How can we explore local Indonesian bioethanol sources

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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…!!!

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Banana

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Pepaya

Jeruk

Components Total (%)

Glucose 6,84%

Fructose 5,12%

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Components Total (%)

Glucose 6,84%

Fructose 5,12%

sucrose 1,05%

Wijana, 1998

orange

Citrus 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

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Ditimbun…???

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Apa akan dibakar….??

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Burning Wastes

¾

Mass burn incineration

¾

Mass burn incineration

¾

Air

pollution

¾

Air

pollution

¾

Waste to

energy

¾

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, , chemicalschemicals

fuels

fuels, , chemicalschemicals

chemicals

transport

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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 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, Jeffries TW., Bacteria engineered for fuel ethanol production: current status. Appl Microbiol Biotechnol., 2003, 63(3): 258-66.

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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.

¾dark brown liquid ¾combustible

¾not miscible with hydrocarbons ¾heating value ~ 17 MJ/kg ¾density ~ 1.2 kg/l

¾pH ~ 2.5 ¾pungent odour

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Fast Pyrolysis Liquid

Bio-oil consists of many oxygenated organic chemicals and is water miscible.

¾dark brown liquid ¾combustible

¾not miscible with hydrocarbons ¾heating value ~ 17 MJ/kg ¾density ~ 1.2 kg/l

¾pH ~ 2.5 ¾pungent odour

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BIOMASS

gas

coke

oil

aqueous

phase

Fractionation of Oils

Oil

Water solubles

Water insolubles

HMWL

Extractives,

LMW

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Oreganum stalk, wheat straw and

corncob.

Oregano is an aromatic and medical plant.

Oreganumstalks are abundant agricultural wastes from harvest

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

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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

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200 nm

McCann et al. 1990

McCann et al. 1990 J. Cell Sci.J. Cell Sci.9696, , 323323--334334

Molecular Architecture of Plant Cell Walls

(

lignocellulosic

biomass)

•

• Mo st a b unda nt in Ind o ne sia Mo st a b unda nt in Ind o ne sia

(> 70 m illio n

(> 70 m illio n to nne sto nne sa nnua lly)a nnua lly)

•

• Pro duc tio n o f b io m a ss Pro duc tio n o f b io m a ss

thro ug ho ut the ye a r

•

• Ma in c o ntrib uto r o f b io m a ss Ma in c o ntrib uto r o f b io m a ss –– pa lm o il industry

pa lm o il industry

–

– O il Pa lm Em pty fruit O il Pa lm Em pty fruit b unc he s (O PEFB)

b unc he s (O PEFB)

–

– Pa lm o il m ill e fflue nt (PO ME)Pa lm o il m ill e fflue nt (PO ME) –

– Me so c a rpMe so c a rpfib e rfib e r

–

– Pa lm ke rne l she llsPa lm ke rne l she lls

– Pa lm ke rne l c a ke (re sidue )Pa lm ke rne l c a ke (re sidue )

Palm Oil 94% Rice 1% Sugarcane 1% Wood industry 4%

Bio m a ss re so urc e s: Ag ric ultura l re sidue s

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Pa lm O il Industry: Bio m a ss

•

• Bio m a ss pro duc tio n (2007)Bio m a ss pro duc tio n (2007)

–

– Em pty fruit b unc h (EFB) Em pty fruit b unc h (EFB) ––15 m illio n 15 m illio n to nne sto nne s

–

– Pa lm ke rne l she ll -Pa lm ke rne l she ll - 8 m illio n 8 m illio n to nne sto nne s

–

– Me so c a rpMe so c a rpfib e r –fib e r –5 m illio n to nne s5 m illio n to nne s

–

– Ab unda nt a nd c o nc e ntra te d in the m ills Ab unda nt a nd c o nc e ntra te d in the m ills (b usine ss a s usua l)

(b usine ss a s usua l)

36

Ne w Busine ss a nd Pro duc ts fro m Pa lm Bio m a ss Ne w Busine ss a nd Pro duc ts fro m Pa lm Bio m a ss

O il Pa lm Em pty Fruit Bunc h 16 m illio n t/ yr

Pa lm O il Mill Efflue nt 50 m illio n t/ yr Sta nda rdise d b io m a ss a va ila b le

“b usine ss a s usua l”

Sug a rs Bio pla stic (PLA)

o r Bio e tha no l

Pre - tre a tm e nt a nd Sa c c ha rific a tio n

Fe rm e nta tio n in b io re a c to rs

Bio m a ss Ene rg y

Bio - a c ids

Bio pla stic (PHA) Bio g a s, C H4(+ Bio hydro g e n)

“ze ro e m issio n”ze ro e m issio n wa ste

wa ste--toto--we a lthwe a lth

+ water recycling

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37

Adding Va lue to Pa lm Bio m a ss

•

• Pa ra dig m shift to wa rds b io m a ssPa ra dig m shift to wa rds b io m a ss

–

– No t wa steNo t wa ste –

– Re ne wa b leRe ne wa b le –

– Susta ina b leSusta ina b le –

– Und e rUnd e r--utilise dutilise dre so urc ere so urc e

•

• Unc e rta intie s o f b io m a ssUnc e rta intie s o f b io m a ss

–

– Te c hno lo g ic a l pro ve nTe c hno lo g ic a l pro ve n??

–

– Ec o no m ic a lly fe a sib leEc o no m ic a lly fe a sib le??

–

– Q ua lity a nd q ua ntity ?Q ua lity a nd q ua ntity ? –

– Ava ila b ility & distrib utio n ?Ava ila b ility & distrib utio n ?

Ï

Ï va lue c ha inva lue c ha in

fine c he m ic a ls fine c he m ic a ls fo o d

fo o d fib e r fib e r fe e d

fe e d fue l fue l

Lignin and Cellulose Molecules

• Average molecular composition, soft maple lignin: CH_1.2O_0.27 – Cellulose composition: CH_1.7O_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

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Converting Biomass Using Biorefinery

Concept

R.

R. AgrawalAgrawaland N. Singh, and N. Singh, AIChEAIChEJournalJournal, 2009, 55, 1898, 2009, 55, 1898

Biological Conversion of Cellulose to

Biofuel

McCann et al.

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Thermal Conversion of Lignin to Jet Fuel

41

Huber, GW. “Catalysis for Production of JP-8 Range Molecules from Lignocellulosic Biomass.” 12 March 2009.

Thermochemical Transformation of

Lignocellulosic Biomass

¾

Traditional paths entail high temperatures and suffer from carbon

¾

CPOX forms no carbon

Biomass

Pyrolysis High T

Oil

Char Tar

Fuel

Cat. upgrade

Syngas

Char

Gasification Methanol

Synfuel

CPOX Syngas

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Sorbitol HO O HO OH OH OH Glucose _Mannitol Hydrolysis isomerization H2 Hydrogenation OH OH Ethylene glycol

+ _polyolsother

OH HO O O HO _OH O OH n Cellulose O H2O Fructose

CH2OH O CH2OH

OH OH HO H2 Hydrogenation OH OH OH OH OH OH OH OH OH OH OH OH -H2O Dehydration H2 Hydrogenation H2 Hydrogenolysis Light alkanes CO2, etc. H+ C-C cleavage+oxdation Organic acids (unidentified) 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

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Microbial Fuel Cell

1. 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

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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