Woody and agricultural biomass torrefaction: a new approach to … · 2018-09-18 · Woody and...

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


Energy Chemicals Materials

Biomassdiversity

Production•seasonal•delocalized•Low amounts

FLEXIBLE and MOBILEtreatment technology

Context1


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


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


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


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.


3.1


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


4.11.Rawbiomass

Results

Biomass diversity 4representativefamiliesDeciduous wood Coniferous wood

Herbaceous crops Agriculturalby-products

Solidtransformation

pine

ash wood

wheat straw

miscanthus

beech



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»


Cellulosefractioncharacterization:Mmdistribution,Polymerization Degree,Crystallinity (DRX)



[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]



Similar behavior oftheextracted celluloses

Cellulose

Ash-woodBeechMiscanthusPineWheat strawCommercialcompound






CI

H1H2L

E

A

CI

H1H2E

L

CI

H1H2

E

CI

H2

H1

CII

H2Dioxane

Acetone/H2Ochlorite

DMSO

NaOH

EXTRACTIONPROCEDURE

Raw biomassDMSOresidue

Lignin

« CelluloseII»



HT=H1 +H2Totalhemicelluloses






HemicellulosesT

Sugarmassbalance, = , , + , ( ,

Hemicelluloses1 Hemicelluloses2

Ash-wood Beech Miscanthus Pine Wheat straw

Strongly degraded intorrefactionbehavior dependent onthesugar composition

Hemicelluloses:



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


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


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


4.2 Volatilespecies release Results

Cellulose LigninHemicellulosespineash woodwheat strawmiscanthusbeech


• 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

Marί[email protected]

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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Woody and agricultural biomass torrefaction: a new approach to … · 2018-09-18 · Woody and...

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