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1
How can we explore local Indonesian bioethanol sources?
Basic idea
• Any such things contain polysaccharide can be converted to bioethanol(CH3CH2OH) using enzymes…!!!
• Where now we can get that polysaccharide from…???
2
BananaBanana plant can grow all of the year in tropical season.
Classification• Kingdom : Plantae• Divisi : Spermatophyta• Sub. Divisi : Angiospermae• Kelas : Monocotylae• Bangsa : Musales• Suku : Musaceae• Marga : Musa• Jenis : Musa paradisiacal
Banana
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Components Total (%)Glucose 6,84%Fructose 5,12%sucrose 1,05%
Wijana, 1998
orangeCitrus sp
NOT EFFICIENT
Degrading bacteria working optimum at pH 5,5‐8.
Zymomonas mobilis
able to change glucose, fructose, sucrose to be ethanol
Able to live at pH 3,5-7,5
Zymomonas mobilis
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Burning Wastes
Mass burn incineration Mass burn incineration
Air pollutionAir pollution
Waste to energyWaste to energy
Advantages
Reduced trashvolume
Less need forlandfills
Low waterpollution
Disadvantages
High cost
Air pollution(especiallytoxic dioxins)
Produces ahighly toxic ash
Encourageswaste production
Concept for the use of biomass
Biomass
fermentation
pyrolysis
gasification synthesis
ethanolethanol, , chemicalschemicals
fuelsfuels, , chemicalschemicals
chemicalschemicals
transport transport fuelsfuels
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(A) Typical fermentation products made by a K12 E. coli fermenting glucose. Products are in moles produced per 100 mol fermented glucose (Dien et al. 2003; Gottschalk 1986) with 91% of the carbon accounted for as fermentation products.
Metabolism of ethanol
(B) Transforming E. coli with pet operondiverts almost all glucose to ethanol. This strain (KO11) also carries a mutation that blocks succinateproduction.
Lin Y, Tanaka S., Ethanol fermentation from biomass resources: current state and prospects. Appl MicrobiolBiotechnol., 2005, 69 (6): 627-42.
Dien BS, Cotta MA, Jeffries TW., Bacteria engineered for fuel ethanol production: current status. ApplMicrobiol Biotechnol., 2003, 63(3): 258-66.
Metabolism of xylose to ethanol
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131275moderate temperature, short residence time
Fast pyrolysis
85105high temperature ,longresidence time
Gasification
353530low temperature ,longresidence time
Carbonisation
GasCharliquidyield, %Conditions
Biomass Pyrolysis Products
http://www.pyne.co.uk
Fast Pyrolysis LiquidBio-oil consists of many oxygenated organicchemicals and is water miscible.
dark brown liquid
combustible
not miscible with hydrocarbons
heating value ~ 17 MJ/kg
density ~ 1.2 kg/l
pH ~ 2.5
pungent odour
viscosity increases with time
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Fast Pyrolysis LiquidBio-oil consists of many oxygenated organicchemicals and is water miscible.
dark brown liquid
combustible
not miscible with hydrocarbons
heating value ~ 17 MJ/kg
density ~ 1.2 kg/l
pH ~ 2.5
pungent odour
viscosity increases with time
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BIOMASSgas coke
oil aqueousphase
Fractionation of Oils
Oil
Water solubles Water insolubles
HMWLExtractives, LMW
K. Sipila, E. Kuoppala, L. Fagernas, A. Oasmaa, Characterization of biomass-based flashpyrolysis oils, Biomass Bioenergy, 1998, 14, 103–113”.
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Oreganum stalk, wheat straw andcorncob.
Oregano is an aromatic and medical plant.
Oreganum stalks are abundant agricultural wastesfrom harvest
20 ±0.423 ±1.523 ±1.9Char
StrawCorncobOreganumstalk
Feed
35 ±1.341 ±0.939 ±3.1Oil6 ±0.56 ±1.36 ±0.3Aqueous phase
393032Gas*
* Calculated from mass balance ;
Comparison: Product distributions frompyrolysis of agricultural wastes, wt%
Oil yields----------- 13-17 wt% from rapeseed14 wt% from sugarcane bagasse, coconut shell57 wt% (containing 43 wt% waer) from rice straw66 wt% (containing 20 wt% water) from pine sawdust
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1.250.031.300.661.450.13Furans
0.050.01ndnd0.04ndPyrans
0.590.220.200.290.500.42propanal, 3-hydroxy5.121.897.375.546.892.46Nonaromatic ketones
4.404.63-0.822.231.94hydroxyacetaldehyde
Nonaromatic aldehydes
0.290.110.320.310.440.20propanoic2.602.242.564.075.092.93acetic
Acids
WSAPWSAPWSAP
StrawOreganumCorncob
The compounds detected by GC/MS, wt.%Characterization of pyrolytic oil
AP:aqueous phase; WS:water soluble fractions
13.500.0812.54nil0.660.18Total phenols, wt.%1.292.491.303.051.702.04Methanol, v/v%6.212.52n.dn.d1.223.15Formaldehyde,wt%1.780.460.150.031.220.34Formic acid, wt.%14.73.31.02.45.07.3Acetone, v/v %
WSAPWSAPWSAP
StrawOreganumCorncob
The concentration of some compounds detected by HPLC and photometer, wt.%
Characterization of pyrolytic oil
AP:aqueous phase; WS:water soluble fractions
17
200 nm200 nm
McCann et al. 1990 McCann et al. 1990 J. Cell Sci.J. Cell Sci. 9696, , 323323--334334
Molecular Architecture of Plant Cell Walls Molecular Architecture of Plant Cell Walls ((lignocellulosiclignocellulosic biomass)biomass)
•• Most abundant in Indonesia Most abundant in Indonesia (> 70 million (> 70 million tonnestonnes annually)annually)
•• Production of biomass Production of biomass throughout the year throughout the year
•• Main contributor of biomass Main contributor of biomass ––palm oil industrypalm oil industry–– Oil Palm Empty fruit Oil Palm Empty fruit
bunches (OPEFB)bunches (OPEFB)–– Palm oil mill effluent (POME)Palm oil mill effluent (POME)–– MesocarpMesocarp fiberfiber–– Palm kernel shellsPalm kernel shells–– Palm kernel cake (residue)Palm kernel cake (residue)
•• Mainly Mainly lignoligno--cellulosic cellulosic materialsmaterials
Palm Oil 94%
Rice 1%
Sugarcane 1%
Wood industry
4%
Biomass resources: Agricultural residuesBiomass resources: Agricultural residues
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Palm Oil Industry: BiomassPalm Oil Industry: Biomass
•• Biomass production (2007)Biomass production (2007)–– Empty fruit bunch (EFB) Empty fruit bunch (EFB) –– 15 million 15 million tonnestonnes–– Palm kernel shell Palm kernel shell -- 8 million 8 million tonnestonnes–– MesocarpMesocarp fiber fiber –– 5 million 5 million tonnestonnes–– Abundant and concentrated in the mills Abundant and concentrated in the mills
(business as usual)(business as usual)
3636
New Business and Products from Palm BiomassNew Business and Products from Palm Biomass
Oil Palm Empty Fruit Bunch 16 million t/yr
Palm Oil Mill Effluent50 million t/yr
Standardised biomass available “business as usual”
Sugars
Bioplastic (PLA) or Bioethanol
Pre-treatment and Saccharification
Fermentation in bioreactors
Biomass Energy
Bio-acids
Bioplastic(PHA) Biogas, CH4 (+ Biohydrogen)
“zero emissionzero emission”wastewaste--toto--wealthwealth
+ water recycling+ water recyclingCompost
19
3737
Adding Value to Palm BiomassAdding Value to Palm Biomass•• Paradigm shift towards biomassParadigm shift towards biomass
–– Not wasteNot waste–– RenewableRenewable–– SustainableSustainable–– UnderUnder--utilisedutilised resourceresource
•• Uncertainties of biomassUncertainties of biomass–– Technological provenTechnological proven ??–– Economically feasibleEconomically feasible ??–– Quality and quantity ?Quality and quantity ?–– Availability & distribution ?Availability & distribution ?
value chainvalue chainfine chemicalsfine chemicals
foodfoodfiber fiber
feedfeedfuelfuel
Lignin and Cellulose Molecules
38
• Average molecular composition, soft maple lignin: CH1.2O0.27
– Cellulose composition: CH1.7 O0.83
• Up to 30% of the mass of wood, and 40% of the energy content• Wood processing plants produce 50 million tons of lignin waste
annually
Holladay et al. “Top Value-Added Chemicals from Biomass: Volume II- Results of Screening Potential Candidates from Biorefinery Lignin.” Pacific Northwest National Laboratory. October 2007.
20
Converting Biomass Using BiorefineryConcept
R. R. AgrawalAgrawal and N. Singh, and N. Singh, AIChEAIChE JournalJournal, 2009, 55, 1898, 2009, 55, 1898
Biological Conversion of Cellulose to Biological Conversion of Cellulose to BiofuelBiofuel
McCann et al.McCann et al.
21
Thermal Conversion of Lignin to Jet Fuel
41Huber, GW. “Catalysis for Production of JP-8 Range Molecules from Lignocellulosic Biomass.” 12 March 2009.
Thermochemical Transformation of Lignocellulosic Biomass
Traditional paths entail high temperatures and suffer from carbonCPOX forms no carbon
Biomass
PyrolysisHigh T
OilCharTar
FuelCat. upgrade
SyngasCharGasification Methanol
Synfuel
CPOX SyngasVery high T
22
Sorbitol
HOO
HO OHOH
OH
Glucose Mannitol
Hydrolysis
isomerization
H2
Hydrogenation
OH
OH
Ethylene glycol
+other
polyols
OH
HOO
O
HO OH
O
OH
n
Cellulose
O
H2O
Fructose
CH2OH
OCH2OH
OH
OH
HO
H2
Hydrogenation
OHOH
OH
OH OH
OH
OHOH
OH
OH OH
OH
-H2O
Dehydration
H2
Hydrogenation
H2
HydrogenolysisLight alkanes
CO2, etc.
H+
C-C cleavage+oxdationOrganic acids(unidentified)
OOH O
OOH OH
HMF DHM-THF
OH
Catalytic Conversion of Cellulose to Chemicals
Conversion of cellulose to ethylene glycol on Ni-WC & Ni-W2C:Na et al. Angew. Chem. Int. Ed. (2008); Catalysis Today (2009)
Commodity chemicals from ethanolCH3CH2OH
CH2=CH2 CH3CHO CH3CO2H
Ethyl benzeneEthyl bromideEthyl chlorideEthylene chlorohydrinEthylene diamineEthylene dibromideEthylene dichlorideEthylene glycolEthyleneimineEthylene oxideDiethyl ketoneDiethylene glycolGlycol ethers, estersMEA, DEA, TEAVinyl acetatePolymers, copolymers
Acetic acidAcetic anhydrideAldol productsButyl acetateButyl alcoholButyraldehydeChloralEthyleneiminePyridines
AcetamideAcetanilideAcetyl chlorideAcetic anhydrideDimethyl acetamideCellulose acetatesEsters
23
Microbial Fuel Cell1. 用微生物當作觸媒的微生物燃料電池系統2. 用微生物產物當作燃料的微生物燃料電池系統
用微生物當作觸媒的微生物燃料電池系統
Rabaey K, Verstraete W. Microbial fuel cells: novel biotechnology for energy generation. Trends Biotechnol., 2005,23(6):291-8.
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用微生物產物當作燃料的微生物燃料電池系統 1
E. Nakada, S. Nishikat, Y. Asada, J.Miyake Photosynthetic bacterial hydrogen production combined with a fuel cell. International Journal of Hydrogen Energy. 1999, 24: 1053-1057.
用光合細菌直接生產的氫氣來產生能量。
用微生物產物當作燃料的微生物燃料電池系統 2
Microbial Fuel Cell: High Yield Hydrogen Source And Wastewater Cleaner
http://www.sciencedaily.com/releases/2005/04/050422165917.htm