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Utilizing Biorenewable Materials for theProduction of Bio-Based Products in SustainableWays: Learning Its Opportunities and ChallengesJustinus A. Satrio, Ph.D.Biomass Resources & Conversion Technologies LaboratoryandDepartment of Chemical EngineeringPresented atFaculty of Agricultural TechnologiesBrawijaya UniversityMalang, Indonesia, April 24th 20141
Lecture Outline1. Introduction – About Villanova University2. Technical presentation– Background: Why Biomass? Issues: Sustainability and climate change– Biomass: What is biomass and how is its potential?– Biomass Conversion Technologies– Sustainability issues with biomass utilization2
Why Biomass?Issues:Thinking about Sustainabilityand Climate Change (?)3
“We cannot solve our problems with thesame thinking that we used when wecreated them.” – Albert Einstein4
What is Sustainability orSustainable Development?Terms Now Used Interchangeably5
Natural SinksEliminate tropical deforestation ANDdouble the rate of new forest plantingORUse conservation tillage on all cropland(1600 MhaOne wedge would require of new forests over an area thesize of the continental U.S.Conservation tillage is currently practiced onless than 10% of global croplandn.a. / / !*Photo courtesy of NREL, SUNY Stonybrook, United Nations, FAO6
Sustainable Development(United Nations)How to meet the needsof the present generation without compromisingthe ability of futuregenerations to meet theirs7
Sustainability:The triple bottom line Society depends on theeconomy The economy dependson the globalecosystem, whosehealth represents theultimate bottom line.Coined by John Elkington,SustainAbility8
Big Picture: The “Master” EquationI PxAxTI total environmental impact from humanactivitiesP populationA affluence or per capita consumptionT environmental damage from technologyper unit of consumptionSource: Ehrlich and Holdren (1971)9
I PxAxT---Unique Role for theScientific Profession!!! In the “Master” Equation, T, is the homedomain of the scientific profession Our critical professional challenge is to reduceT in terms of “environmental impact” per unitof GDP For I to stay constant, the inevitable increasesin P x A must be offset by correspondingreductions in T10
Sustainability: Current Issues ofConcern Climate Change or DisruptionWaterOzone DepletionSoil Degradation and Food SupplySpecies ExtinctionOceans and Fishery ResourcesConcentration of ToxicsDepletion and Degradation of Natural ResourcesEtc11
Climate Change12
What changes climate? Changes in:– Sun’s output– Earth’s orbit– Drifting continents– Volcanic eruptions– Greenhouse gases13
“Greenhouseeffect”Increasing greenhousegases trap moreheat14
Greenhouse GasesNitrous oxideCarbon dioxideWaterMethaneSulfur hexafluoride15
Could the warming be natural?16
Winter 2014 in PA – Snowiest Winter in Recent HistoryClimate Change Effect?17
Fossil FuelBurning8billiontons go in4 billion tons addedevery year800billion tons carbonOceanLand Biosphere (net)2 2 4billion tons go out18
Past, Present, and Potential FutureCarbon Levels in the Atmosphere1200“Doubled” )GlacialBillions of tons of carbonbillions of tonscarbon( ppm )19
Princeton Institute:15 Approaches for reducing CO2 emissions1.2.3.4.5.6.7.8.Auto Fuel EfficiencyTransport ConservationBuildings EfficiencyElectric Power fuelsFuel Switching—NaturalGas Power Plants9. Nuclear Energy10. Wind Electricity11. Solar Electricity12. Wind Hydrogen13.Biomass Fuels14. Forest Storage15. Soil Storage20
BiofuelsReducing CO2 emissionsby 1 Gtons/year requiresscaling up current globalethanol production by 30timesPhoto courtesy of NRELT, H / Using current practices, reducing CO2emissions by 1 Gtons/year requires plantingan area the size of India with biofuels crops21
Take Home Messages In order to avoid a doubling of atmospheric CO2, we need torapidly deploy low-carbon energy technologies and/orenhance natural sinks We already have an adequate portfolio of technologies tomake large cuts in emissions No one technology can do the whole job – a variety ofstrategies will need to be used to stay on a path that avoids aCO2 doubling Every “wedge” has associated impacts and costs22
Biomass, Biofuels and Sustainability23
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Alternative Energy SourcesWind EnergyNuclear EnergyBiomass EnergySolar EnergyGeothermal EnergyOcean/Waves Energy How much do you think the total contribution ofthese alternative energy sources to the totalproduction of energy in the World?Hydro Energy25
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What separates biomass from othersustainable resources?28
Sustainable Alternative Resources forTransportation learElectricityHydrogenBatteries29
Among sustainable resources, biomass is the only resource thatproduces carbon, which is the primary chemical element intransportation (liquid) fuels.Until our transportation systems are no longer energized by liquidfuels, we will continue rely on carbon-based resources.30
The goal is not ethanol or biodiesel!Ethanol and Biodiesel are 1st Generation Biofuels1st Generation biofuels have issues31
1st Generation Biofuels: Main Issuehttp://www.naturalnews.com/023092 corn ethanol biofuels.html32
Fuels Produced from BiomassNot only Ethanol and Methanol0.79620.1109-Butanol0.813696 - 105-Mixed Alcohols 0.8027-3696-109-Fischer-Tropsch Diesel0.77043.9-74.6Hydrogen0.07 (liq)120 130-Methane0.42 (liq)49.5 120-Dimethyl Ether0.66 (liq)28.9- 55Gasoline0.72-0.7843.591-100-0.8545-37-56Diesel
2nd Generation Biofuels Developed to overcome thelimitations of 1st generationbiofuels (fuel vs. food) Feedstock: non-food crops, e.gwoods, organic waste,agricultural waste & specificbiomass crops34
Lignocellulosic BiomassComplex aromatic structurep-hydroxyphenylpropenebuilding blocksPolymer of 5- and6-carbon 0%Polymer of glucose3535
Components of BiomassAny type of plants may contain some or all of thefollowing components: Cellulose Hemicellulose Lignin Starch Pectins Vegetable Oil/Fats36
Our Biomass Resources Currently the U.S. consumes 190 million dry tons of biomass forenergy consumption, which is approximately 3% of total energyconsumption. Total potential in U.S. is in excess of 1.3 billion tons (about 21 EJ 20 quadrillion BTU)37
Our Biomass ResourcesGrains for biofuels79Dedicated crops343Crop residues389Forest thinning55Lodging Residues58Urban Wood43Milling residuesFuel wood13247Ag.process residues &manure-509650150250350450Million Dry Tons per Year38
Herbaceous CropsSwitchgrassMischantusCoastal Bermuda Grass39
Energy CropsWillowPoplarPineSugarcaneEucalyptusJatropha Curcas40
Other Energy CropsCamelinaMesquite(Considered weeds, not energy crops)AlgaeHemp41
How about biomass potential in Indonesia?42
Routes to Make a BiofuelsWater-gas shiftSyn-gasGasification CO H22Lignocellulosic Biomass(woody plants, ast PyrolysisMeOH SynthesisFischer-Tropsch t &HydrolysisBagasseCornCornGrain odeoxygenationBlending/Direct UseOlefinsAlkanesZeolite upgradingHydrodeoxygenationZeolite upgradingC5 Sugars Dehydration(Xylose)Aromatics, light alkanes,cokeDirect UseAlkyl benzenes, parrafinsAromatics, cokeFurfural HydrogenationC6 Sugars Dehydration Levulinic EsterificationAcid(Glucose, Fructose)HydrogenationSucrose (90%)Glucose (10)SugarcaneLipids/Triglycerides(VegetableOils, Algae)MethanolGasolineAromatics, genAlkyl esters (Bio-diesel)C1-C14 Alkanes/AlkenesAll SugarsFermentationMTHF (methyltetrahydrofuran)LevulinicEstersMTHF (methyltetrahydrofuran)Ethanol,ButanolC12-C18 n-AlkanesDirect Use43G.W. Huber, S. Iborra, A. Corma; Chemical Reviews 106, 4044 (2006).
Bio-Refinery“A processing and conversion facility that (1) efficientlyseparates its biomass raw material into individual componentsand (2) converts these components into marketplace products,including biofuels, biopower, and conventional and newbioproducts.”The Biomass Research and DevelopmentTechnical Advisory Committee (2002)U.S. Departments of Energy andAgriculture44
Approaches to Biorefineries Chemical (lipid platform) Biochemical (sugar platform) Thermochemicalo Gasificationo Pyrolysis Hybrids (e.g. biochemicalthermochemical)45
Lipid-based Approach46
Lipid-based Biorefinery Extract lipids from plants like soybean, palm oil, jatropha ormicroalgae or from animal fats, then convert the lipids tofuel, called biodiesel, by reaction called transesterification.47
Lipid-based Biorefinery Extract lipids from plants like soybean, palm oil, jatropha ormicroalgae or from animal fats, then convert the lipids tofuel, called biodiesel, by reaction called transesterification.Methanol , Catalyst65o C, 30-60 min.48
Biochemical Approach(Fermentation)49
Starch-based Biochemical BiorefineryEtOHDistillationDDGS (byproduct)StarchEnzymesGrainPretreatmentCorn OilCO2CookingDryingFermenterWholeStillage50
Cellulose-based Biochemical Biorefinery Similarities with conventional corn ethanol plant:– Pretreatment– Saccharification (release C5 and C6 sugars)– Fermentation (both C5 and C6 sugars)DistillationLignin (byproduct)FermenterCO2Cellulose EnzymesPretreatmentCellulosicBiomassEthanol &otherfermentationproductsSaccharificationC5 & C6 Sugarswater51
Thermochemical Biorefineries
Thermo-Chemical Conversion Modes[2] Bridgewater
Process ParametersFast: 500C, 1sec13%Liquid12%Gasification: 750-900C5%10%Solid75%Torrefaction (slow):290C, 10-60min20%Gas85%80%Figures [2] Bridgewater
Gasification Approach: ChallengeAirCOMBUSTIONCO2 SteamGasCleaningCO H2REFORMING WGSH2 CO2FUEL CELLSCharCATALYSIS/FERMENTATIONOrganic acidsAlcoholsEstersHydrocarbonsFUELS &CHEMICALSSyngas needs to be cleaned and pressurized to be used asfeedstock for power, fuels and chemical production COSTLY!!
Fast Pyrolysis Approach56
Why Liquefying Biomass? Biomass is bulky with low energy density,which makes transporting them costly Liquefying biomass increases theenergy density by 10 folds,reducing the cost of transportation
Fast Pyrolysis Rapid thermal decomposition oforganic compounds in theabsence of oxygen to produceliquids, char, and gas– Small particles: 1 - 3 mm– Short residence times: 0.5 - 2s– Moderate temperatures(400-500 oC)– Rapid quenching at the end of theprocessTypical yieldsOil: 60 - 70%Char: 12 -15%Gas: 13 - 25%
Fast Pyrolysis-based BiorefineryBio-oil eryHigh WaterContent ydrogenHydrocrackerCentralized(Large-scale) FacilityDistributed(Small-scale) FacilitiesGreendieselPhaseSeparationLow WaterContent PhaseTransportAir59
Applications of Bio-OilBiomassCatalytic PyrolysisConventionalHydropyrolysisBio-Oil from FastPyrolysis of tHydrogenChemicalsFuels for Turbine, Engine, Heat, Electricity and Transport
Composition of Bio-Crude OilWt%Water20-30Lignin fragments: insoluble pyrolytic lignin15-30Aldehydes: formaldehyde, acetaldehyde, hydroxyacetaldehyde, glyoxal15-20Carboxylic acids: formic, acetic, propionic, butyric, pentanoic, hexanoic10-15Carbohydrates: cellobiosan, levoglucosan, oligosaccharides5-10Phenols: phenol, cresol, guaiacols, syringols2-5Furfurals1-4Alcohols: methanol, ethanol2-5Ketones: acetol (1-hydroxy-2-propanone), cyclopentanone1-5Direct use of bio-crude oil presents difficulties due to high viscosity,poor heating value, incomplete volatility, corrosiveness, and chemicalinstability.61
Properties of Bio-oil vs. of Diesel Fuel OilPhysical PropertyMoisture Content, wt %Bio oil (from wood)Diesel Fuel15-300.1pH2.5-Specific HHV, MJ/kg16-1940Viscosity (at 50% C), cP40-1001800.2-11Up to 50%1Elemental composition, wt %Solids, wt%Distillation residue, wt %
Challenges in Utilizing Bio-Oil Direct use of bio-oil present difficulties due to high viscosity,poor heating value, incomplete volatility corrosiveness, andchemical instability. Presence of water in bio-oil (15-30%) lowers the heating value.It reduces the viscosity and enhances fluidity. High levels of oxygen (35-40%) is the major factor responsiblefor instability and corrosiveness. It also leads to the lowerenergy density and immiscibility with hydrocarbon fuels.Upgrading is needed top make bio-oil more useful andcommercially feasible for final applications
Reactivity Scale of Oxygenates under esAliphatic EthersAliphatic oxylic GroupsPhenolic Ethers350oC400oCPhenolsDi-Phenyl EtherDibenzofuranDouglas C. Elliott (2007)
Primary Challenge in Upgrading Bio-Oil Chemical components in bio-oil come from various classes. Manycomponents are “stable”; some are “un-stable” due to activefunctional groups. “Bad” components in bio-oil to be removed/modified typically arehighly oxygenated with functionalities that make them ‘unstable’. A ONE for ALL treatment may be difficult to be applied.Individual treatments needed to serve individual needs.65
Research Explorations Explore strategies in fast pyrolysis to produce bio-oil withmore stable components Can we control the mechanistic of reactions during fastpyrolysis in order to produce the desirable componentsbased on the end of use of the bio-oil? Explore ways to make certain bio-oil components morestable during upgrading reactions Can we modify/transform certain components into newforms that lead to desirable pathways instead of to nondesirable ones?66
Fast Pyrolysis Reaction Mechanisms(Observed at veryhigh heating rates)(dT/dt) H BiomassM MoltenBiomassT 430oCOligomersH M Monomers/IsomersM : Catalyzed by Alkaline CationsH : Catalyzed by AcidsTM : Catalyzed by Zero Valent Transition MetalsThermomechanicalEjectionVaporizationLow Mol.Wt SpeciesAerosolsHigh MWSpeciesCO H2ReformingTM Gases/VaporsSynthesis GasRing-opened ChainsVolatile ProductsFast pyrolysis reactions are very complex Bi-oil is formed as vapors and aerosols Source: Raedlin, 1999
Research ExplorationBio-Oil Upgrading Understand the mechanism and relative rates of reactionsinvolved for certain key components of bio-oil Understand effects of levels of catalyst functionalities(metals and acids) Synthesize upgrading reaction catalysts specificallydesigned to handle multiple functionalities in bio-oils.68
Biomass Utilization for Bioenergy andchemicals is not only about technologydevelopment !
Research in Biomass Resources and Conversion Technologies(BRCT) LaboratoryA system for utilizing biomass to energy, chemical and fuels.RecycleCO2, H2OBiomassProductionCO2, H2O,Plant NutrientsCO2, H2O,Plant essesPreconditioningSunlightWaterEnergy forfertilizerLiquid fuels for Electricityproduction andtransportationCO2, H2OProductsUtilizationThermal energyfor processesVarious aspects to make the system successful, economically andenvironmentally, need to be researched in concerted manners.
Agricultural and Bioenergy Value ocessingEnergycompaniesAgriculturalcompaniesLack of focus on economic driversOverly simplistic assumptions bybio-fuel industries“If one step of the value chain does not work, the entire valuechain does not work”
Applications and Technology to Choose What are potential final products that can beproduced from each biomass? What are the technologies that can be utilizedfor each feedstock? What are the processes?
Life Cycle Assessment of BiofuelsPlantsFarming PracticesWhere is the energy put into this cycle?In what form?Feedstock TransportHow is energy used in thecycle?How much are the greenhouse gases emitted fromthe cycle?)AutomobilesRefiningProduct Transport
Take Home Messages Biomass is the only renewable resources that can be used directly tosubstitute fossil fuels for the production liquid transport fuels Lignocellulosic biomass is the largest source of biomass that are potential tobe used for the production of liquid fuels. The chemical nature oflignocellulosic biomass makes it difficult to process. There are many potential conversion technologies that can be used forutilizing lignocellulosic biomass. Thermochemical process, particularly fastpyrolysis, is very promising technology to do the job. Whether or not biomass as a right solution for our energy issues isdependent on how ‘sustainable and environmentally friendly’ is theutilization process chain. Evaluation of a process by using Life Cycle Analysis(LCA) can be used to determine the sustainability of biomass utilization.74
Questions/Comments?
Thank you for Listening!Biomass Resources and Conversion TechnologiesBRCT Laboratoryhttp://www3.villanova.edu/biomass/
Questions/Comments?Contact:Dr. Justinus A. Satrio, Ph.D.Villanova UniversityDept of Chemical Engineering800 E. Lancaster AvenueVillanova, PA 19085E-mail: justinus.satrio@villanova.eduPhone: 610-519-6658
Not only Ethanol and Biodiesel! Fuel Specific Gravity LHV (MJ/kg) Octane Number Cetane Number Ethanol 0.794 27 109 - Biodiesel 0.886 37 - 55 Methanol 0.796 20.1 109 - Butanol 0.81 36 96 - 105 - Mixed Alcohols 0.80 27-36 96-109 - Fischer-Tropsch Diesel 0.770 43.9 - 74.6 Hydrogen 0.07 (liq) 120 130 -
