Woody and agricultural biomass torrefaction:a new approach to model solid conversion and volatiles
formation based on biomass extracted components
María González Martínez1,2,3, Capucine Dupont4, Sébastien Thiéry1,Denilson Da Silva Perez5, Xuan-mi Meyer2,3, Christophe Gourdon2,3
(1) Laboratoire de Préparation des Bioressources; CEA, Grenoble, FRANCE(2) Université de Toulouse; INPT, UPS; Laboratoire de Génie Chimique, Toulouse, France / (3) CNRS; Laboratoire de Génie Chimique, Toulouse, FRANCE
(4) IHE Delft Institute for Water Education, Department of Environmental Engineering and Water Technology, Delft, THE NETHERLANDS(5) FCBA, InTechFibres, Grenoble, FRANCE
July 2-5, 2018 Prague - Czech Republic7th International Conference on Engineering for Waste and Biomass Valorisation
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 2
BIOMASSin Europe BIOMASS
Diversity
ß Deciduous wood
ß Coniferous wood
ß Agriculturalby-products
ß Herbaceous crops
Context1
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 3
Energy Chemicals Materials
Biomassdiversity
Production•seasonal•delocalized•Low amounts
FLEXIBLE and MOBILEtreatment technology
Context1
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 4
BIOMASS TORREFACTION
200– 300°C
P(atm)10min– 1h
Inert atmosphere
ß ↑heating value
ß hydrophobic
ß ↑flowability
ß ↑grindability
ß usesRaw biomass
Torrefiedsolid
Gaseous products
ß harmful fortheprocessß chemicals (added value)
↓transportcost
Energy
Chemicals
Materials
~70%mass
Permanentgases (CO,CO2)Volatilespecies (furans,ketones,phenols)
Context1
Water
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 5
ProductionTorrefiedsolid production
Volatilespecies release
Optimaloperatingconditions
Temperature
Residence time
Heating rate
Biomassmacromolecular
composition
Cellulose
Lignin
Hemicelluloses
EXTRACTED fromeach biomass
Rbiomass =Rcellulose .%cellulose +Rhemicellulose .%hemicellulose +Rlignin .% lignin [1]
[1]Nocquet T.,DupontC.,Commandre J-M.,Grateau M.,Thiery S.,SalvadorS.,2014,Volatilespeciesreleaseduringtorrefactionofbiomassanditsmacromolecularconstituents:Part2- Modelingstudy.Energy72,188-194.
Ri:torrefactionyield ofi%i:initialmassfractionofii:cellulose,hemicellulose,lignin
Comprehension+Modelling
Biomasstorrefaction 200-300°C,inert atmosphere (He),<1h
pine
ashwood
wheatstraw
miscanthus
Objectiveandapproach
MODEL validation20 European biomases
from Mobile Flip project
5 reference biomasses
beech
2
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 6
Shrublands + oak (biomasses involved in forest fires)
Representative biomasses
Deciduous wood (behavior) Herbaceous crops(behavior)
yellow broom white broom oak ferngorse heather
MaterialsBiomass diversity
3.1
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 7
MaterialsExtractionprocedure
•Considerations:•Final available extracted fractions (they were torrefied) in dark blue boxes (L, H1, H2, CII, DMSO residue).•Cellulose crystallinity indicated by the super-index I and II.•Hemicelluloses recuperated in two fractions, indicated by the sub-index 1 and 2.•Ash and extractives considered as inert fractions in biomass torrefaction.
5 reference biomasses
3.1
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 8
GCMSHeatedStorageLoops
TGA
3°C/min
200
300TGA-GC/MS
Thermobalance+Gas chromatography/mass
spectrometry
Biomass torrefactionSolidweight loss analysis and
volatilespecies production
TGA– Heated storage loops - GCMS
11gaseous samples perexperiment(following non-isothermal torrefaction)
Methodology
Torrefaction:200-300°C,3°C/min+300°C/30min
3.2
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 9
4.11.Rawbiomass
Results
Biomass diversity 4representativefamiliesDeciduous wood Coniferous wood
Herbaceous crops Agriculturalby-products
Solidtransformation
pine
ash wood
wheat straw
miscanthus
beech
5 reference biomasses
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 10
Cellulose LigninHemicelluloses
4.1 ResultsSolidtransformation
pineash wood wheat strawmiscanthusbeech
2.Extractedmacromolecularcomponents
CI
H1H2L
E
A
CI
H1H2E
L
CI
H1H2
E
CI
H2
H1
CII
H2Dioxane
Acetone/H2Ochlorite
DMSO
NaOH
EXTRACTIONPROCEDURE
Raw biomassDMSOresidue
Lignin
« CelluloseII»
« Hemicelluloses 1»
« Hemicelluloses 2»
Cellulosefractioncharacterization:Mmdistribution,Polymerization Degree,Crystallinity (DRX)
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 11
Cellulose LigninHemicelluloses
[2]GonzalezMartinezM.,DupontC.,Thiery S.,DaSilvaPerezD.,KarakashovB.,MeyerX.M.,GourdonC.,2016,TorrefactionofVariousWoodyandAgriculturalBiomassesandoftheirextractedCellulose,HemicelluloseandLigninthroughTGA-GCMS.21st InternationalSymposiumonAnalyticalandAppliedPyrolysis– Nancy,France,9-12May2016(oralpresentation).
Avicel (commercialmicrocristallinecellulose)is notarepresentative modelofcellulosebehaviour inbiomass torrefaction [2]
4.1 ResultsSolidtransformation
pineash wood wheat strawmiscanthusbeech
Similar behavior oftheextracted celluloses
Cellulose
Ash-woodBeechMiscanthusPineWheat strawCommercialcompound
2.Extractedmacromolecularcomponents
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 12
Cellulose LigninHemicelluloses
4.1 ResultsSolidtransformation
pineash wood wheat strawmiscanthusbeech
CI
H1H2L
E
A
CI
H1H2E
L
CI
H1H2
E
CI
H2
H1
CII
H2Dioxane
Acetone/H2Ochlorite
DMSO
NaOH
EXTRACTIONPROCEDURE
Raw biomassDMSOresidue
Lignin
« CelluloseII»
« Hemicelluloses 1»
« Hemicelluloses 2»
HT=H1 +H2Totalhemicelluloses
2.Extractedmacromolecularcomponents
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 13
Cellulose LigninHemicelluloses
4.1 ResultsSolidtransformation
pineash wood wheat strawmiscanthusbeech
HemicellulosesT
Sugarmassbalance, = , , + , ( ,
Hemicelluloses1 Hemicelluloses2
Ash-wood Beech Miscanthus Pine Wheat straw
Strongly degraded intorrefactionbehavior dependent onthesugar composition
Hemicelluloses:
2.Extractedmacromolecularcomponents
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 14
4.12.Extractedmacromolecularcomponents
ResultsSolidtransformation
Ash-wood Beech Miscanthus Pine Wheat straw
Cellulose LigninHemicellulosespineash woodwheat strawmiscanthusbeech
Similar behaviorOnly fewdegraded intorrefaction
rawb (t,T) = %cell0(rawb) CII(t,T) + %hemic0,T(rawb) HT(t,T) + %lign0(rawb) L(t,T)
Cellulose Hemicelluloses Lignin
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 15
SOLID
rawb (t,T) = %cell0(rawb) CII(t,T) + %hemic0,T(rawb) HT(t,T) + %lign0(rawb) L(t,T)
Modelling5Solidtransformationmodelling
pineash wood
wheat strawmiscanthus
beech
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 169
Chemical family Chemicalcompound //Sample cellulose hemicelluloses lignin rawbiomass
Acidaceticacid X X X Xformicacid X Xpropionicacid * X X
Alcohol methanol X X X XAldehyde formaldehyde X X X
Furan
furan * X * X3-furaldehyde X * *furfural X X X X2-furanmethanol * X Xacetylfuran * * * *2(5H)-furanone X X * X
Phenol
phenol * * X Xphenol,2-methoxy(guaiacol) * * X X2-methoxy-4-vinylphenol X Xeugenol X Xcathecol X Xphenol,2,6-dimethoxy- (syringol) * X Xisoeugenol(cis+trans) * X XVanillin * X X
Linear ketone2,3-pentanedione * X * Xhydroxyacetone X X * X2-propanone,1-(acetyloxy)- X X * X
Cyclic ketone 4-cyclopentene-1,3-dione X X * X
4.2 Volatilespecies release ResultsChemical family Chemicalcompound
Acidaceticacidformicacidpropionicacid
Alcohol methanolAldehyde formaldehyde
Furan
furan3-furaldehydefurfural2-furanmethanolacetylfuran2(5H)-furanone
Phenol
phenolphenol,2-methoxy(guaiacol)2-methoxy-4-vinylphenoleugenolcathecolphenol,2,6-dimethoxy- (syringol)isoeugenol(cis+trans)Vanillin
Linear ketone2,3-pentanedionehydroxyacetone2-propanone,1-(acetyloxy)-
Cyclic ketone 4-cyclopentene-1,3-dione
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 17
4.2 Volatilespecies release Results
Cellulose LigninHemicellulosespineash woodwheat strawmiscanthusbeech
María GONZALEZ MARTINEZ Woody and Agricultural Biomass Torrefaction:A New Approach to Model Solid Conversion and Volatiles Formation Based on Biomass Extracted Components 18
• Goodknowledgeoftherawbiomassvariabilityrequiredfortorrefactionmodelling
• Promisingmethodology:TGA-GC/MScouplingthroughheatedstorageloopsÆ Solidandvolatilespeciesevolutionintorrefactionf(T,t)
• Macromolecularcomponentsapproachtobiomasstorrefaction:Æ Biomassrepresentationimprovedwith extracted fractionsÆ Microcrystallinecelluloseisnotsatisfactorytorepresentcellulose torrefactionbehaviorÆ Macromolecularcomponentsaredegradedindifferentextents
Æ Hemicellulosessugarcompositionisdeterminant
Conclusions
Conclusionsandperspectives6
Perspectives• Refiningofthesolidkineticsmodel:
Æ Interactions(interandintramacromolecularcomponents)Æ Celluloseproperties(Mm,polymerizationdegree,crystallinity)
• Modelvalidationwith20biomasses• Modellingvolatilespeciesproduction
Thank you foryour attention
ACKNOWLEDGEMENTS: This project has received funding from the European Union’s Horizon 2020 research and innovation program under grantagreement No 637020−MOBILE FLIP. P
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