H - Montpellier SupAgro

La chimie de la biomasseet ses enjeuxRainer HöferEditorial Ecosiris« La chimie ça se cultive »L’évènement Chimie verte de l’Année 2011AIC 2011 – Agronomie et Chimie pour un développement durable: la chimie verteEcole Nationale Supérieure de Chimie (ENSCM) /Ecole Nationale Supérieure d'Agronomie (SupAgro)Montpellier, 8 Mars 2011TM1

The Agrarian Revolution And The Birth Of CivilizationThe Neolithic transition (10,000–4,000 B.C.)from hunting and gathering to agricultural communitiesMap of the world showing approximate centers of origin of agriculture and its spread in prehistory:eastern USA (4000–3000 BP), Central Mexico (5000–4000 BP), Northern South America (5000–4000 BP),sub-Saharan Africa (5000–4000 BP, exact location unknown), the Fertile Crescent (11000 BP),the Yangtze and Yellow River basins (9000 BP) and the New Guinea Highlands (9000–6000 BP).(Adapted from : BlankMap-World 6, compact.svg and J. Diamond, P. Bellwood ,Farmers and Their Languages: The First Expansions, Science 300: 597–603 (2003) by Joey Roe)TM2

The Industrial AgeWorld population, per capita consumption andproduction of plastics, fibres,oils and fatsDevelopment of coating consumptionworld populationin bn.33,74,55,36 6,325 mio. t11800 1960 1970 1980 1990 2000 200629,3per capitaconsumption[kg/capita]plasticsoils and fats18,820,6131117,39,815,27,94122,2 81,92,7 3,51,11800 1960 1970 1980 1990 2000 2003 20061000 A. C.synthetic andsemi-syntheticfibresproductionin mio. t18013010060105438150305931 14,8 18,96,73,3 8,41800 1960 1970 1980 1990 2000 2003 200615000B.C.4000B.C.Birth of todayChrist1800A. C.TM4

Economic Growth and Natural ResourcesWater:Forestry:Fishing:Farming:Diversity in Nature:Climate:global consumption of water tripled since mid of lastcenturydemand for wood as construction material doubleddemand for wood for heat generation tripleddemand for wood as pulp & paper raw material six timesincrease – all since mid of last centuryconsumption of sea fish has increased by five times overlast 50 yearsSteady decrease of farmland quality due to intensivelivestock farmingannually >1.000 animals or plants close to exterminationsince the beginning of the industrial age concentration ofcarbon dioxide in the atmosphere has steadily increased(green house effect, climate change)TM5

Geological formation of petroleumSource: http://earthguide.ucsd.edu/fuels/oil.htmlPetroleum, or oil, forms from theremains of plants and animals thatlived in the ocean between 10 to 160million years ago. When organismsdied and sank to the bottom, theywere covered in mud, sand, and othermineral deposits. This rapid burialprevented immediate decay, whichwould normally occur if organismsremained exposed on the sea floor.The lack of oxygen in the sedimentarylayers caused organisms to slowlydecay into carbon-rich compounds.These compounds mixed withsurrounding sediments and formedsource rock, which is a type of finegrainedshale. As more layers weredeposited on top of one another,pressure and heat acting on thesource rock compressed the organicmaterial into crude oil.TM6

Life cycle of non-Renewable Raw Materials – Petrochemicalsmineral oil,coal, gasprocessingDEPLETIONpetrochemicalsburningprocessingCO 2 , H 2 OproductsACCUMULATION = POLLUTIONdegradationwasteutilisationTM7

Limits to Growthhttp://www.eia.doe.gov/oiaf/ieo/oil.htmlWorld Consumption of Mineral Oil in 2004: approx. 4 bn mtC. J. Campbell, World: Oil and Gas - Peak Oil: an Outlookon Crude Oil Depletion, revised February 2002,http://www.mbendi.com/indy/oilg/p0070.htmTM8

Development of the world’s energy needs1250ExaJoules1000750500Exa = 10 18The Spirit of the Coming Age1 Exajoule = 34,12 Mio t SKENewRenewablesHydroNuclearGasOilH. Heinrich, Sustainable Fuels for Road Traffic, Solvsafe Annual Meeting Prelude Convention, Düsseldorf (2007); ShellTM25001970 1990 2010 2030 20509Coal CH 4 /H 2CoalTraditionalRenewables

Life cycle of Renewable Feedstock – Example: OleochemicalsdegradationCO 2 , H 2 Onutrientsenergybiosynthesiswastebiomassutilisationextractionoleochem. specialtiesproductsprocessingoleochemicalstriglycerideswaxesprocessingTM10

Finite vs. renewable raw materials and energy carriersEnergyChemistry+EnergyFood & Feed+Chemistry+EnergySolar powerHydropowerWind powerGeothermal eneryTydal powerNuclear energyFossil BiomassAnthracite (black coal)Lignite (brown coal)CharcoalPeatCrude oilNatural gasRenewable Biomass- Wood, straw, molasse- Energy plants, algae- Maize, wheat, potatoes- Sugar beat, sugar cane- Plant proteins, latex- Hide, wool, silk- Active ingredients,- Natural fats & oils- Manure, effluent sludgeTM11

Global trade fossil crude oilTM12

Global trade grains and oilseedsReproduced with the kind permission of RabobankTM13

Utilization of carbonic raw materials sourcesPetroleum7 %chemistry93 %energyAgriculturalproducts:5 %others95 %food + feedOleochemicals(2004):14 %chemistry86 %food + feedOleochemicals(2019):10 %chemistry25 %biodiesel65 %food + feedTM14

The magic triangle of sustainabilityECOLOGYEco system integritySocial EquityCross-cultural interactionParticipationQuality of lifeLOHAS-MegatrendLifestyle of Health& SustainabilitySustainabilityMeet the needs of the presentwithout compromising the ability of futuregenerations to meet their own needsEconomySustainable GrowthChemical IndustryResponsible Care ®24 Principles ofGreen Chemistry & GreenEngineering“Principle of Balance“EcologicEconomicSocialrealityexploitation of finite fossil resources,CO 2 emissionviolating principle of balanceglobal warmingfinancial crisisTM15

1660 Jean-Baptiste Colbert :« La France périrafaute de bois ».1669 Ordonnancesur le fait des Eaux etForetsLouis XIV,St. Germain en Laie1713 Hannß Carlvon Carlowitz„Sylviculturaoeconomica“NachhaltigkeitSustainabilityDéveloppementdurableMediaeval Market Square FreibergTMSkyline Dresden16

Thermo-chemical transformation of fossil and renewable biomassm pmC H O (n ) O n CO H O heatn m p2224 22Partial oxidation of solid carbon: C + ½ O 2 CO H = -111 kJ/molComplete oxidation of solid carbon C + O 2 CO 2H = -197 kJ/molOxidation of carbon monoxide: CO + ½ O 2 CO 2H = -283 kJ/molOxidation of hydrogen: H 2+ ½ O 2 H 2O H = -242 kJ/molOxidation of methane: CH 4+ 2 O 2 CO 2+ 2 H 2O H = -802 kJ/molBoudouard reaction: C + CO 2 2 CO H = 173 kJ/molHeterogeneous water gas reaction : C + H 2O CO + H 2H = 131 kJ/molHeterogeneous methane production: C + 2 H 2 CH 4H = -87 kJ/molSiemens Power GenerationGasification Test CentreFreiberg/DMethanation: CO + 3 H 2 CH 4+ H 2O H = -206 kJ/molHomogeneous water gas reaction(CO shift conversion reaction) : CO + H 2O CO 2+ H 2H = -42 kJ/molTM17

Typical parameters of untreated biomass compared with fossil fuelsType of biomass Heating value Ash content Volatile compoundsin MJ/kg in % in %Poplar wood (Short rotation) 18.5 1.8 81.2Wheat straw 17.2 5.7 77.0Triticale straw 17.1 5.9 75.2Miscanthus 17.6 3.9 77.6Hard coal (anthracite) 29.7 8.3 34.7Lignite 20.6 5.1 52.1Crude oil 42Sources: M. Kaltschmitt, H. Hartmann, H. Hofbauer, eds., Energie aus Biomasse, 2. Aufl., Springer, Berlin, Heidelberg, 2009Wikipedia, Heat of combustion (retrieved 25.09.09)TM18

Renewable FeedstockWorld production [Mio. tpa]1990 2007sugar 110 161starch 20 64fats & oils 80 153Forest 39 Mio km 2 (25% global surface); wood 3.400 Mio m 3 p.a.TM19

Utilization of wood in competitive marketsWood-based composite materialsSolid wood productsPulp and PaperWOODBIOMASSRegenerativeresourcesEnergyChemical productsFossilressourcesSource : E. Windeisen, G. Wegener, Wood, in R. Höfer Sustainable Solutions for Modern Economies, RSC, Cambridge, 2009TM20

Wood plastic composites (WPC) deck boardTrex Accents®: Fire Defense%u2122The perfect blend of beauty and brawn.Trex Accents®, exceeds the strict fire regulations set by the State of California and San Diego County.- Offers superior safety performance:-Exceeds ASTM E84 Class B Flame Spread.-Exceeds 12-7A-4 Part A (underflame) and Part B (Burning Brand).- Self-extinguishing even under extreme fire exposure.- Approved for use by the California State Fire Marshal's Office and San Diego County.Source http://www.archiexpo.com/prod/trex/wood-composite-deck-boards-56755-130461.htmlTM21

Lignocellulose biomassHOHOCH 2OHOHO HOCH 2HOOHOOOOHOOHOCH 2 HOHOCH 2OHOOH 2 C OHHCOHCOHHOCH 2HOHOCH 2HOHOOOHOHOOOAcHOMeOOH HOCH 2HOOHOOOOHOOHOCH 2 HOHOCH 2HO HOCH 2HOOHOOOOHOOHOCH 2 HOHOCH 2OHOCOOHCelluloseOHOOOOAcOOOAcOHOHemicellulose: Hardwood xylanOHOOOHOOOOHH 3 COHCOHCHCH 2 C OHOCHHCOHH 2 C OHOCHH 3 COHCH 2 COHHCOCH 3HCOH 2 C OHH 3 COHCOOCHH 2 C OHCHHCOHH 3 COOHH 2 C OHHCOHCOHHOOCH 3OH 3 COH 2 C OHHCHCOHOCH 3H 3 COH 2 C OHHCOHCOHH 3 COOHOH 2 CCHCHOOH 2 CHCH 2 C OHHCCHOHCOHOOOHCHCHCH 2OCH 3OCH 3HOCH 2 OHOH 3 COOH 2 C OHCHH 2 C OHHCH 3 COOHOHOOHCCOHOCH 2CH 2OHHOCH 2OHHOCHOO2OOOOOHOHOAcOHOOAcOHHemicellulose: Softwood glucomannanH 3 COOCH 3OHOHSection of softwood ligninTM22

The Pine Tree Value ChainSpirits ofTurpentineWoodRosinStubslumberPine TreePine Balsam(Turpentine) byLiving TreeTappingSpirits ofTurpentineGumRosinKraft SulfatePulpingSulfitePulpingPaperPulpCrude SulfateTurpentine, CSTPulpPaperCrude Tall OilLignosulfonatesTall OilFractionationTall OilHeads10 %TOFA (TallOil Fatty Acid)35 %Tall OilRosin30 %DistilledTall Oil5 %Pitch (incl.Sterols)20 %TM23

Nordic WoodHair & Body ShampooCARGO PlantLoveBotanical LipsticksOude ArabiqueRare. Mystical. Sacred.Oude is a sacred scent and, in some cultures,revered as the aroma of GOD.Norwegian Spruce,Balsam Fir, White Pine,Cedarwood & CamphorMuir WoodsTop notes:Middle notes:Base notes:MasticOude (Agarwood),Tamil Nadu SandalwoodAustralian Sandalwood,Buddahwood,Himalayan Cedar,Tolu BalsamTM24

The papermaking processSource http://individual.utoronto.ca/abdel_rahman/paper/fpmp.htmlTM25

Renewable raw materials: Natural RubbernRubber tree plantation located between Dalat and Ho Chi Minh CitySource: http://www.learnnc.org/lp/multimedia/1797TM26

Starch biomassRepresentative partial structure of amylopectinRepresentative partial structure of amyloseTM27

Usage of StarchStarch consumption (EU 2006)mtoFood 4.500.000Paper & Board 2.400.000Pharma & Chemicals 1.150.000Industrial Binders 550.000Source: A. Gozzo, D. Glittenberg, Starch: A Versatile Product from Renewable Resourcesin R. Höfer, Sustainable Solutions for Modern Economies, RSC Publ., Cambridge (2009)TM28

Starch application in paper coatingSource: http://www.risiinfo.com/community/technologyarchives/papermaking/PPIMagMay-From-researchto-the-market-Cargill-Industrial-Starches-aims-to-improvevalue-proposition-to-customers.htmlTMCalendering Unit at Cargill’s Application and DevelopmentCenter , Krefeld29

Sucrose biomassH OH OH O6'4 55'36H O OOH O 2' 4'O HO H23'O1'1O HSucrose(-D -fructofuranosyl -D -glucopyranoside)Uses of sucroseFood > 98%EthanolPharmaceuticalsAgrochemicalsPlasticsFoundry & CastingsTM30

Production of Bioethanolstartingmaterialproduction of sugar containing substrateProduction of ethanolC 6 H 12 O 6 → 2 C 2 H 5 OH + 2 CO 2sugar containingbiomasswashing,crushingextraction ofsugar juicefermentationETBEstarch containingbiomasswashing,crushingdry-millingwet-millingseparationyeastlignocellulosecontainingbiomasspretratmentdelignificationacid/enzymatichydrolysisdistillation /rectificationmashdehydrationCropEnergies 260.000 m 3 /yearbioethanol plant in Zeitz/D.VOGELBUSCH continuousfermentation process design;http://www.vogelbusch.com/showcase/BioethanolETBEisobutenTMAdapted from E. Dinjus, U. Arnold, N. Dahmen, R. Höfer, W. Wach,Green Fuels – Sustainable Solutions 31 for Transportation, in R. Höfer, ed.,Sustainable Solutions for Modern Economies, RSC Publ., Cambridge (2009)