biofuels in brazil “van’t hoff institute for molecular sciences” amsterdam, 2007 prof. donato...
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Biofuels in BrazilBiofuels in Brazil
“van’t Hoff Institute for Molecular Sciences”
Amsterdam, 2007
Prof. Donato ArandaFederal Univ. Rio de Janeiro
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
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
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
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.
Esterification CatalystsEsterification Catalysts
Heterogeneous Catalyst Reusable Zero Soap Easy to remove No neutralization
step Nobic AcidNobic Acid(CBMM)(CBMM)
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