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

3

Pepaya

JerukComponents 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

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

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 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

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 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

11

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

12

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

13

14

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”.

15

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

16

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

18

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.

24

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