1

How can we explore local

Indonesian bioethanol sources?
Basic idea
Any such things contain polysaccharide
can be converted to bioethanol
(CH
3
CH
2
OH) using enzymes!!!
Where now we can get that
polysaccharide from???
2
Banana
anana plant can grow all ol
the year in tropical season.
Classilication
Kingdom : Plantae
Divisi : 5permatophyta
5ub. Divisi : Angiospermae
Kelas : Monocotylae
angsa : Musales
5uku : Musaceae
Marga : Musa
1enis : Musa paradisiacal
Banana
3
Pepaya
Jeruk
Components Total (%)
Glucose 6,84%
Fructose 5,12%
Sucrose 1,05%
Wijana,1998
4
Components Total (%)
Glucose 6,84%
Fructose 5,12%
sucrose 1,05%
Wijana,1998
orange
Citrus sp
NOT EFFICIENT
Degrading bacteria
working optimum
at pH5,58.
Zymomonas mobilis
able to change glucose,
fructose, sucrose to be
ethanol
Able to live at pH
3,5-7,5
Zymomonas mobilis
5
Sampah Rumah Tangga
6
7
Ditimbun???
Municipal waste
(common in Indonesia)
8
Apa akan dibakar.??
Pembakaran?
9
Burning Wastes
Mass burn incineration
Mass burn incineration
Air
pollution
Air
pollution
Waste to
energy
Waste to
energy
Advantages
Reduced trash
volume
Less need for
landfills
Low water
pollution
Disadvantages
High cost
Air pollution
(especially
toxic dioxins)
Produces a
highly toxic ash
Encourages
waste production
Concept for the use of biomass
Biomass
fermentation
pyrolysis
gasification synthesis
ethanol ethanol , , chemicals chemicals
fuels fuels, , chemicals chemicals
chemicals chemicals
transport transport fuels fuels
10
(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 operon
diverts almost all glucose to ethanol.
This strain (KO11) also carries a
mutation that blocks succinate
production.
Lin Y, Tanaka S., Ethanol fermentation from biomass resources: current state and prospects. Appl Microbiol
Biotechnol., 2005, 69 (6): 627-42.
Dien BS, Cotta MA, J effries TW., Bacteria engineered for fuel ethanol production: current status. Appl
Microbiol Biotechnol., 2003, 63(3): 258-66.
Metabolism of xylose to ethanol
11
13 12 75
moderate temperature,
short residence time
Fast pyrolysis
85 10 5
high temperature ,long
residence time
Gasification
35 35 30
low temperature ,long
residence time
Carbonisation
Gas Char liquid
yield, % Conditions
Biomass Pyrolysis Products
http://www.pyne.co.uk
Fast Pyrolysis Liquid
Bio-oil consists of many oxygenated organic
chemicals 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
12
Fast Pyrolysis Liquid
Bio-oil consists of many oxygenated organic
chemicals 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
13
14
BIOMASS
gas
coke
oil aqueous
phase
Fractionation of Oils
Oil
Water solubles
Water insolubles
HMWL Extractives,
LMW
K. Sipila, E. Kuoppala, L. Fagernas, A. Oasmaa, Characterization of biomass-based flash
pyrolysis oils, Biomass Bioenergy, 1998, 14, 103113.
15
Oreganum stalk, wheat strawand
corncob.
Oregano is an aromatic and medical plant.
Oreganum stalks are abundant agricultural wastes
fromharvest
20 0.4 23 1.5 23 1.9 Char
Straw Corncob Oreganum
stalk
Feed
35 1.3 41 0.9 39 3.1 Oil
6 0.5 6 1.3 6 0.3 Aqueous phase
39 30 32 Gas
*
* Calculated from mass balance ;
Comparison: Product distributions from
pyrolysis of agricultural wastes, wt%
Oil yields----------- 13-17 wt% from rapeseed
14 wt% from sugarcane bagasse, coconut shell
57 wt% (containing 43 wt% waer) from rice straw
66 wt% (containing 20 wt% water) from pine sawdust
16
1.25 0.03 1.30 0.66 1.45 0.13 Furans
0.05 0.01 nd nd 0.04 nd Pyrans
0.59 0.22 0.20 0.29 0.50 0.42 propanal, 3-hydroxy
5.12 1.89 7.37 5.54 6.89 2.46 Nonaromatic ketones
4.40 4.63 - 0.82 2.23 1.94 hydroxyacetaldehyde
Nonaromatic aldehydes
0.29 0.11 0.32 0.31 0.44 0.20 propanoic
2.60 2.24 2.56 4.07 5.09 2.93 acetic
Acids
WS AP WS AP WS AP
Straw Oreganum Corncob
The compounds detected by GC/MS, wt.%
Characterization of pyrolytic oil
AP:aqueous phase; WS:water soluble fractions
13.50 0.08 12.54 nil 0.66 0.18 Total phenols, wt.%
1.29 2.49 1.30 3.05 1.70 2.04 Methanol, v/v%
6.21 2.52 n.d n.d 1.22 3.15 Formaldehyde,wt%
1.78 0.46 0.15 0.03 1.22 0.34 Formic acid, wt.%
14.7 3.3 1.0 2.4 5.0 7.3 Acetone, v/v %
WS AP WS AP WS AP
Straw Oreganum Corncob
The concentration of some compounds detected
by HPLC and photometer, wt.%
Characterization of pyrolytic oil
AP:aqueous phase; WS:water soluble fractions
17
200 nm 200 nm
McCann et al. 1990 McCann et al. 1990 J. Cell Sci. J. Cell Sci. 96 96, , 323 323- -334 334
Molecular Architecture of Plant Cell Walls Molecular Architecture of Plant Cell Walls
( (lignocellulosic lignocellulosic biomass) biomass)
Most abundant in Indonesia Most abundant in Indonesia
(> 70 million (> 70 million tonnes tonnesannually) annually)
Production of biomass Production of biomass
throughout the year throughout the year
Main contributor of biomass Main contributor of biomass
palm oil industry palm oil industry
Oil Palm Empty fruit Oil Palm Empty fruit
bunches (OPEFB) bunches (OPEFB)
Palm oil mill effluent (POME) Palm oil mill effluent (POME)
Mesocarp Mesocarp fiber fiber
Palm kernel shells Palm kernel shells
Palm kernel cake (residue) Palm kernel cake (residue)
Mainly Mainly ligno ligno- -cellulosic cellulosic
materials materials
Palm Oil
94%
Rice 1%
Sugarcane
1%
Wood
industry
4%
Biomass resources: Agricultural residues Biomass resources: Agricultural residues
18
Palm Oil Industry: Biomass Palm Oil Industry: Biomass
Biomass production (2007) Biomass production (2007)
Empty fruit bunch (EFB) Empty fruit bunch (EFB) 15 million 15 million tonnes tonnes
Palm kernel shell Palm kernel shell - - 8 million 8 million tonnes tonnes
Mesocarp Mesocarp fiber fiber 5 million 5 million tonnes tonnes
Abundant and concentrated in the mills Abundant and concentrated in the mills
(business as usual) (business as usual)
36 36
New Business and Products from Palm Biomass New Business and Products from Palm Biomass
Oil Palm Empty Fruit Bunch
16 million t/yr
Palm Oil Mill Effluent
50 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, CH
4
(+Biohydrogen)
zero emission zero emission
waste waste- -to to- -wealth wealth
+ water recycling + water recycling
Compost
19
37 37
Adding Value to Palm Biomass Adding Value to Palm Biomass
Paradigm shift towards biomass Paradigm shift towards biomass
Not waste Not waste
Renewable Renewable
Sustainable Sustainable
Under Under- -utilised utilised resource resource
Uncertainties of biomass Uncertainties of biomass
Technological proven Technological proven ? ?
Economically feasible Economically feasible ? ?
Quality and quantity ? Quality and quantity ?
Availability & distribution ? Availability & distribution ?
value chain value chain
fine chemicals fine chemicals
food food
fiber fiber
feed feed
fuel fuel
Lignin and Cellulose Molecules
38
Average molecular composition, soft maple lignin: CH
1.2
O
0.27
Cellulose composition: CH
1.7
O
0.83
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 BiorefineryLignin. Pacific Northwest National
Laboratory. October 2007.
20
Converting Biomass Using Biorefinery
Concept
R. R. Agrawal Agrawal and N. Singh, and N. Singh, AIChE AIChE Journal Journal, 2009, 55, 1898 , 2009, 55, 1898
Biological Conversion of Cellulose to Biological Conversion of Cellulose to Biofuel Biofuel
McCann et al. McCann et al.
21
Thermal Conversion of Lignin to J et Fuel
41 Huber, GW. Catalysis for Production of J P-8 Range Molecules from Lignocellulosic Biomass.12 March 2009.
Thermochemical Transformation of
Lignocellulosic Biomass
Traditional paths entail high temperatures and suffer from carbon
CPOX forms no carbon
Biomass
Pyrolysis
High T
Oil
Char
Tar
Fuel
Cat. upgrade
Syngas
Char
Gasification
Methanol
Synfuel
CPOX Syngas
Very high T
22
Sorbitol
HO
O
HO
OH
OH
OH
Gl ucose
Mannitol
Hydrolysis
isomerization
H
2
Hydrogenation
OH
OH
Ethyl ene gl ycol
+
other
pol yols
OH
HO
O
O
HO
OH
O
OH
n
Cel lulose
O
H2O
Fructose
CH2OH
O
CH2OH
OH
OH
HO
H
2
Hydrogenation
OH
OH
OH
OH OH
OH
OH
OH
OH
OH OH
OH
-H
2
O
Dehydration
H
2
Hydrogenation
H
2
Hydrogenolysis
Light al kanes
CO2, etc.
H
+
C-C cleavage+oxdation
Organic aci ds
(uni denti fied)
O
OH O
O
OH OH
HMF DHM-THF
OH
Catalytic Conversion of Cellulose to Chemicals
Conversion of cellulose to ethylene glycol on Ni-WC & Ni-W
2
C:
Na et al. Angew. Chem. Int. Ed. (2008); Catalysis Today (2009)
Commodity chemicals from ethanol
CH
3
CH
2
OH
CH
2
=CH
2 CH
3
CHO CH
3
CO
2
H
Ethyl benzene
Ethyl bromide
Ethyl chloride
Ethylene chlorohydrin
Ethylene diamine
Ethylene dibromide
Ethylene dichloride
Ethylene glycol
Ethyleneimine
Ethylene oxide
Diethyl ketone
Diethylene glycol
Glycol ethers, esters
MEA, DEA, TEA
Vinyl acetate
Polymers, copolymers
Acetic acid
Acetic anhydride
Aldol products
Butyl acetate
Butyl alcohol
Butyraldehyde
Chloral
Ethyleneimine
Pyridines
Acetamide
Acetanilide
Acetyl chloride
Acetic anhydride
Dimethyl acetamide
Cellulose acetates
Esters
23
Microbial Fuel Cell
1.
2.

RabaeyK, VerstraeteW. Microbial fuel cells: novel biotechnology for energy generation. Trends Biotechnol., 2005,
23(6):291-8.
24

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.

2
Microbial Fuel Cell: High Yield Hydrogen
Source And Wastewater Cleaner
http://www.sciencedaily.com/releases/2005/04/050422165917.htm