Biofuels in BrazilBiofuels in Brazil

“van’t Hoff Institute for Molecular Sciences”

Amsterdam, 2007

Prof. Donato ArandaFederal Univ. Rio de Janeiro

Energy MixEnergy Mix

1925: First experiments with ethanol/gasoline blends 1975: Ethanol program started after the 1st oil crisis 1989: Leaded Gasoline forbiden. 1993: E-20 to E-25 mandatory in all the country (33,000

gas stations) 2003: Flex Fuel engines 2006: 80% of new vehicles are Flex (2.5 million/year) 615 million ton of CO2 avoided emissions, so far

Ethanol Program in BrazilEthanol Program in Brazil

Sugar Cane Output/Input Energy ~ 8.2*Sugar Cane Output/Input Energy ~ 8.2*

Ethanol production in 2006: 16 billion liters

*Goldenberg, J.L.C Renewable Energies, Island Press, 1993

Ethanol Plants Ethanol Plants

313 Ethanol Plants

1 million employees

60,000 agric. producers

5 million ha (0.6 % of Br. area)

89 New plants are being contructed

Raw Material Production / ha (kg)

Quantity of Product / liter

of EthanolQuantity of Ethanol / ha

SUGAR CANE 85,000 12 kg 7,080 liter

CORN 10,000 2.8 kg 3,570 liter

Source: Brazilian Agricultural Ministry

Physical ProductivityPhysical Productivity

0 1 2 3 4 5 6 7 8

Trigo

Milho (EUA)

Beterraba

Cana-de-Açúcar (Brasil)

Source: F.O.Licht (in “New trends to the ethanol supply chain in Brazil”, Simoes, R.B., Master Thesis, Universiteit Van Tilburg, Holanda, Jul-2006)

Wheat

Corn

Sugar Beet

Sugar Cane (Brazil)

Ethanol Energetic Balance

Output/Input Energy

Sugar Cane EnergySugar Cane Energy1 mton of Sugar Cane:1.7 103 kcal ~ 1.2 barrel of petroleum

Sugar cane bagasse is producing ~ 2,500 MW

Breakthrough: ethanol from bagasse and other residual biomass

Sugar Cane EnergySugar Cane EnergySugar Sugar Cane Biomass Cane Biomass ((yearyear))

~350 x 10~350 x 1066 mtonmton (40% (40% waterwater))

““Per Per capitacapita”” biomassbiomass~2 ~2 tonton// personperson// yearyear

147 x 147 x 101066 tons of tons of sugarssugars

World World sugar sugar productionproduction::140 x 140 x 101066 tons/tons/ yearyear

EthanolEthanol ((potentialpotential) 92 x 10) 92 x 1099 L/L/ yearyear

WithWith lowlow fermentation efficiencyfermentation efficiency 60 x 1060 x 1099 LitersLiters

Fonte: Pereira & Pereira J r. (2006)

Basic Biomass CompositionBasic Biomass Composition

Cellulose (40-60%)Cellulose (40-60%)

Hemicellulose (20-40%)Hemicellulose (20-40%)

Lignin (10-25%)Lignin (10-25%)

Hemicellulose convertion to ethanol: Brazilian Patent: Petrobras/UFRJ Hemicellulose convertion to ethanol: Brazilian Patent: Petrobras/UFRJ nno o PI0505299-8 (11/2005)PI0505299-8 (11/2005)

LigninLignin

O

OCH3

H2CO

CO

CHCH

CH

O

H2COH

H2COH

O

CH

CH

CH2OH

O

CH3O OCH3

HC HC

HC

CH2OHO

CH2

H3CO OCH3

OH

OHC

CH2OH

CHO

OCH3

OCH3

O

H2COH

CO

CH

H3CO

O CH

CH

CH2OH

CH3O OCH3

O

CH

CH2OH

CHO

OCH3

H3CO

HC

CH2OH

CH

CH3OOH

OCH3 O

CH COOHHOCH

CO

HC

CH2OH

O

O

CH

CO

CH2OH

CH3OO CH

HC

CH2OH

O

CH3O OCH3

OH

OCH3

CH

HC

CH2OH

OCH3

O CH

HC

O

CH CHOHOCH2

CH3O

CH2O

COHCHOCH2

O

OCH3CH3O

HOHC

HC

HOH2C

OCH3

O CH

HC

OCH3

CH2OH

O

OCH3

HC O

HC

HOH2C

OH

CH

CH

CHO

OOCH3CH3O

HC

HC

H2C

OCH2

CH

CHO

OCH3CH2O

O CH

CH

CH2OH

O

OCH3CH3OOH

CH3O

HC O

HC

HOH2C

CH

HC

CH2OH

OCH3

HC

HC

CH2OH

CH3O OCH3

O-

CH

CH2OH

HC

OH

OCH3

a1

CH2

HC

CH3O OCH3

O-

CH

CH2

OH

OCH3

CH2H2C

O

a5

Coniferilic AlcoholCumaric Alcohol

Sinapilic Alcohol

Flash Pyrolysis

PYROLYSIS OIL

~ 30% OxygenpH ~ 2

Collaboration with Brem, C. and Brammer, J.G, Collaboration with Brem, C. and Brammer, J.G, Twente UniversityTwente University

Ethanol/Biodiesel IntegrationEthanol/Biodiesel Integration

Barralcool (Mato Grosso State)

Produces:100,000 mt/year of Ethanol50,000 mt/year of Biodiesel

Biodiesel ProgramBiodiesel Program

B2 mandatory at Jan/2008 (850,000 ton/year) B5 mandatory at Jan/2010 (2013, originaly)

Now: 10 biodiesel plants working (500,000 ton/year) 4,000 gas stations providing B2 Some transportation companies using B30 (More than 2,000

buses) Projects: More than 100 new biodiesel plants

LOW FEDERAL TAXES FOR SOCIAL PROJECTS AND POOR LOW FEDERAL TAXES FOR SOCIAL PROJECTS AND POOR REGIONSREGIONS

Soybean,Soybean,Tallow,Tallow,CottonCotton

PalmPalmCastorCastor

SunflowerSunflower

JatrophaJatropha

CanolaCanola

BabassuBabassu

PeanutPeanut

Soybean Biodiesel (Output/input energy ~ 3)*Soybean Biodiesel (Output/input energy ~ 3)*

* NREL (USA) http://www.nrel.gov/docs/legosti/fy98/24089.pdf

Jatropha curcas BiodieselJatropha curcas Biodiesel

Output/Input Energy ~ 5- 6*

*Ref: Ouedraogo, 1991

Palm Oil BiodieselPalm Oil Biodiesel

Output/Input Energy ~ 8*Output/Input Energy ~ 8*

*Ref: Lor, E.E.S. et al, World Bioenergy http://www.svebio.se/attachments/33/295.pdf

PalmPalm

- Production Costs US$ 240/ton of oil 5,000 – 8,000 Liters/ha

11stst Biodiesel Plant – Heterogeneous Biodiesel Plant – Heterogeneous Catalyst/Residual FeedstockCatalyst/Residual Feedstock

(Crude Palm Fatty Acids) (Crude Palm Fatty Acids)

Patent: D. A. G. Aranda et al; PI0301103-8, 2003. D. A. G. Aranda et al, WO2004096962, 2004.

AGROPALMA: BIODIESEL FROM RESIDUESAGROPALMA: BIODIESEL FROM RESIDUES

Esterification CatalystsEsterification Catalysts

Heterogeneous Catalyst Reusable Zero Soap Easy to remove No neutralization

step Nobic AcidNobic Acid(CBMM)(CBMM)

HOMOmethanol

LUMOprotonated acid

E= -0,264 eV

E= -0,230 eV

12

10

8

6

4

2

0

-2

-4

-6

-8

-10

12

Me

tan

ol

Me

tóx

ido

Etó

xid

o

Eta

no

l

MG

Pa

lm

MG

Olé

ic

MG

Lin

ol

-11,12

3,75

-10,86

3,56

-2,04

10,88

-2,12

9,52

-10,83

1,06

-8,71

0,05

-9,58

0,79

HOMO (eV) LUMO (eV)

Ene

rgia

, eV

12

10

8

6

4

2

0

-2

-4

-6

-8

-10

12

Me

tan

ol

Me

tóx

ido

Etó

xid

o

Eta

no

l

MG

Pa

lm

MG

Olé

ic

MG

Lin

ol

-11,12

3,75

-10,86

3,56

-2,04

10,88

-2,12

9,52

-10,83

1,06

-8,71

0,05

-9,58

0,79

HOMO (eV) LUMO (eV)

Ene

rgia

, eV

HOMO and LUMO from Alcohols and Glycerides

HydrolysisHydrolysis

HH33C-CHC-CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22-- CHCH22-C-COCHOCH22

HH33C-CHC-CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22-COCH-COCH

HH33C-CHC-CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22- CH- CH22-COCH-COCH22

O

O

O

HH22O + LypasesO + Lypases

Hydrolysis Industrial Process: 99% conversion: 3 plants in Brazil(Non-catalytic process)

HydroesterificationHydroesterification

Esterificationof

Fatty Acids(AGROPALMA

)

IndustrialHydrolysis

Why don’t integrate these process ???Why don’t integrate these process ???

+

Triglyceride Fatty Acid

FA

FA + FA

FA

Water Glycerol

Hydroesterification

+ 3G

H2O

G 3

FA A FA A

H2O

+

Fatty Acid Alcohol Biodiesel Water

(No acidity restriction in feedstock)

Much better with Catalytic Distillation !!Much better with Catalytic Distillation !!

Custos Operacionais: Hidroesterificação vs Custos Operacionais: Hidroesterificação vs Transesterificação (50,000 mton/year)Transesterificação (50,000 mton/year)

Transesterification Hydrolysis + Esterification

Chemicals (¢/L) 4 1

Energy (¢/L) 1 2

Oper.Costs (¢/L) 5 3

If biodiesel plant is integrated with an ethanol plant, operatingcosts will be less than 2 ¢/L.

No acidity limits in the feedstocks

My team:My team:

Postdocs: Luciana Camacho and Ricardo Valdez

Ph D students: Neyda Om, Yordanka Reyes, Gisel Chenard, Immacolata Manco, Rosana Amorim, Marcia Castoldi, Marcelo Tondello, Rafael Monteiro, Elisa Cruz, Anderson Kurunczi

M Sc students: Ana Encarnação, Rafael João, Jussara Gonçalves, Layla Rocha, Luana Rocha, Leonardi Almeida, Carla Pereira, Margarida Castello, Marlon Almeida

Thank you !Thank you !

www.greentec-ufrj.comwww.greentec-ufrj.com

“ God causes all things to work together for good to those who love Him” ( Rm 8,28)

Biodiesel plant 100,000 t/year, oil costs: US$ 250/t and Biodiesel plant 100,000 t/year, oil costs: US$ 250/t and Biodiesel sold at US$ 0.60/L (Biodiesel sold at US$ 0.60/L (No incentive scenarioNo incentive scenario))

EBITDA e EBIT

39,4

23,4

39,4 39,4 39,4 39,4 39,4 38,9 38,9 38,9

23,8

37,4 37,4 37,4 37,4 37,4 37,4 37,4 37,4 37,4

8,0

13,0

18,0

23,0

28,0

33,0

38,0

43,0

48,0

2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

R$

mi

EBITIDA EBIT

EBITDA e EBIT

42,6

25,4

42,6 42,6 42,6 42,6 42,6 42,1 42,1 42,1

25,9

40,6 40,6 40,6 40,6 40,6 40,6 40,6 40,6 40,6

8,0

13,0

18,0

23,0

28,0

33,0

38,0

43,0

48,0

2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

R$

mi

EBITIDA EBIT

EBITDA e EBIT

31,6

18,5

31,6 31,6 31,6 31,6 31,6 31,1 31,1 31,1

19,0

29,6 29,6 29,6 29,6 29,6 29,6 29,6 29,6 29,6

8,0

13,0

18,0

23,0

28,0

33,0

38,0

43,0

48,0

2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

R$

mi

EBITIDA EBIT

Gross Margin: 30.8%

Gross Margin: 24.1 % Gross Margin: 33.3 %

a) Regular Transesterification

b) Hydroesterification

c) Hydroesterification integrated withEthanol plant