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
Laboratrio Nacional de Cincia 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 C
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 C
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
Otvio Cavalett
Rubens Maciel Filho
Antonio Bonomi