Bioenergy from Agricultural Wastes

Bioenergy from Agricultural Wastes

PRESTED BY-DEEPAK KESHRIPRESTED BY-DEEPAK KESHRI

World Energy Prospects World Energy Prospects

60%63-

160%

Increase in

Population Energy demand

Source: •CIA's The World Factbook• World POPClock Projection, U.S. Census Bureau • Energy Sources, 26:1119-1129,2004

World's Population

10

6.7

0

2

4

6

8

10

12

2008 2050Year

Po

pu

lati

on

(b

illi

on

)

Other concernsOther concerns

Pollution Climate change Resource depletion

Pollution Climate change Resource depletion

Renewable energy sourcesRenewable energy sources

Summary of energy resources consumption in United States, 2004

Source: USDA-DOE, 2005, http://www.eere.energy.gov/biomass/publications.html.

•By 2030, bio-energy, 15-20% energy consumption

OverviewOverviewBioenergy history Ag wastes and other

biomassBiomass to Bioenergy

Conversion processesPros & Cons

ApplicationsBiofuelsBioheatBioelectricity

Bioenergy history Ag wastes and other

biomassBiomass to Bioenergy

Conversion processesPros & Cons

ApplicationsBiofuelsBioheatBioelectricity

Some U.S. bioenergy

history

Some U.S. bioenergy

history

1850s: Ethanol used for lighting (http://www.eia.doe.gov/ kids/energyfacts/sources/renewable/ethanol.html#motorfuel)

1860s-1906: Ethanol tax enacted (making it no longer competitive with kerosene for lights)

1896: 1st ethanol-fueled automobile, the Ford Quadricycle (http://www.nesea.org/greencarclub/factsheets_ethanol.pdf)

1850s: Ethanol used for lighting (http://www.eia.doe.gov/ kids/energyfacts/sources/renewable/ethanol.html#motorfuel)

1860s-1906: Ethanol tax enacted (making it no longer competitive with kerosene for lights)

1896: 1st ethanol-fueled automobile, the Ford Quadricycle (http://www.nesea.org/greencarclub/factsheets_ethanol.pdf)

Bioenergy is not new!

More bioenergy

history

More bioenergy

history

1908: 1st flex-fuel car, the Ford Model T1919-1933: Prohibition banned ethanol unless

mixed with petroleum WWI and WWII: Ethanol used due to high oil

costsEarly 1960s: Acetone-Butanol-Ethanol industrial

fermentation discontinued in USToday, about 110 new U.S. ethanol refineries in

operation and 75 more planned

1908: 1st flex-fuel car, the Ford Model T1919-1933: Prohibition banned ethanol unless

mixed with petroleum WWI and WWII: Ethanol used due to high oil

costsEarly 1960s: Acetone-Butanol-Ethanol industrial

fermentation discontinued in USToday, about 110 new U.S. ethanol refineries in

operation and 75 more planned

(photo from http://www.modelt.org/gallery/picz.asp?iPic=129)

Ag wastes and other biomassAg wastes and other biomass

Waste BiomassCrop and forestry residues, animal

manure, food processing waste, yard waste, municipal and C&D solid wastes, sewage, industrial waste

New Biomass: (Terrestrial & Aquatic)Solar energy and CO2 converted via

photosynthesis to organic compoundsConventionally harvested for food, feed,

fiber, & construction materials

Waste BiomassCrop and forestry residues, animal

manure, food processing waste, yard waste, municipal and C&D solid wastes, sewage, industrial waste

New Biomass: (Terrestrial & Aquatic)Solar energy and CO2 converted via

photosynthesis to organic compoundsConventionally harvested for food, feed,

fiber, & construction materials

Agricultural and Forestry Wastes

Agricultural and Forestry Wastes

Crop residuesAnimal manuresFood / feed processing

residuesLogging residues (harvesting

and clearing)Wood processing mill residuesPaper & pulping waste slurries

Crop residuesAnimal manuresFood / feed processing

residuesLogging residues (harvesting

and clearing)Wood processing mill residuesPaper & pulping waste slurries

Municipal garbage & other landfilled wastes

Municipal garbage & other landfilled wastes

Municipal Solid Waste Landfill gas-to-energy

Pre- and post-consumer residuesUrban wood residues

Construction & Demolition wastesTree trimmingsYard wastePackagingDiscarded furniture

Municipal Solid Waste Landfill gas-to-energy

Pre- and post-consumer residuesUrban wood residues

Construction & Demolition wastesTree trimmingsYard wastePackagingDiscarded furniture

U.S. DataU.S. Datacrop residue

animal manure

forest residue

MSW, C&D

Category Millions of dry tons/yr

U.S. (%)

Crop residues

218.9 43

Animal manures

35.1 7

Forest residues

178.8 35

Landfill wastes

78 15

%

(modified from Perlack et al.,

2005)

(modified from Perlack et al.,

2005)

Ohio data

(modified from Jeanty et al., 2004)

Ohio data

(modified from Jeanty et al., 2004)

crop residue

animal manure

forest residue

MSW, C&D

Category Billions of BTUs

Ohio (%)

Crop residues 53,717 18

Animal manures

2,393 1

Forest residues 33,988 12

Landfill wastes 199,707 69

%

Biomass to BioenergyBiomass to BioenergyBiomass: renewable energy sources

coming from biological material such as plants, animals, microorganisms and

municipal wastes

Biomass: renewable energy sources coming from biological material such as plants, animals, microorganisms and

municipal wastes

Bioenergy TypesBioenergy TypesBiofuels

LiquidsMethanol, Ethanol, Butanol,

Biodiesel

GasesMethane, Hydrogen

BioheatWood burning

BioelectricityCombustion in Boiler to TurbineMicrobial Fuel Cells (MFCs)

BiofuelsLiquids

Methanol, Ethanol, Butanol, Biodiesel

GasesMethane, Hydrogen

BioheatWood burning

BioelectricityCombustion in Boiler to TurbineMicrobial Fuel Cells (MFCs)

Conversion ProcessesConversion Processes Biological conversion

Fermentation (methanol, ethanol, butanol)

Anaerobic digestion (methane)

Anaerobic respiration (bio-battery)

Chemical conversionTransesterification

(biodiesel)Thermal conversion

CombustionGasificationPyrolysis

Biological conversionFermentation (methanol,

ethanol, butanol)Anaerobic digestion

(methane)Anaerobic respiration (bio-

battery)Chemical conversion

Transesterification (biodiesel)

Thermal conversionCombustionGasificationPyrolysis

Wet biomass(organic waste, manure)

Solid biomass(wood, straw)

Sugar and starch plants(sugar-cane, cereals)

Oil crops and algae(sunflower, soybean)

Biomass

Biomass-to-Bioenergy RoutesBiomass-to-Bioenergy Routes

EthanolButanol

Methyl ester(biodiesel)

Pyrolytic oil

BiogasH2, CH4

Fuel gas

Sugar

Pure Oil

Conversion processes

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iofu

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Biofuels and Bioenergy Application

Anaerobic

fermentation

Gasification

Combustion

Pyrolysis

Hydrolysis

Hydrolysis

Extraction

Crushing

Refining

fermentation

Transesterification

Photosynthesis

6CO

2 +

6H

2O

C

6H

12O

6 +

6O

2

co2

Advantages of Biomass   Advantages of Biomass  

Widespread availability in many parts of the world

Contribution to the security of energy supplies Generally low fuel cost compared with fossil fuels Biomass as a resource can be stored in large

amounts, and bioenergy produced on demand Creation of stable jobs, especially in rural areas Developing technologies and knowledge base

offers opportunities for technology exports Carbon dioxide mitigation and other emission

reductions (SOx, etc.)

Widespread availability in many parts of the world

Contribution to the security of energy supplies Generally low fuel cost compared with fossil fuels Biomass as a resource can be stored in large

amounts, and bioenergy produced on demand Creation of stable jobs, especially in rural areas Developing technologies and knowledge base

offers opportunities for technology exports Carbon dioxide mitigation and other emission

reductions (SOx, etc.)

Environmental Benefits

Drawbacks of BiomassDrawbacks of Biomass

Generally low energy content Competition for the resource with

food, feed, and material applications like particle board or paper

Generally higher investment costs for conversion into final energy in comparison with fossil alternatives

Generally low energy content Competition for the resource with

food, feed, and material applications like particle board or paper

Generally higher investment costs for conversion into final energy in comparison with fossil alternatives

ApplicationsApplications

Biofuel Applications: LiquidsBiofuel Applications: Liquids

Ethanol and Butanol: can be used in gasoline engines either at low blends (up to 10%), in high blends in Flexible Fuel Vehicles or in pure form in adapted engines

Biodiesel: can be used, both blended with fossil diesel and in pure form. Its acceptance by car manufacturers is growing

Ethanol and Butanol: can be used in gasoline engines either at low blends (up to 10%), in high blends in Flexible Fuel Vehicles or in pure form in adapted engines

Biodiesel: can be used, both blended with fossil diesel and in pure form. Its acceptance by car manufacturers is growing

Process for cellulosic bioethanol

Process for cellulosic bioethanol

http://www1.eere.energy.gov/biomass/abcs_biofuels.html http://www1.eere.energy.gov/biomass/abcs_biofuels.html

Why Butanol? Why Butanol?

More similar to gasoline than ethanolButanol can:

Be transported via existing pipelines (ethanol cannot)

Fuel engines designed for use with gasoline without modification (ethanol cannot)

Produced from biomass (biobutanol) as well as petroleum (petrobutanol)

Toxicity issues (no worse than gasoline)

More similar to gasoline than ethanolButanol can:

Be transported via existing pipelines (ethanol cannot)

Fuel engines designed for use with gasoline without modification (ethanol cannot)

Produced from biomass (biobutanol) as well as petroleum (petrobutanol)

Toxicity issues (no worse than gasoline)

Triglyceride consists of glycerol backbone + 3 fatty acid tails

The OH- from the NaOH (or KOH) catalyst facilitates the breaking of the bonds between fatty acids and glycerol

Methanol then binds to the free end of the fatty acid to produce a methyl ester (aka biodiesel)

Multi-step reaction mechanism: Triglyceride→Diglyceride →Monoglyceride →Methyl esters+ glycerine

Triglyceride consists of glycerol backbone + 3 fatty acid tails

The OH- from the NaOH (or KOH) catalyst facilitates the breaking of the bonds between fatty acids and glycerol

Methanol then binds to the free end of the fatty acid to produce a methyl ester (aka biodiesel)

Multi-step reaction mechanism: Triglyceride→Diglyceride →Monoglyceride →Methyl esters+ glycerine

GlycerineMethyl Ester

Triglyceride

Methoxide

Biodiesel from triglyceride oilsBiodiesel from triglyceride oils

Biodiesel ProductionBiodiesel Production

Biodiesel, Biodiesel, glyceringlycerin

Fuel GradeFuel GradeBiodieselBiodiesel

Fertilizer Fertilizer KK33POPO33

waterwater

Catalyst MixingCatalyst Mixing

MethanolMethanol

NeutralizationNeutralization

Acid (phosphoric)Acid (phosphoric)

Biodiesel,Biodiesel,impuritiesimpurities

Methanol RecoveryMethanol Recovery

Crude GlycerineCrude Glycerine

RecoveredRecoveredmethanolmethanol

Wash waterWash water

Phase SeparationPhase Separationgravity or centrifugegravity or centrifuge

PurificationPurification(washing)(washing)

Catalyst NaOHCatalyst NaOH

Crude Biodiesel (methyl ester)Crude Biodiesel (methyl ester)Crude glycerinCrude glycerinExcess methanolExcess methanolCatalyst KOHCatalyst KOH

Raw OilRaw Oil

Transesterification Transesterification ReactionReaction

Biofuel Applications: GasesBiofuel Applications: Gases

Hydrogen: can be used in fuel cells for generating electricity

Methane: can be combusted directly or converted to ethanol

Hydrogen: can be used in fuel cells for generating electricity

Methane: can be combusted directly or converted to ethanol

Bioheat ApplicationsBioheat ApplicationsSmall-scale heating

systems for households typically use firewood or pellets

Medium-scale users typically burn wood chips in grate boilers

Large-scale boilers are able to burn a larger variety of fuels, including wood waste and refuse-derived fuel

Small-scale heating systems for households typically use firewood or pellets

Medium-scale users typically burn wood chips in grate boilers

Large-scale boilers are able to burn a larger variety of fuels, including wood waste and refuse-derived fuel

Biomass Boiler

(for more info: Dr. Harold M. Keener, OSU Wooster, E-mail  keener.3@osu.edu)

Bioelectricity ApplicationsBioelectricity Applications

Co-generation: Combustion followed by a water vapor cycle driven turbine engine is the main technology at present

Microbial Fuel Cells (MFCs): Direct conversion of biomass to electricity

Co-generation: Combustion followed by a water vapor cycle driven turbine engine is the main technology at present

Microbial Fuel Cells (MFCs): Direct conversion of biomass to electricity

Microbial fuel cells (MFCs)Microbial fuel cells (MFCs)

Electrons flow from an anode through a resistor to a cathode where electron acceptors are reduced. Protons flow across a proton exchange membrane (PEM) to complete the circuit.

PE

M

Bio-electro-chemical devicesBacteria as biocatalysts convert the

biomass “fuel” directly to electricityOxidation-Reduction reaction

switches from normal electron acceptor (e.g., O2, nitrate, sulfate) to a solid electron acceptor: Graphite anode

Bio-electro-chemical devicesBacteria as biocatalysts convert the

biomass “fuel” directly to electricityOxidation-Reduction reaction

switches from normal electron acceptor (e.g., O2, nitrate, sulfate) to a solid electron acceptor: Graphite anode

It’s all about REDOX CHEMISTRY!

Microbial fuel cells in the lab Microbial fuel cells in the lab •Two-compartment MFC • Proton exchange membrane:

Nafion 117 or Ultrex• Electrodes: Graphite plate

84 cm2

• Working volume: 400 ml

ANODE CATHODE

Membrane

Anode

Cathode

Ano

de

Proton ExchangeMembrane

Cat

hod

e

Anodecompartment

Cathodecompartment

Cellulose

β-Glucan(n≤7)

β-Glucan (n ≤7)

Glucose

Cellodextrin

β- Glucan (n-1)

n≥2

n=1

6CO2 + 24e- + 24H+

Butyrate

4CO2 + 18e- + 18H+

Propionate

Acetate

3CO2 + 28e- + 28H+

2CO2 + 8e- + 8H+

O2

H2O

e-

e-

Not to Scale

Bacteria Cell

BacteriaCell Wall

H+ e-

H+ e-

H+

e-

e-

H+

My own MFC storyMy own MFC storyUndergraduate in-class presentation, 2003

Bond, D.R. Holmes, D.E., Tender L.M., Lovley D.R. 2002. Electrode-reducing microorganisms that harvest energy from marine sediments. Science 295: 483–485.

Extra-curricular student team project, 2004-2005USEPA - P3 first round winner 2005#1 in ASABE’s Gunlogson National Competition 2005

Research program, 2005 to present3 Ph.D. students, 2 undergrad honors theses, 4 facultyOver $200,000 in grant fundingHigh school science class project online resource

Undergraduate in-class presentation, 2003 Bond, D.R. Holmes, D.E., Tender L.M., Lovley D.R. 2002. Electrode-reducing

microorganisms that harvest energy from marine sediments. Science 295: 483–485.

Extra-curricular student team project, 2004-2005USEPA - P3 first round winner 2005#1 in ASABE’s Gunlogson National Competition 2005

Research program, 2005 to present3 Ph.D. students, 2 undergrad honors theses, 4 facultyOver $200,000 in grant fundingHigh school science class project online resource

http://digitalunion.osu.edu/r2/summer07/nskrinak/index.html

ReferencesReferences Ezeji, T., N. Qureshi, H.P. Blaschek. 2007. Butanol production from agricultural

residues: Impact of degradation products on Clostridum beijerinckii growth and butanol fermentation. Biotechnol. Bioeng. 97, 1460-1469.

Jeanty, P.W., D. Warren, and F. Hitzhusen. 2004. Assessing Ohio’s biomass resources for energy potential using GIS. OSU Dept of Ag, Env., and Development Economics, for Ohio Dept of Development. http://www.puc.state.oh.us/emplibrary/files/media/biomass/bioenergyresourceassessment.pdf

Klass, Donald L. 1998. Biomass for Renewable Energy, Fuels, and Chemicals. Academic Press. ISBN: 9780124109506.

Perlack et al. 2005. Biomass as feedstock for a bioenergy and bioproducts industry: The technical feasibility of a billion-ton annual supply. USDOE-USDA. http://www.puc.state.oh.us/emplibrary/files/media/biomass/BiomassFeedstock.pdf

Rabaey, K., Verstraete, W. 2005. Microbial fuel cells: Novel biotechnology for energy generation. Trends. Biotechnol. 23:291-298.

Rismani-Yazdi, H., Christy, A. D., Dehority, B.A., Morrison, M., Yu, Z. and Tuovinen, O. H. 2007. Electricity generation from cellulose by rumen microorganisms in microbial fuel cells. Biotechnol. Bioeng. 97, 1398-1407.

Skrinak, N. 2007. OSU Microbial Fuel Cell Learning Center <http://digitalunion.osu.edu/r2/summer07/nskrinak/index.html>

USDOE Biomass Program. ABCs of Biofuels <http://www1.eere.energy.gov/biomass/abcs_biofuels.html>. Accessed April 2008.

Ezeji, T., N. Qureshi, H.P. Blaschek. 2007. Butanol production from agricultural residues: Impact of degradation products on Clostridum beijerinckii growth and butanol fermentation. Biotechnol. Bioeng. 97, 1460-1469.

Jeanty, P.W., D. Warren, and F. Hitzhusen. 2004. Assessing Ohio’s biomass resources for energy potential using GIS. OSU Dept of Ag, Env., and Development Economics, for Ohio Dept of Development. http://www.puc.state.oh.us/emplibrary/files/media/biomass/bioenergyresourceassessment.pdf

Klass, Donald L. 1998. Biomass for Renewable Energy, Fuels, and Chemicals. Academic Press. ISBN: 9780124109506.

Perlack et al. 2005. Biomass as feedstock for a bioenergy and bioproducts industry: The technical feasibility of a billion-ton annual supply. USDOE-USDA. http://www.puc.state.oh.us/emplibrary/files/media/biomass/BiomassFeedstock.pdf

Rabaey, K., Verstraete, W. 2005. Microbial fuel cells: Novel biotechnology for energy generation. Trends. Biotechnol. 23:291-298.

Rismani-Yazdi, H., Christy, A. D., Dehority, B.A., Morrison, M., Yu, Z. and Tuovinen, O. H. 2007. Electricity generation from cellulose by rumen microorganisms in microbial fuel cells. Biotechnol. Bioeng. 97, 1398-1407.

Skrinak, N. 2007. OSU Microbial Fuel Cell Learning Center <http://digitalunion.osu.edu/r2/summer07/nskrinak/index.html>

USDOE Biomass Program. ABCs of Biofuels <http://www1.eere.energy.gov/biomass/abcs_biofuels.html>. Accessed April 2008.

For more info (or to request reference

list)

For more info (or to request reference

list)

Ann D. Christy, Ph.D., P.E.

Associate ProfessorDept of Food, Agricultural, and

Biological Engineering

614-292-3171Email: christy.14@osu.edu