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Butanol production using ethanol

as feedstock in a sugarcane biorefinery


ISAF
20
th
International Symposium on Alcohol Fuels

Antonio Bonomi
Centro Nacional de Pesquisa em Energia e Materiais – CNPEM
Laboratório Nacional de Ciência e Tecnologia do Bioetanol – CTBE


Spier Estate, South Africa, March 2013
VSB – Virtual Sugarcane Biorefinery

Butanol production from sugarcane

Sugarcane
Bagasse
Sucrose Ethanol
Butanol
ABE
Butanol
catalysis
2G Ethanol
Sucrochemistry X Alcoholchemistry routes
2G Butanol
ABE
Butanol
catalysis
ABE – Acetone – Butanol – Ethanol fermentation process

• Mostly studied process
• Conventional microorganism strains:
– Low productivity
– Low butanol concentration in the reactor
– Product inhibition
• Engineered strains
– Hyper-butanol producers
• Use of integrated reaction-separation process
– Vacuum extractive fermentation significantly reduces energy
consumption


• Use of catalysts – hydroxyapatite, hydrotalcites, etc – for
ethanol conversion into hydrocarbons


• Other important products: 2-ethyl-butanol, hexanol,
butenol, 2-ethyl-hexanol, octanol, acetaldehyde, 1,3-
butadiene
• Co-product: mixed alcohols (mixture of hydrocarbons
heavier than butanol), may be used as fuel or as
feedstock



Alcoholchemistry – production of butanol from ethanol

Simulation of a sugarcane biorefinery for production of
ethanol, sugar, electricity and butanol







Annexed 50/50 distillery
500 t sugarcane/h
Hydroxyapatite catalyst for butanol production –
vapor-phase catalysis




20% ethanol conversion
69.8% butanol selectivity


Reaction conditions:
298 ºC
1.78 s
1 bar
Tsuchida et al., Journal of Catalysis 2008, 259, 183-189
Ni/Al
2
O
3
catalyst for butanol production – liquid-
phase catalysis




25% ethanol conversion
80% butanol selectivity


Reaction conditions:
250 ºC
72 h
70 bar
Riittonen et al., Catalysts 2012, 2, 68-84
Hexanol






P
r
o
d
u
c
t
s

Reactor 1
Reactor 2
Reactor 3
Reactor 4
Reactor 5
Reactor 6
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Butanol
Mixed alcohols
Purification
Reactors scheme
Liquid phase catalysis

Vapor-phase catalysis
Series-parallel


Reactor
Ethanol
Ethanol
Butanol
Purification
Vapor-phase catalysis
Single reactor
Mixed alcohols


Reactor
Ethanol
Ethanol
Butanol
Purification
Technical results
Steam consumption: 7.5 22.4 12.0
(Butanol Plant: kg steam/L butanol)


Equipment:
– Packed bed reactor
– Distillation columns
– Absorption columns
– Heat exchangers

Investment estimate – butanol plant
Product Price Unity
Anhydrous ethanol
1
0.66 US$/L
Hydrated ethanol
1
0.59 US$/L
VVHP Sugar
1
0.48 US$/kg
Electricity
2
60.98 US$/MWh
Sugarcane
3
27.26 US$/t
Sugarcane trash 18.29 US$/t
Butanol (fuel) 1.03 US$/kg
Butanol (chemical)
4
1.65 US$/kg
Mixed alcohols 0.91 US$/L
Hexanol
5
3.29 US$/kg
1
Six-years moving average prices (jan2002-dec2011) (CEPEA,
2012)
2
Weighted average of auction based on energy from sugarcane
bagasse between 2005 and 2011 (2011 value)
3
Six-years moving average prices (jan2002-dec2011) (UDOP,
2012)
4
Mariano et al., 2012
5
ICIS, 2012
Prices Investment estimate
Annexed distillery
Total investment US$ 180 million
(US$ 85/TC - UNICA)
Item Investment
Fraction
(%)
Equipment 60
Electromechanical set-up 7
Civil works 13
Electrical installations 8
Instrumentation 2
Engineering, services, etc 10
Results – economic analysis
Results – economic analysis
Sensitivity – butanol price
Chemical price: 2011 sale price of butanol in Brazil.
Fuel price: proportional to anhydrous ethanol fuel price in 2011 in Brazil (LHV basis).
Results – life cycle analysis
Comparison with petrochemical butanol
ADP: abiotic depletion; AP: acidification; EP: eutrophication; GWP: global warming; ODP: ozone
layer depletion; HTP: human toxicity; FAWET: fresh water aquatic toxicity; MAET: marine aquatic
ecotoxicity; TET: terrestrial ecotoxicity; POP: photochemical oxidation.
Results – life cycle analysis
Impacts scores per kilometer for dedicated and flex vehicles: butanol
(vapor-phase catalysis), ethanol 1G and gasoline
Efficiency of engines (fleet average):
flex (2.74 MJ/km)
gasoline (3.46 MJ/km)
ethanol (3.09 MJ/km)

Energy content of fuels:
hydrated ethanol (26.38 MJ/kg)
gasoline C (43.54 MJ/kg)
butanol (34.32 MJ/kg)

Transport: 300 km

Emissions for each type of fuel: CO
2
, CH
4
, CO, NOx,
RCHO, NMVOC, MP

Offshore
Imported
Onshore
Refinery Biorefinery
Crude oil
Imported
Gasoline
Storage Storage
Sugarcane
Distribution
Use
Transport
Results – life cycle analysis
Impacts scores per kilometer for dedicated and flex vehicles: butanol
(vapor-phase catalysis), ethanol 1G and gasoline
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Butanol
Flex
Butanol
dedicated
Ethanol
Flex
Ethanol
dedicated
Gasoline
dedicated
Gasoline
Flex
Global Warming Eutrophication
Final remarks

• IRR of the process with vapor-phase catalysis in series of
reactors is similar to the annexed distillery, considering
butanol sale in the current chemical market
• For butanol fuel, investment in the butanol plant must be
decreased for the process to be competitive
• Increase in butanol price due to its renewable origin will
significantly improve IRR
• Most of the impacts of butanol production are related with
the agricultural stage of sugarcane cultivation
• Further studies, regarding the use of catalysts in industrial
scale, are required


Thank you

antonio.bonomi@bioetanol.org.br



Marina O.S. Dias
Lucas G. Pereira
Tassia L. Junqueira
Lucas G. Pavanello
Mateus F. Chagas
Otávio Cavalett
Rubens Maciel Filho
Antonio Bonomi