Nowadays, there is an increasing awareness on the importance of biomass waste as a renewable source of energy, materials and chemicals. In this context, the European project MOBILE FLIP aims at developing and demonstrating mobile conversion processes suitable with various underexploited agro- and forest based biomass resources in order to produce energy carriers, materials and chemicals. One of these processes is torrefaction, which consists in a mild thermal treatment, occurring typically between 200 and 300°C during a few tens of minutes in a default-oxygen atmosphere.
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Dupont, Capucine

González Martínez, María

Gourdon, Christophe

Meyer, Xuan Mi

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital ArchivesBiochar: Production, Characterization andApplications Proceedings8-20-2017Woody and agricultural biomass diversity intorrefaction: A complete study in solid conversionand volatiles formation on TGA-GCMSMaría González MartínezLaboratory of Bioresources Preparation, CEA Grenoble, FranceCapucine DupontLaboratory of Bioresources Preparation, CEA Grenoble, FranceXuan Mi MeyerLaboratory of Chemical Engineering, INP Toulouse/CNRS, FranceChristophe GourdonLaboratory of Chemical Engineering, INP Toulouse/CNRS, FranceFollow this and additional works at: http://dc.engconfintl.org/biocharPart of the Engineering CommonsThis Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusionin Biochar: Production, Characterization and Applications by an authorized administrator of ECI Digital Archives. For more information, pleasecontact franco@bepress.com.Recommended CitationMaría González Martínez, Capucine Dupont, Xuan Mi Meyer, and Christophe Gourdon, "Woody and agricultural biomass diversity intorrefaction: A complete study in solid conversion and volatiles formation on TGA-GCMS" in "Biochar: Production, Characterizationand Applications", Franco Berruti, Western University, London, Ontario, Canada Raffaella Ocone, Heriot-Watt University, Edinburgh,UK Ondrej Masek, University of Edinburgh, Edinburgh, UK Eds, ECI Symposium Series, (2017). http://dc.engconfintl.org/biochar/80Woody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA‐GCMSMaría González Martínez1,2, Capucine Dupont1, Xuan‐Mi Meyer2, Christophe Gourdon21Laboratory of Bioresources Preparation (LPB), CEA, Grenoble (France)2Laboratory of Chemical Engineering (LGC), INP Toulouse/CNRS (France)August 20-25, 2017, Alba, ItalyBiochar: Production, Characterization and ApplicationsMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMS1BIOMASS in Europe BIOMASSDiversity Deciduous wood Coniferous wood Agricultural by-products Herbaceous cropsContextMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSEnergy Chemicals MaterialsDiversityof the ressourceProduction• Seasonal• Delocalised• Low amountsFLEXIBLE and MOBILEtreatment technology2ContextMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMS3BIOMASS TORREFACTIONContext200	– 300	°CP(atm)10	min	– 1	hInert atmosphere ↑	heating value hydrophobic ↑	flowability ↑	grindability usesRaw biomassTorrefied	solidGaseous products harmful for	the	process chemicals (added value)↓	transport	costEnergyChemicalsMaterials~	70%	massPermanent	gases (CO,	CO2)Volatile	species (furans,	ketones,	phenols)María GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMS4ProductionTorrefied productVolatiles releasedOptimal operating conditionsTemperatureResidence timeHeating rateModellingBIOMASS TORREFACTION200‐300°C, inert atmosphere (He), < 1hObjective and approach10 dry Mobile Flip biomasses4 representative biomassesBIOMASS DIVERSITY6 dry Mobile Flip complementary biomassesyellow broom white broom oakfern gorse heathercorn cob cakeSunflower seed shellsGrape seed cake wheat straw MFscots pine bark poplar salixforest residues beechRed canary grassMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSGCMSHeatedStorage LoopsTGA3 °C/min2003005TGA‐GC/MSThermobalance + Gas chromatography/mass spectrometryBiomass torrefactionSolid weight loss analysisand volatile productionTGA – Heated storage loops ‐ GCMS11 gaseous samples per experiment(following non‐isothermal torrefaction)Material and MethodsMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSBiomass characterization macromolecular compositionBiomass ash cellulose hemicelluloses lignin extractives glucan xylan mannan galactan arabinanRepresentative biomasses % wmf % wmf % wmf % wmf % wmf % wmf % wmf % wmf % wmfAsh-wood 2.8 39.0 21.9 26.3 10.0 14.3 1.2 0.6 1.6Pine 1.3 36.7 26.1 27.5 8.4 5.0 10.3 1.7 1.0Wheat straw 8.3 33.8 21.7 20.5 15.7 16.0 0.4 0.9 2.3Miscanthus 2.8 45.7 22.8 20.2 8.6 17.2 0.3 0.4 1.9Mobile Flip biomasses mg/kg % % % % % % % % %Poplar 2.80 45.55 23.20 26.90 4.35 47.39 15.58 2.94 1.36 1.48Beech 0.80 44.40 27.25 26.51 1.85 45.76 20.85 2.17 1.42 1.45Pine forest residues 2.20 23.81 29.83 27.46 18.90 31.54 5.72 7.73 4.65 4.01Scots pine bark 2.80 23.97 20.08 40.72 15.23 28.31 3.49 4.33 3.12 4.80Corn cob cake 1.85 40.54 36.73 15.87 6.85 40.54 30.41 0.00 1.94 4.39Grape seed cake 4.15 7.78 21.90 62.74 7.58 9.98 14.32 2.20 1.53 1.65Sunflower shells 3.16 37.03 26.36 25.87 10.74 37.69 19.46 0.66 1.40 4.17Wheat straw MF 9.30 42.34 27.41 22.42 7.82 42.56 22.64 0.22 1.10 3.23Reed canary grass 6.60 41.77 27.17 24.69 6.37 42.04 20.63 0.27 2.13 3.87Salix 2.30 44.28 22.60 25.09 8.03 46.18 14.56 1.90 2.00 2.24Complementary biomasses mg/kg % % % % % % % % %Heather 1.30 20.70 20.40 35.85 18.34 20.70 11.67 0.00 1.68 1.26Fern 4.50 21.49 23.91 30.10 15.07 27.24 6.87 5.76 1.14 0.72Gorse 1.40 27.22 19.92 29.95 14.51 27.22 10.50 0.00 1.76 2.85Yellow broom 1.30 39.77 27.98 22.05 7.43 39.77 18.73 0.00 1.05 1.56White broom 1.20 33.00 27.20 25.05 11.76 33.00 16.58 0.00 1.67 3.04Oak 3.60 27.41 23.35 25.35 14.01 27.41 13.06 0.00 2.21 2.59Material and Methods6María GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMS7ResultsSolid transformation Remaining solid mass, TGA0501001502002503000%20%40%60%80%100%0 10 20 30 40 50 60 70T (°C)residualsolidmass (%)t (min)Heather Fern GorseYellow broom White broom OakSalix Wheat Straw MF Forest residuesGrape seed cake Corn Cob Cake Sunflower Seed ShellsRed Canary Grass Scots pine bark BeechPoplar Ash wood Wheat StrawPine Miscanthus TMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMS8ResultsSolid transformation‐3020701201702202703200.0%0.5%1.0%1.5%2.0%2.5%3.0%0 10 20 30 40 50 60 70T (°C)degradationrates (% m/min)t (min)Heather FernGorse Yellow broomWhite broom OakSalix Wheat straw MFForest residues Grape seed cakeCorn Cob Cake Sunflower Seed ShellsRed Canary Grass Scots pine barkBeech PoplarAsh wood Wheat strawPine MiscanthusTDegradation rates, TGAMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMS9ResultsDetected volatile	compoundCellRaw Detected volatile	compoundCellRaw Detected volatile	compoundCellRaw Detected volatile	compoundCellRawMethanol	(mixed	pic) X X Furfural X X 2‐Butanone,	1‐(acetyloxy)‐ X Levoglucosenone XFuran X X Furan,	2‐propyl‐ X 2‐Cyclopenten‐1‐one,	3‐methyl‐ X Phenol,	2‐methoxy‐4Or5‐methyl‐ XFuran,	2‐methyl‐ X X 2‐Propenoic	acid,	methyl ester X Butanoic acid,	4‐hydroxy‐ X Phenol,	4‐ethyl‐2‐methoxy‐ X2,3‐Butanedione X X Phenol X 2(5H)‐Furanone X X 1,4:3,6‐Dianhydro‐α‐d‐glucopyranose X X2‐Butanone X Isocrotonic Acid X X 2(3H)‐Furanone,	5‐acetyldihydro‐ X 2‐Methoxy‐4‐vinylphenol XPropanoic anhydride	OR	3‐pentanone X 2‐Furanmethanol X 2,5‐Furandione,	3‐methyl‐ X X Eugenol XFormic	acid X 2(3H)‐Furanone,	5‐methyl‐ X 4H‐Pyran‐4‐one X 5‐Hydroxymethylfurfural X X2‐Butenal X X 2‐Propanone,	1‐(acetyloxy)‐ X X 2‐Cyclopenten‐1‐one,	2‐hydroxy‐3‐methyl‐ X X Catechol XAcetic acid X X 2‐Cyclopenten‐1‐one,	2‐methyl‐ X 2(5H)‐Furanone,	3‐methyl‐ X Phenol,	2,6‐dimethoxy‐ X2,3‐Pentanedione X X 2‐Butanone X 2‐Cyclopenten‐1‐one,	3‐ethyl‐2‐hydroxy‐ X Cis‐Isoeugenol XHydroxyacetone X X 2(5H)‐Furanone,	5‐methyl‐ X X 2‐Furanone,	2,5‐dihydro‐3,5‐dimethyl X Trans‐Isoeugenol XAcetic	acid,	hydroxy‐,	methyl	ester X Acetylfuran X X 3‐Furancarboxylic	acid X 1,2,4‐Trimethoxybenzene X2‐Butenoic	acid,	ethenyl	ester X 4‐Cyclopentene‐1,3‐dione X X Phenol X Vainillin XFuran,	3‐methyl‐ X 2(3H)‐Furanone,	dihydro‐4‐hydroxy‐ X Phenol,	2‐methoxy‐ X Benzaldehyde,	3‐hydroxy‐ XPropionic acid X X 2‐Cyclopenten‐1‐one,	2‐hydroxy‐ X Phenol,	2‐methyl‐ X X Benzoic	acid,	4‐hydroxy‐3‐methoxy‐,	methyl	ester X2‐propenoic	acid X X 1,2‐Cyclopentanedione X Larixic acid (Maltol) X X Ethanone,	1‐(4‐hydroxy‐3‐methoxyphenyl)‐ X1,2‐Ethanediol X Isomaltol X 2‐Hydroxy‐gamma‐butyrolactone X Phenol,	2,6‐dimethoxy‐4‐(2‐propenyl)‐ X1‐Hydroxy‐2‐butanone X X 2‐Furanmethanol,	acetate X 2,5‐Furandicarboxaldehyde X X 2H‐1‐Benzopyran‐2‐one,	3,4‐dihydro‐6‐hydroxy‐ X1,2‐Ethanediol,	monoacetate X 2‐Pentenoic	Acid X Propanoic acid,	2‐methyl‐,	anhydride X Benzaldehyde,	4‐hydroxy‐3,5‐dimethoxy‐ X2‐Cyclopenten‐1‐one,	2‐hydroxy‐ X 3‐Furancarboxylic	acid,	methyl ester X 5‐Hydroxymethyldihydrofuran‐2‐one X 4‐Hydroxy‐2‐methoxycinnamaldehyde X3‐Furaldehyde X X 2‐Furancarboxaldehyde,	5‐methyl‐ X X 2,5‐Furandione,	dihydro‐3‐methyl‐ X X X	=	detected compound	in	GC/MS;		for	Avicel, all	thesedetected compounds	are	under the	detection limitGonzalez	Martinez	M.,	Dupont	C.,	Thiery S.,	Da	Silva	Perez	D.,		Karakashov	B.,	Meyer	X.M.,	Gourdon	C.,	2016,	Torrefaction	of	Various	Woody	and	Agricultural	Biomasses	and	of	their	extracted	Cellulose,	Hemicell lose	and	Lignin	t rough	TGA‐GCMS.	21st International	Symposium	on	Analytical	and	Applied	Pyrolysis	– Nancy,	France,	9‐12	May	2016	(oral	presentation).Volatiles production GC/MSMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMS10ResultsVolatiles production ‐ Furfural0.000.010.020.030.040.050.060.070.080.090.10160 180 200 220 240 260 280 300Concentration (g/L)T (°C)heatherferngorseyellow broomwhite broomoaksalixwheat straw MFforest residuesgrape seed cakecorn cob cakesunflower seed shellsRed canary grassbeechpoplarash woodwheat strawmiscanthusGC/MSMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSBiomass characterization macromolecular compositionBiomass ash cellulose hemicelluloses lignin extractives glucan xylan mannan galactan arabinanRepresentative biomasses % wmf % wmf % wmf % wmf % wmf % wmf % wmf % wmf % wmfAsh‐wood 2.8 39.0 21.9 26.3 10.0 14.3 1.2 0.6 1.6Pine 1.3 36.7 26.1 27.5 8.4 5.0 10.3 1.7 1.0Wheat straw 8.3 33.8 21.7 20.5 15.7 16.0 0.4 0.9 2.3Miscanthus 2.8 45.7 22.8 20.2 8.6 17.2 0.3 0.4 1.9Mobile Flip biomasses mg/kg % % % % % % % % %Poplar 2.80 45.55 23.20 26.90 4.35 47.39 15.58 2.94 1.36 1.48Beech 0.80 44.40 27.25 26.51 1.85 45.76 20.85 2.17 1.42 1.45Pine forest residues 2.20 23.81 29.83 27.46 18.90 31.54 5.72 7.73 4.65 4.01Scots pine bark 2.80 23.97 20.08 40.72 15.23 28.31 3.49 4.33 3.12 4.80Corn cob cake 1.85 40.54 36.73 15.87 6.85 40.54 30.41 0.00 1.94 4.39Grape seed cake 4.15 7.78 21.90 62.74 7.58 9.98 14.32 2.20 1.53 1.65Sunflower shells 3.16 37.03 26.36 25.87 10.74 37.69 19.46 0.66 1.40 4.17Wheat straw MF 9.30 42.34 27.41 22.42 7.82 42.56 22.64 0.22 1.10 3.23Reed canary grass 6.60 41.77 27.17 24.69 6.37 42.04 20.63 0.27 2.13 3.87Salix 2.30 44.28 22.60 25.09 8.03 46.18 14.56 1.90 2.00 2.24Complementary biomasses mg/kg % % % % % % % % %Heather 1.30 20.70 20.40 35.85 18.34 20.70 11.67 0.00 1.68 1.26Fern 4.50 21.49 23.91 30.10 15.07 27.24 6.87 5.76 1.14 0.72Gorse 1.40 27.22 19.92 29.95 14.51 27.22 10.50 0.00 1.76 2.85Yellow broom 1.30 39.77 27.98 22.05 7.43 39.77 18.73 0.00 1.05 1.56White broom 1.20 33.00 27.20 25.05 11.76 33.00 16.58 0.00 1.67 3.04Oak 3.60 27.41 23.35 25.35 14.01 27.41 13.06 0.00 2.21 2.59Material and MethodsDeciduous wood Coniferous wood Agricultural by‐products Herbaceous crops11María GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSResultsDeciduouswoodAgricultural biomassesHerbaceous cropsConiferouswood12María GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSProductionTorrefied productVolatiles releasedOptimal operating conditionsTemperatureResidence timeHeating rateBiomassmacromolecularcompositionCelluloseLigninHemicelluloseEXTRACTED fromeach biomassRbiomass = Rcellulose . %cellulose + Rhemicellulose . %hemicellulose + Rlignin . % lignin [1][1] Nocquet T., Dupont C., Commandre J‐M., Grateau M., Thiery S., Salvador S., 2014, Volatile species release during torrefaction of biomass and its macromolecular constituents: Part 2 ‐Modeling study. Energy 72, 188‐194.Ri : torrefaction yield of i%i : initial mass fraction of ii : cellulose, hemicellulose, ligninModellingBIOMASS TORREFACTION 200‐300°C, inert atmosphere (He), < 1hpine ash woodwheat straw miscanthusObjective and approachMODEL validation10 dry Mobile Flip biomasses+ 6 complementary biomasses4 reference biomasses13María GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSpine ash woodmiscanthuswheat strawCellulose LigninHemicellulosesRaw biomasses[2] Gonzalez Martinez M., Dupont C., Thiery S., Da Silva Perez D.,  Karakashov B., Meyer X.M., Gourdon C., 2016, Torrefaction of Various Woody and Agricultural Biomasses and of their extracted Cellulose, Hemicellulose and Lignin through TGA‐GCMS. 21st International Symposium on Analytical and Applied Pyrolysis – Nancy, France, 9‐12 May 2016 (oral presentation).1) Solid transformation – experimental results: Avicel (commercial cellulose) is not a representative model of cellulose behaviour in biomasstorrefaction [2]Results60%70%80%90%100%200 220 240 260 280 300Residualsolidmass (% m)T (°C)Remaining solid in non‐isothermal torrefaction for extracted celluloses and Avicel P101Wheat StrawMiscanthusAsh woodPineP101Avicel0114María GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSpine ash woodmiscanthuswheat strawCellulose LigninHemicellulosesRaw biomasses1) Solid transformation – experimental results: Cellulose, hemicelluloses and lignin profilesResults0501001502002503003500%20%40%60%80%100%0 10 20 30 40 50 60T (°C)% mt (min)Extracted lignin from ashwoodExtracted lignin from wheatstrawExtracted lignin frommiscanthusExtracted lignin from pineT0501001502002503003500%20%40%60%80%100%0 10 20 30 40 50 60 70T (°C)% mt (min)Extracted cellulose fromash woodExtracted cellulose fromwheat strawExtracted cellulose frommiscanthusExtracted cellulose frompineT0501001502002503003500%20%40%60%80%100%0 10 20 30 40 50 60T (°C)% mt (min)Extracted hemicellulose frompineTunder progress15María GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMS16Resultspine ash woodmiscanthuswheat strawCellulose LigninHemicellulosesRaw biomasses1) Solid transformation – modelling: Surestimation of the extracted compounds but representative tendences First approximation of the model to be refined by adding the influence of interactions, impurities…Remaining solid mass Degradation ratesunder progressRbiomass = Rcellulose . %cellulose + Rhemicellulose . %hemicellulose + Rlignin . % ligninRi : torrefaction yield of i%i : initial mass fraction of ii : cellulose, hemicellulose, ligninMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSpine ash woodmiscanthuswheat strawCellulose LigninHemicellulosesRaw biomasses2) Volatiles modelling: example for PINE17Resultsunder progressMaría GONZALEZ MARTINEZWoody and agricultural biomass diversity in torrefaction: a complete study in solid conversion and volatiles formation on TGA-GCMSConclusionsCONCLUSIONS• Good knowledge of the raw material variability for biomass torrefaction modelling required.• Promising methodology: TGA‐GC/MS coupling through heated storage loops →Measurement of solid and volatile species evolution during torrefaction versus T, t• Different behaviour in torrefaction of the extracted celluloses from different biomasses regarding the mass loss and volatiles released → modelling through Avicel is not satisfactory → extracted components (cellulose, hemicellulose lignin) are expected to improve biomass representation compared with commercial components.Future work• Modelling the 3 other representative biomasses (wheat straw, miscanthus, ash wood)• Model refining (interactions…)• Model validation with 20 biomasses18Thank you for	your attentionMarίa	GONZALEZ	MARTINEZmaria.gonzalez‐martinez@cea.frACKNOWLEDGEMENTS: This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 637020−MOBILE FLIP. Photo : Chandrexade Queixa(Ourense–España)

Woody and agricultural biomass diversity in torrefaction: A complete study in solid conversion and volatiles formation on TGA-GCMS

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Woody and agricultural biomass diversity in torrefaction: A complete study in solid conversion and volatiles formation on TGA-GCMS

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