.46 76.04 23.50 0.26 75.84 23.90
225C30min 0.50 74.82 24.68 0.21 72.83 26.96
Data for dry raw feedstock: Ash: 0.68%, VM: 85.18%, FC: 14.14%
(B)
150 25
(A)
Specific grinding energy (kWh/t)
WT in N2
Moisture uptake level (%)
WT in CO2
20
100
15
10
50
5 Raw
175C - in CO2 175C - in N2
200C - in CO2 200C - in N2
0 225C - in CO2 225C - in N2
0
Raw 175
-- 200
-- 225
--
0 1 2 3 4 5 6 7
Temperature (C) Days
Fig. 3. Effect of WT temperature on the specific grinding energy (A) and the moisture uptake level (B)
The specific grinding energy (SGE) and the moisture uptake level of raw and torrefied FR are
presented in Fig. 3A and 3B, respectively. The reductions in SGE and moisture uptake level show similar
trends for the materials torrefied in CO2 or N2. However, the samples torrefied in CO2 exhibit lower SGE
values than those in N2. The most significant reduction in SGE is 6.5kWh/t recorded for the samples
torrefied in the conditions of 200C and 30 min. Further increases in temperature led to no more reduction
4 Q. V. Bach et al./ Energy Procedia 00 (2014) 000000
in SGE. Nevertheless, the equilibrium moisture content (EMC) of the samples torrefied in CO2 is
significantly lower than that in N2. The difference in EMC becomes more significant, being up to 1.4%
when the temperature is increased from 175 to 225C. The effects of holding time on the grindability and
hydrophobicity show similar trends but less pronounced compared with the effects of temperature.
4. Discussion
The use of CO2 for WT of biomass instead of N2 results in lower yield and slightly decreased heating
value of the solid product in identical WT conditions. This can be translated to positive effects of CO2
addition on the reaction rate of WT. Similar effects of CO2 addition have been found for DT [7], in which
increased weight loss and improved grindability when adding CO2 was reported. For WT in the present
work, the effects of CO2 may be explained by the fact that dissolved CO2 in water has an acidic catalyst
effect and enhances the reaction rate of biomass treatment in hydrothermal conditions [9, 10]. This
catalytic enhancement effect is also valid for the solubility of inorganic ions present in biomass during
hydrothermal pre-treatment. It suggests that WT in CO2 is capable of removing even more ash elements
in the solid biomass fuel, compared with WT in N2. If utilizing hot flue gases, the positive CO2 effect on
the WT process will depend on its CO2 content.
5. Conclusion
Wet torrefaction of Norwegian forest residues in different conditions and atmospheres were
experimentally investigated. WT in CO2 produced 4.6-6.0% less solid product with decreased heating
value but improved hydrophobicity and better hydrophobicity than in N2. An increase of up to 1.4% in
EMC and a reduction of 6.5kWh/t in SGE were observed for the solid product obtained from WT in CO2
compared with that in N2. The proximate analyses show higher fixed carbon and lower volatile matter
contents for the solid products obtained from WT in CO2. Additionally, the ash content of these products
is significantly reduced, compared with that in N2.
6. Acknowledgement
This work is financially supported by the Research Council of Norway and industry partners through the KMB project STOP
(STable OPerating conditions for biomass combustion plants), which is gratefully acknowledged.
7. References
[1] W. Yan, T. C. Acharjee, C. J. Coronella, and V. R. Vsquez, "Thermal pretreatment of lignocellulosic biomass," Environmental
Progress & Sustainable Energy, vol. 28, pp. 435-440, 2009.
[2] Q. V. Bach, K.-Q. Tran, R. A. Khalil, . Skreiberg, and G. Seisenbaeva, "Comparative assessment of wet torrefaction," Energy
& Fuels, vol. 27, pp. 6743-6753, 2013.
[3] S. K. Hoekman, A. Broch, and C. Robbins, "Hydrothermal Carbonization (HTC) of Lignocellulosic Biomass," Energy & Fuels,
vol. 25, pp. 1802-1810, 2011/04/21 2011.
[4] W. Yan, J. T. Hastings, T. C. Acharjee, C. J. Coronella, and V. R. Vsquez, "Mass and Energy Balances of Wet Torrefaction of
Lignocellulosic Biomass," Energy & Fuels, vol. 24, pp. 4738-4742, 2010.
[5] G. Xu, S. Huang, Y. Yang, Y. Wu, K. Zhang, and C. Xu, "Techno-economic analysis and optimization of the heat recovery of
utility boiler flue gas," Applied Energy, vol. 112, pp. 907-917, 2013.
[6] B. Kilkovsky, P. Stehlik, Z. Jegla, L. L. Tovazhnyansky, O. Arsenyeva, and P. O. Kapustenko, "Heat exchangers for energy
recovery in waste and biomass to energy technologies I. Energy recovery from flue gas," Applied Thermal Engineering.
[7] D. Eseltine, S. S. Thanapal, K. Annamalai, and D. Ranjan, "Torrefaction of woody biomass (Juniper and Mesquite) using inert
and non-inert gases," Fuel, vol. 113, pp. 379-388, 2013.
[8] A. Sarvaramini and F. Larachi, "Integrated biomass torrefaction Chemical looping combustion as a method to recover
torrefaction volatiles energy," Fuel, vol. 116, pp. 158-167, 2014.
[9] T. Miyazawa and T. Funazukuri, "Polysaccharide Hydrolysis Accelerated by Adding Carbon Dioxide under Hydrothermal
Conditions," Biotechnology Progress, vol. 21, pp. 1782-1785, 2005.
[10] S. E. Hunter and P. E. Savage, "Quantifying rate enhancements for acid catalysis in CO2-enriched high-temperature water,"
AIChE Journal, vol. 54, pp. 516-528, 2008.
PaperVI
Influencesofwettorrefactiononpelletabilityandpellet
propertiesofNorwegianforestresidues
QuangVuBach,NevenaMiljenovi,KhanhQuangTran,CarlosSalasBringas,
andyvindSkreiberg.
AnnualTransactionsTheNordicRheologySociety2014,22,6168.
ANNUAL TRANSACTIONS OF THE NORDIC RHEOLOGY SOCIETY, VOL. 22, 2014
Table 1. WT conditions and fuel properties of the raw forest residues and their hydrochars
Sample Solid yielda MCb Asha VMa FCa HHVc
Raw 10.30 0.23 86.50 13.27 20.42
Torrefied for 30 min in water at 70 bar and different temperatures
Spruce
6
higher than that of the raw spruce. This
4 increasing trend continued and got close to
2
the compressibility of the spruce
hydrochars, produced at the other
0
temperatures, at the highest compressing
1 10 100 1000
Particle size (m) pressure (240 MPa). Similar trends were
observed for birch but the improvements in
the compressibility by WT were more
10
(B) Birch pronounced than those for spruce.
Raw
175C
200C
However, unlike spruce, the birch torrefied
8
225C at 225C was better compressible than the
Volume density (%)
1000 1000
Density (kg/m3)
Density (kg/m3)
800 800
600 600
1400 1400
(C) Birch, pelletized at 120C (D) Birch, pelletized at 180C
1200 1200
1000 1000
Density (kg/m3)
Density (kg/m3)
800 800
600 600
Since the density and mechanical same density value, hydrochar pellets were
strength of the pellets were both increased mechanically stronger than the raw
with pelletizing pressure, the correlation material pellets. The effect of WT
between these two properties was temperature was more pronounced for
evaluated. Results from this evaluation are spruce than birch. Below the density of
presented in Fig 6, in which fitting curves 1000 kg/m3, large increases in density
also are included. The figure shows an results in only small increases in the
exponential relationship between the two strength. However, this relationship was
properties. The pellets with higher density reversed when the density was higher than
also had higher mechanical strength. At the 1000 kg/m3.
ANNUAL TRANSACTIONS OF THE NORDIC RHEOLOGY SOCIETY, VOL. 22, 2014
150 150
(A) Spruce, pelletized at 120C (B) Spruce, pelletized at 180C
120 120
90 90
60 60
Raw Raw
30 30 175C
175C
200C 200C
225C 225C
0 0
0 50 100 150 200 250 0 50 100 150 200 250
Compacting pressure (MPa) Compacting pressure (MPa)
150 150
(C) Birch, pelletized at 120C Raw (D) Birch, pelletized at 180C
175C
120 200C 120
90 90
60 60
Raw
30 30 175C
200C
225C
0 0
0 50 100 150 200 250 0 50 100 150 200 250
Compacting pressure (MPa) Compacting pressure (MPa)
Fig 5. Mechanical strength of pellets made from different compacting pressures and
temperatures.
150 150
(A) Spruce, pelletized at 120C (B) Spruce, pelletized at 180C
120 120
Strength (N/mm)
Strength (N/mm)
90 90
Raw Raw
175C 175C
200C 200C
60 60
225C 225C
30 30
0 0
0 300 600 900 1200 1500 0 300 600 900 1200 1500
Density (kg/m3) Density (kg/m3)
150 150
(C) Bich, pelletized at 120C (D) Bich, pelletized at 180C
120 120
Strength (N/mm)
Strength (N/mm)
90 90
Raw Raw
175C 175C
200C 200C
60 60 225C
225C
30 30
0 0
0 300 600 900 1200 1500 0 300 600 900 1200 1500
Density (kg/m3) Density (kg/m3)
Fig 6. Relationship between density and strength of pellets produced at different compacting
temperatures.
Increasing the pelletizing temperature pressure higher than 80 MPa for the
from 120 to 180C had a little effect on the production of pellets due to the benefit
pellet density but improves the pellet form the exponential relationship between
strength. This is addressed to the the pellet strength and density.
behaviours of lignin below and above its
glass transition temperature (Tg), which is CONCLUSION
around 135-165C8. At a temperature WT improved the fuel properties and
higher than the Tg, lignin softens and reduced specific grinding energy of the
enhances the inter-particles binding, which FRs. The average particle size of ground
improves the mechanical strength of hydrochar was smaller than that for raw
pellets13. Therefore, the pellets made at FR and gradually decreased with
180C were stronger than pellets produced increasing WT temperature. The pellets of
at 120C, at the same compacting pressure. wet-torrefied FR were better compressible
Pelletization at higher compacting and stronger than the pellets of raw FR.
pressure produced pellets with higher Increases in density for the hydrochar
density and strength. It is also shown that a pellets compared to the pellets of raw
small increase in density resulted in a large materials was up to 159 kg/m3 for spruce
increase in strength if the density of pellet and 213 kg/m3 for birch. Improvements in
was higher than 1000 kg/m3, which can be the strength of torrefied pellet compared to
achieved by applying a compacting raw pellet were up to 3.4 and 2.7 times for
pressure above 80 MPa. Although more spruce and birch, respectively. The effect
energy is required, it is recommended a of pelleting temperature on pellet density
was unpronounced but the effect on pellet blends", Biomass and Bioenergy, 63(0): p.
strength was significant due to different 229-238.
behaviours of lignin below and above its
glass transition temperature. Increasing 7. Liu, Z., A. Quek, and R.
compacting pressure increased the mass Balasubramanian, (2014), "Preparation and
density and strength of the pellets. characterization of fuel pellets from woody
biomass, agro-residues and their
ACKNOWLEDGMENTS corresponding hydrochars", Applied
This work is financially supported by Energy, 113(0): p. 1315-1322.
the Research Council of Norway and 8. Reza, M.T., J.G. Lynam, V.R. Vasquez,
industry partners through the KMB project and C.J. Coronella, (2012), "Pelletization
STOP (STable OPerating conditions for of biochar from hydrothermally carbonized
biomass combustion plants. wood", Environmental Progress &
Sustainable Energy, 31(2): p. 225-234.
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