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Study GuideStudy GuideBiofuel vs PetroleumBiofuel vs Petroleum--based fuelbased fuelExam questions will relate the lectures Exam questions will relate the lectures to each otherto each other–– Advantages and disadvantages of the Advantages and disadvantages of the

different fuels (methanol, ethanol, different fuels (methanol, ethanol, bioethanol, and biodiesel) and compared bioethanol, and biodiesel) and compared to petroleumto petroleum

–– How are they similar and different from How are they similar and different from each other? Make a table to compareeach other? Make a table to compare

EXAM # 2 IS ON TUESDAY NOVEMBER 30TH: Endophyte-Assisted Phytoremediation plus the three bioenergy lectures so far

Bioenergy LecturesBioenergy LecturesThTh Nov 16Nov 16-- OverviewOverviewTuTu Nov 18Nov 18-- BiodieselBiodieselThTh Nov 23Nov 23-- Bioethanol and methanolBioethanol and methanolTuTu Nov 25Nov 25-- HolidayHolidayNov 30Nov 30-- EXAM #2 (EXAM #2 (PhytoPhyto with endophytes; with endophytes; first 3 first 3 bioenergy lectures)bioenergy lectures)

Dec 2Dec 2--Ways to improve the efficiency of biofuel Ways to improve the efficiency of biofuel productionproductionDec 7Dec 7-- (cont.)(cont.)Dec 9Dec 9-- Environmental applications of trees; paper Environmental applications of trees; paper assignment givenassignment given

Dec 13Dec 13-- Final exam (75 pts) on last 3 Final exam (75 pts) on last 3 lectures (in lectures (in class for both ESRM and CFR);class for both ESRM and CFR); Paper (50 pts) is duePaper (50 pts) is due

BioethanolBioethanol

((Many of the following slidesMany of the following slides are from are from Prof. Renata Bura)Prof. Renata Bura)

OverviewOverview

What is bioconversion?What is bioconversion?Why bioconversion?Why bioconversion?Biomass compositionBiomass compositionBioconversion to ethanol processBioconversion to ethanol process–– PretreatmentPretreatment–– HydrolysisHydrolysis–– FermentationFermentation

Pros and cons of bioethanolPros and cons of bioethanolComparison to other Comparison to other biofuelsbiofuels

What is bioconversion?What is bioconversion?

General: a process which uses biological General: a process which uses biological agents (microorganisms or protein) to agents (microorganisms or protein) to transform a feedstock into desirable transform a feedstock into desirable products.products.

BioethanolBioethanolA chemical/biochemical process by which A chemical/biochemical process by which lignocellulosic materials are converted to lignocellulosic materials are converted to ethanol and other coethanol and other co--products.products.

BioconversionBioconversion

Biomass

Pretreatment

Hydrolysis

Fermentation Distillation

Ethanol

Ethanol (CHEthanol (CH33CHCH22OH)OH)

Ethyl alcohol, grain alcoholEthyl alcohol, grain alcohol–– Clear, colorless liquidClear, colorless liquid

Ethanol made from cellulosic biomass instead of Ethanol made from cellulosic biomass instead of starch cropsstarch crops--bioethanolbioethanolAdvantages of bioethanolAdvantages of bioethanol–– Domestic renewable fuel sourcesDomestic renewable fuel sources–– Reduces reliance on foreign oilReduces reliance on foreign oil–– Cleaner fuel sourcesCleaner fuel sources–– Easily produced and storedEasily produced and stored–– Increases fuel octane number for little costIncreases fuel octane number for little cost

Energy contentEnergy content

Gasoline Ethanol Biodiesel

100% 67% 86%

“We can get fuel from apples, weeds, “We can get fuel from apples, weeds, sawdust, almost anything…..sawdust, almost anything…..And it remains for someone to find how this And it remains for someone to find how this fuel can be produced commerciallyfuel can be produced commercially--better fuel at a better price than we now better fuel at a better price than we now know.”know.”

Henry FordHenry Ford

Why bioconversion?Why bioconversion?EnergyEnergy–– An alternative source of energy for the An alternative source of energy for the

transportation sector produced locallytransportation sector produced locallyAir pollutionAir pollution–– Reduction in greenhouse gas emissionReduction in greenhouse gas emissionWaste eliminationWaste elimination–– Elimination of problems with field Elimination of problems with field

burning/incineration, stockpiling, etc.burning/incineration, stockpiling, etc.Socio/economical benefitsSocio/economical benefits–– Creation of new jobs, rural developmentCreation of new jobs, rural development

Possible Possible feedstocksfeedstocks

Agricultural residues (corn stover, corn Agricultural residues (corn stover, corn fibre, wheat straw, rice straw)fibre, wheat straw, rice straw)Wood residues:Wood residues:–– Hardwood (poplar, willow)Hardwood (poplar, willow)–– Softwood (DouglasSoftwood (Douglas--fir, fir, lodgepolelodgepole pine)pine)

Paper wastePaper wasteMunicipal solids wasteMunicipal solids waste

OverviewOverview

Biomass compositionBiomass composition

CelluloseCellulose

HemicelluloseHemicellulose

LigninLignin

LigninLigninA major A major barrier to barrier to accessing the accessing the cellulosecelluloseProvides Provides strength and strength and rigidityrigidity

OverviewOverview

Bioconversion of biomass to Bioconversion of biomass to ethanol (pretreatment)ethanol (pretreatment)

Biomass

Pretreatment

Liquid phase

Solid phaseCellulose

Sugars EthanolFermentation

EthanolSugarsFermentation

Hydrolysis

LigninRecovery

PretreatmentPretreatment

Helps in separation of main biomass Helps in separation of main biomass components (cellulose, hemicellulose and components (cellulose, hemicellulose and lignin)lignin)Increase available surface areaIncrease available surface areaReduce particle size Reduce particle size Ideally pretreatment:Ideally pretreatment:–– SolubilizesSolubilizes hemicellulosehemicellulose–– Increases enzymatic Increases enzymatic hydrolysibilityhydrolysibility of of

cellulosecellulose

Pretreatment Pretreatment ––”disruption””disruption”

Possible methods:Possible methods:–– Mechanical (milling)Mechanical (milling)–– Chemical (acid and base)Chemical (acid and base)–– Biological Biological –– Combination Combination

Steam explosionSteam explosion

Treatment of biomass with highTreatment of biomass with high--pressure pressure steam for a short period of time followed by steam for a short period of time followed by sudden decompressionsudden decompressionAcid (HAcid (H22SOSO44, SO, SO22) impregnation of biomass ) impregnation of biomass increases SE efficiencyincreases SE efficiencyTypical conditions:Typical conditions:–– Temperature: 170Temperature: 170--250250ooC, 338C, 338--482 F482 F–– Time: 10secTime: 10sec--10min10min

Steam gunSteam gun

KarinFill valve

Steam valve

Blow valve

Receiving vessel

Pretreated corn stover

OverviewOverview

Bioconversion of biomass to Bioconversion of biomass to ethanol (hydrolysis)ethanol (hydrolysis)

Biomass

Pretreatment

Liquid phase

Hydrolysis

LigninRecovery

CelluloseCellulose

The goal of the hydrolysis step is to break the cellulose into simple sugars prior to

fermentation

Must be able to break cellulose to Must be able to break cellulose to get the energyget the energy

Cows, deer, sheepCows, deer, sheepRumen is a Rumen is a fermentation vatfermentation vatMicrobes break Microbes break down the cellulose down the cellulose using the enzyme, using the enzyme, cellulasecellulase

Fungi can break down cellulose tooFungi can break down cellulose too

CellulasesCellulases are are enzymes that enzymes that break down break down cellulosecelluloseWhite rot fungi: White rot fungi: good source of good source of enzymesenzymes

What are What are cellulasescellulases??

Enzymes made by many strains of bacteria Enzymes made by many strains of bacteria and fungiand fungiCatalyzes the Catalyzes the depolymerizationdepolymerization of cellulose of cellulose chainschains–– (details in Renata Bura(details in Renata Bura’’s class)s class)

OverviewOverview

Bioconversion of biomass to Bioconversion of biomass to ethanolethanol (fermentation)(fermentation)

Biomass

Pretreatment

Liquid phase

Hydrolysis

LigninRecovery

FermentationFermentation

Defined as:Defined as:Cellular metabolism under anaerobic conditions Cellular metabolism under anaerobic conditions (absence of oxygen) for the production of energy (absence of oxygen) for the production of energy and metabolic intermediatesand metabolic intermediates

Many organisms can “ferment” Many organisms can “ferment” Not all produce ethanol as an endNot all produce ethanol as an end--productproduct

Strain selectionStrain selectionTraditionally been a YeastTraditionally been a YeastYeast:Yeast:–– Single cell microorganismSingle cell microorganism–– FungiFungi–– Facultative anaerobeFacultative anaerobe

Most common industrial Most common industrial fermenterfermenter is is Saccharomyces cerevisiae Saccharomyces cerevisiae (baker’s or brewer’s (baker’s or brewer’s yeast)yeast)Why?Why?

Why Why S. cerevisiaeS. cerevisiae??

Has been selected over thousands of yearsHas been selected over thousands of yearsHigh ethanol yield and productivityHigh ethanol yield and productivityRelatively simple to cultureRelatively simple to culture

(Glycolysis first)

FERMENTATIONFERMENTATION

GLYCOLYSIS

Glucose PyruvateGlucose

FERMENTATION

Cellular respiration

If electron acceptor(such as oxygen)

is present

If electron acceptor(such as oxygen)is NOT present

KREBS CYCLE ELECTRON TRANSPORT ANDOXIDATIVE PHOSPHORYLATION

PYRUVATEPROCESSING

Fermentation Regenerates NADFermentation Regenerates NAD++

Fermentation pathways allow cells to regenerate NAD+

for glycolysis.

Fermentationby-product

Intermediate acceptselectrons from NADH

GENERAL PATHWAY

Alcohol fermentation occurs in yeast.

2 Pyruvate

2 Acetylaldehyde2 Ethanol

Conversion factor 0.51

1g/L of glucose: 0.51g/L ethanol (maximum)

OverviewOverview

Challenges (Cons)Challenges (Cons)

Feedstock diversityFeedstock diversityEconomical feasibility of the processEconomical feasibility of the process–– Cost of biomassCost of biomass–– Cost of enzymesCost of enzymes–– Ethanol as a final product = very cheapEthanol as a final product = very cheap

EnergyEnergy–– An alternative source of energy for the An alternative source of energy for the

transportation sector produced locallytransportation sector produced locally

Air pollutionAir pollution–– Reduction in greenhouse gas emissionReduction in greenhouse gas emission

Waste eliminationWaste elimination–– Elimination of problems with field Elimination of problems with field

burning/incineration, stockpiling, etc.burning/incineration, stockpiling, etc.

Socio/economical benefitsSocio/economical benefits–– Creation of new jobs, rural developmentCreation of new jobs, rural development

Pros (again)Pros (again)

Sugar cane & sugar cane Sugar cane & sugar cane bagassebagasse

Sugar cane

bagasse

Processing

Ethanol

Corn plantCorn plant

BiofuelsBiofuels--comparisonscomparisons

2.52.5

22--3636

8.08.0

1.31.3

Energy Energy balancebalance

6868NANA0.50 0.50 BiodieselBiodiesel

9191NANANANALignocellulosic ethanolLignocellulosic ethanol

5555--90900.870.873.963.96Cane ethanolCane ethanol

22221.091.094.86 4.86 Corn Corn grain ethanolgrain ethanol

GHEGHEreduction reduction

(%)(%)

Production Production cost ($)cost ($)

Production Production (billion (billion gallons)gallons)

Part 2. MethanolPart 2. Methanol

Toshiba

Gasifier

Biomass to Liquid Fuel Crude Syngas

(Syngas = CO2 + CO + H2)

Clean Syngas

Scrubber

Bio-Methanol

Methanol Reactor

Wood Biomass

(Wood Alcohol)

Gasifier

How is How is biomethanolbiomethanol made?made?

All the woody biomass is usedAll the woody biomass is usedNOT FROM FERMENTATIONNOT FROM FERMENTATIONWood chips Wood chips gasifiergasifier at high tempat high tempscrubbers scrubbers biomethanolbiomethanolWood to bioethanol yields 99Wood to bioethanol yields 99--142 gal142 galWood to Wood to biomethanolbiomethanol yields 165yields 165--186 186 gal BECAUSE IT USES ALL THE gal BECAUSE IT USES ALL THE BIOMASS, NOT JUST THE SUGARBIOMASS, NOT JUST THE SUGAR

2. 2. Principle of methanol synthesis Principle of methanol synthesis by the gasification methodby the gasification method

Slide adapted from H. Nakagawa

Carbon Hydrates:

(CH2O)n + Oxygen+ water

1000 C

Mixture of Gases:

Hydrogen, carbon monoxide, carbon

dioxide, water Pressure

40-80 atm

Biomethanol

CO + 2H2

TypicalTypical test questionstest questions

How is bioethanol and How is bioethanol and biomethanolbiomethanoldifferent in terms of how they are different in terms of how they are made?made?How is biodiesel different from both How is biodiesel different from both bioethanol and bioethanol and biomethanolbiomethanol in terms in terms of the plant material used? of the plant material used?

Some conversion efficiencies to alcohols

MaterialMaterial EthanolEthanol(gallons / 1 Mg biomass)(gallons / 1 Mg biomass)

MethanolMethanol(gallons/ 1 Mg biomass)(gallons/ 1 Mg biomass)

Sugar caneSugar canewww.itdg.org/docs/technical_information_service/suwww.itdg.org/docs/technical_information_service/sugar_production_from_cane.pdfgar_production_from_cane.pdf, K Vogt estimate, K Vogt estimate

24 24 –– 36 gallons36 gallons(6 (6 -- 9%)9%)

Corner stoverCorner stoverKheshgiKheshgi et al. 2000, et al. 2000, www.ctic.purdue.edu/Core4/StoverNCNU.pdfwww.ctic.purdue.edu/Core4/StoverNCNU.pdf

79 79 –– 119 119 gallonsgallons

WoodWoodwww.cfr.washington.edu/research.Forest_Energywww.cfr.washington.edu/research.Forest_Energy//, , KheshgiKheshgi et al. 2000, K Vogt estimateet al. 2000, K Vogt estimate

Chemistry determines how much liquid by-

product produced

Starch or Cellulose being converted

Cellulose and lignin being converted

NOTE: Ethanol cannot be made from lignin, a major component of waste biomass

Then why the focus on bioethanol Then why the focus on bioethanol instead of instead of biomethanolbiomethanol??

Plants contain a lot of nitrogen (not Plants contain a lot of nitrogen (not just “carbon hydrates”)just “carbon hydrates”)Gasification of nitrogen in the Gasification of nitrogen in the presence of oxygen makes toxic NO presence of oxygen makes toxic NO gases gases Toxic byproductsToxic byproductsLower energyLower energySmaller market (but maybe changing)Smaller market (but maybe changing)

SFR SFR biofuelsbiofuels research agenda research agenda

Vision: Cost effective cellulosic transportation fuelsVision: Cost effective cellulosic transportation fuels

•Use mixed biomass sources•With good process yields

•Profitable at moderate economies of scale

•Co-produce fuels and high value products

•Commodity Chemicals•Polymers•Pulp Fibers

ReviewReview

Ethanol from fermentation of starch from Ethanol from fermentation of starch from grain or sucrose from sugarcanegrain or sucrose from sugarcaneBioethanol from fermentation of Bioethanol from fermentation of any any cellulosiccellulosic biomassbiomass-- can be produced can be produced sustainably; sustainably; can be mixed with gasolinecan be mixed with gasolineBiodiesel from plant oilsBiodiesel from plant oils-- high energy high energy fuel;fuel;notnot compatible with most US compatible with most US cars (yescars (yes--bus)bus)BiomethanolBiomethanol-- lower energy; smaller market; lower energy; smaller market; but efficient production; can be used in but efficient production; can be used in power cellspower cells

Study GuideStudy GuideBiofuel vs PetroleumBiofuel vs Petroleum--based fuelbased fuelExam questions will relate the lectures Exam questions will relate the lectures to each otherto each other–– Advantages and disadvantages of the Advantages and disadvantages of the

different fuels (methanol, ethanol, different fuels (methanol, ethanol, bioethanol, and biodiesel) and compared bioethanol, and biodiesel) and compared to petroleumto petroleum

–– How are they similar and different from How are they similar and different from each other? Make a table to compareeach other? Make a table to compare

EXAM # 2 IS ON TUESDAY NOVEMBER 30TH: Endophyte-Assisted Phytoremediation plus the three bioenergy lectures so far

Comparing FuelsComparing FuelsStructureStructure–– Diesel: saturated hydrocarbons, C10Diesel: saturated hydrocarbons, C10--C15C15–– Biodiesel:Biodiesel:–– Ethanol/Bioethanol:Ethanol/Bioethanol:–– Methanol:Methanol:

Energy contentEnergy content–– Diesel: High energy contentDiesel: High energy content–– Biodiesel:Biodiesel:–– Ethanol/Bioethanol:Ethanol/Bioethanol:–– MethanolMethanol

Air pollutionAir pollution–– Diesel: HighDiesel: High–– Biodiesel:Biodiesel:–– Ethanol/Bioethanol:Ethanol/Bioethanol:–– Methanol:Methanol:

Fuel Comparisons (cont.)Fuel Comparisons (cont.)

What is it? What is it? Sources? Sources? Microbes needed? Microbes needed? How is each different from petroleum How is each different from petroleum or diesel? or diesel? Benefits of the biofuel?Benefits of the biofuel?

References References

www.ento.vt.edu/~salom/SPBbiology/blustain.htmlwww.ento.vt.edu/~salom/SPBbiology/blustain.htmlwww.pherotech.com/new_products.htmlwww.pherotech.com/new_products.htmlwww.dnr.wa.gov/../issues/2002issues.htmlwww.dnr.wa.gov/../issues/2002issues.htmlwww.laco.ufpe.br/prh28/www.laco.ufpe.br/prh28/www.biowww.bio--pro.de/en/region.rhein/magazin/01440pro.de/en/region.rhein/magazin/01440www.maize.agron.iastate.edu/corngrows.htmlwww.maize.agron.iastate.edu/corngrows.htmlwww.nrel.govwww.nrel.govwww.energy.iastae.eduwww.energy.iastae.eduwww.usda.gov/wps/portal/usdahomewww.usda.gov/wps/portal/usdahomewww.ethanolwww.ethanol--gec.org/clean/cf13.htmgec.org/clean/cf13.htmwww.eere.energy.govwww.eere.energy.gov/biomass//biomass/

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