International Journal of Advanced Engineering Research and Technology (IJAERT)

Volume 2 Issue 1, April 2014, ISSN No.: 2348 8190

14
www.ijaert.org
Haruna Ibrahim
1*
and Oluwole Joshua Okunola
2
1&2
National Research Institute for Chemical Technology, Zaria-Nigeria
Abstract:
The increasing cost of petroleum products, its non-
sustainability, political crisis at source locations, couple
with environmental hazard, renew interest is now
focusing on renewable, sustainable and environmental
benign fuels as alternatives. The greatest area that brings
about the rise in price of fossil fuels is the transportation
sector that use gasoline and diesel. While ethanol has
been identified for fuel additive in internal combustion
engines, butanol could be a better alternative as its
properties are closer to that of gasoline than that of
ethanol. However, the commercial fermentation
production of biobutanol has not been encouraged due
its energy intensive which makes it more expensive than
petroleum production process. But recently
bioengineering technology is discovering new
production and separation techniques that have shown a
promising and attractive process for biobutanol
fermentation production.
Keywordsbiobuthanol, history, modern technique,
production
1. INTRODUCTION
The increasing cost of petroleum products, its non-
sustainability, political crisis at source locations, couple
with environmental hazard, renew interest is now
focusing on renewable, sustainable and environmental
benign fuels as alternatives. Biobutanol or biobased
butanol is also called biogasoline is a second generation
alcoholic fuel with very high energy density [1] and low
volatility. It is a colourless and flammable alcohol
widely used in industry as solvents [2]. The renew
interest research on biobutanol production arouses due to
its quality as biofuels that supersede that of ethanol. It
has an established history a chemical and solvent
particularly for use in paints, coatings, printing inks,
adhesives, sealants, textiles and plastics [3]. It is a
biofuel that has the tendency to replace ethanol because
of its numerous advantages over ethanol. These
advantages include; low volatility, high energy density,
eases separation from water mixture. Biobutanol can be
used in internal combustion engines as blend, additive or
wholly. This might be due to its closeness in chemical
similarity to petroleum gasoline. The production and
consumption of biobutanol is expected to reduce the
consumption of oil and natural gas by automobile
industry [2] and also reduce emission of greenhouse
gases that are harmful to environment.
1.1 Isomers of Butanol
Butanol has four isomers with slightly different
properties. They are;
1. n-butanol or butan-1-ol (CH
3
CH
2
CH
2
CH
2
OH), is
colourless, odouless and flammable liquid with
banana smell. It is found useful as solvent in paints,
coatings and varnishes, in plasticizers, in textiles as
swelling agent for coated fabrics, in cosmetics as
makeup, nail care, and shaving, in drugs as
antibiotics, hormones and vitamins and as fuel in
gasoline additive and brake fluid.
2. iso-butanol or 2-methyl propan-1-ol
(OHCH
2
(CH
3
)
2
CCH
3
), is a colourless liquid with
characteristic sweet smell immiscible in water but
miscible in most organic solvents. It is found useful
as solvent for coatings and adhesives, manufacturing
other chemicals, as dispersing agent for cleaning and
floor polishing, as flavor and fragrance and in
pharmaceuticals as pesticides and gasoline additive.
3. Sec-butanol or butan-2-ol (CH
3
(OH)CHCH
2
CH
3
), is
a colourless, flammable liquid, slightly miscible in
water but miscible in organic solvents. It is found
useful as solvent, domestic cleaning in paints
remover and as perfumes and flavours.
4. Tert-butanol or 2-methyl propan-2-ol
(CH
3
(CH
3
)
2
OH), is a clear liquid with characteristic
camphor smell very miscible in water and ethanol
and forms solid at 25
0
C. It is used in denature
ethanol, as paint removal, octane booster in gasoline
and for synthesis of other chemicals.
Table 1 below summarizes the physical properties of
the four isomers of butanol as claimed by Machada
[4].
Biobutanol: a Green Energy Fuel
International Journal of Advanced Engineering Research and Technology (IJAERT)
Volume 2 Issue 1, April 2014, ISSN No.: 2348 8190
15
www.ijaert.org
Table 1: Physical properties of isomers of butanol [4]
Property n-butanol Iso-butanol Sec-butanol Tert-butanol
Density @ 20
0
C (g/cm
3
) 0.810 0.802 0.806 0.781
Boiling point (
0
C) 118 108 99 82
Water solubility (g/100ml) 7.7 8.0 12.5 Miscible
Flash point (
0
C) 35 28 24 11
Octane Number 78 94 - 89
2. HISTORY Of BIOBUTANOL
The use of butanol as biofuel started 2005 when David
Ramey toured the United States in a 13-year old buick
fueled by butanol [5]. It was found to have 9% higher
consumption but lower emissions of carbon mono oxide,
hydrocarbons and nitrogen oxides (NO
x
). It was
reported that, biobutanol production via anaerobic
fermentation has been observed since 1861, when it was
witnessed by Pasteur [6]. During the anaerobic bacteria
fermentation process, butanol is a single product among
many. In 1905, Schardinger produced acetone by similar
process. Kaminiski et al [2] claimed that the interest in
biobutanol in 20
th
century was as a result of inadequate
level of supply of natural rubber that resulted increase in
its market price. Butanol was the raw material for
production of butadiene being a raw material for
synthetic rubber production. The production of butanol
via Acetone, Butanol and Ethanol (ABE) was first
commercialized in the 1910s in the United Kingdom for
the production of acetone which was the solvent needed
for the production of cordite [7]. ABE fermentation was
second to ethanol fermentation by yeast in its scale of
production and is one of the largest biotechnological
process ever emerged [8]. At the beginning of the 20th
century, interest in biobutanol synthesis had risen due to
butanols involvement in the solution for material
shortage of natural rubber. Natural rubber was out of
stock and efforts were taken to make synthetic rubber
from butadiene which could be synthesized from
butanol. This discovery stimulated great interests in the
fermentation production of biobutanol process.
According to Jones [9], the industrial production of
butanol by Clostridium spp. of Acetone-Butanol-Ethanol
(ABE) fermentation process flourished during the first
half of 20th century and continued into second half of
the century until the availability of cheap crude oil made
petrochemical synthesis more economically competitive.
Ibrahim [10] claimed that the ABE production of
biobutanol by fermentation was discovered by Russian
Chemist Chaim Weizman at Manchester University, in
1912. He isolated a bacterium later known as Clostrium
Acetobutylicum which he used to ferment starch into
Acetone, Butanol and Ethanol. Acetone was in high
demand then during the First World War for the
production of cordite, cartridges and propellant. Another
report [6], claimed that between 1912 and 1914 Chaim
Weizmann performed one of his first microorganism
screenings to study microbiology in hopes to better
understand the fermentation process. During the World
War 1, the need for production of the smokeless gun
powder in large quantities as cannot be imported let
British to seek for the assistance of Weizmann to design
a system to increase acetone production by fermentation.
Acetone was used to produce smokeless gun powder, or
cordite. The British Army later adopted and
implemented it at the loyal Naval Cordite Factory.
Industrial fermentation of starchy raw materials as
feedstock using Clostridium acetobutylicum as bacteria
fermentation agent was first commercialized in 1914 [4].
When the U.S joined the war, Britain and U.S started a
joint project for production of acetone.
At the end of the World War 1, large stockpiles of
butanol a by-product of acetone had built up [5]. The
stockpiles of the butanol were employed by E.I. du pont
de Nemours and co which used the butanol as solvent for
cellulose lacquer, which was a quick-drying automobile
finish [4&5]. It was reported [5] that Weizmann
demanded for a home for Jews in the Palestine as a
reward from Great Britain which lead to the Balfour
declaration of 1917 which formed the foundation of the
State of Israel. Weizmann became the first president
after the establishment of the state of Israel. After the
expiration of Weizmanns patent in 1936, the anaerobic
fermentation plants were left opened for production of
acetone and butanol. It was reported [6] that every
company had its own patent microorganism, which was
able to produce acetone and butanol in large amounts
from molasses.
Later again during the Second World War, acetone was
needed for munitions, this spike off production of
acetone and butanol [6]. Great Britain had to import
molasses and U.S. used corn mash to produce acetone. It
was reported that, India, Australia, South Africa and
International Journal of Advanced Engineering Research and Technology (IJAERT)
Volume 2 Issue 1, April 2014, ISSN No.: 2348 8190
16
www.ijaert.org
Japan joined in the production of acetone. After the
Second World War in 1960s, fermentation process of
butanol production gave way to petrochemical process,
because the later process was much easier and cheaper.
Most of the plants in Western countries were closed
because of rising substrate prices and competition by the
growing petrochemical industry [5]. Besides, the price of
molasses had increased, hence the fermentation process
for acetone and butanol production became inefficient
and not economical. Kopke et al [5] reported that, ABE
fermentation was only continued in countries that were
cut off from international supplies for political or
monetary reasons; the South African apartheid regime
ran a plant in Germiston with a capacity of 1,080 m
until 1982. The former USSR operated at least eight
plants, some of them up to the late 1980s. Continuous
fermentations with lignocellulose hydrolates as substrate
and working volumes of more than 2,000 m were
carried out. During the 1960s and 1970s more than
100,000 tons of butanol per year was produced. China
also developed the continuous fermentation process and
about 30 plants produced an annual amount of 170,000
tons of solvents at its peak in the 1980s. Afterwards the
production decreased successively and the last plant was
closed in 2004.
3. WHY THE QUEST FOR BIOBUTANOL
Butanol is a high quality liquid fuel and a widely used
industrial chemical [10]. Biobutanol suits internal
combustion engine more than bioethanol and can be
used as a direct replacement for gasoline. It was recently
used as a fuel in an unmodified car that was driven
across U.S [9]. Butanol is superior to ethanol in almost
every way convertible to jet fuel and gasoline, a valuable
established chemical and solvent and gate way molecule
to a wide range of chemical derivatives [3]. According to
kaminiski et al, [2], researches have shown that the use
of butanol as fuel additive is better than ethanol because
it has high calorific value, 29.2MJ/dm
3
, higher melting
point, -89.5
0
C high boiling point, 117.2
0
C high flash
point, 36
0
C and high self-ignition at 340
0
C. Butanol has
higher energy density, lower water adsorption, and better
blending ability with gasoline than ethanol [12].
Biobutanol is less flammable, less soluble, in water, and
less corrosive [11]. Table 2 compares the properties of
butanol, ethanol and gasoline. It is expected that
production of biobutanol can reduce consumption of oil
and natural gas by the automobile industry and reduce
emissions of harmful gasses into the atmosphere [2].
Table2: Comparison of fuel properties of butanol and others [2 &5].
Fuels Energy density
(MJ/dm
3
)
Mileage (%)] Air-fuel
ratio
Boiling point
(
0
C)
Flash point
(
0
C)
Octane
Rating
Gasoline 32 100 14.6 - -43 81-89
Ethanol 19.6 61-66 9.0 78 13 96
Butanol 29.2 83-91 11.2 117.2 36 78
Its higher flash point makes it safer in the presence of
flame than both gasoline and ethanol. Biobutanol has
better water tolerance than ethanol and biodiesel makes
it easier to separate from water than ethanol. Its low
solubility in water reduces its tendency for spill to
spread in underground water, transportable in petroleum
pipe lines and usable in gasoline blend at any ratio [12].
Also, these properties enable it to be distributed through
pipes. Biobuthanol has properties similar to gasoline
than ethanol. The drawback that biobutanol has over the
gasoline is lower octane rating as shown in table 2
above. This implies that switching from gasoline to
biobutanol would result in larger fuel consumption [13].
However, biobutanol has bigger energy content than
ethanol because of the larger number of carbon atoms in
the molecule (four for biobutanol and two for ethanol).
Biobutanol Bioethanol
International Journal of Advanced Engineering Research and Technology (IJAERT)
Volume 2 Issue 1, April 2014, ISSN No.: 2348 8190
17
www.ijaert.org
The air-fuel ratio of butanol is higher than that of
ethanol, which means that it can be run at richer
mixtures and therefore produce more power [13].
Butanol can be blended in any ratio with gasoline well
ahead of distribution and can be transported by the
existing infrastructure the same cannot be achieved with
ethanol for the fear of contamination. Butanol can be
transported with pipes but ethanol cannot except by
tanks through trucks, rail cars and river badges. With
low vapour pressure butanol is safer to handle than
ethanol. Biobutanol has higher energy density resulting
increase in mileage than ethanol [10]. Butanol is stable
on long time storage and highly combustible but not
explosive [4]. Butanol can be catalytically converted to
jet fuel [7].
4. PRODUCTION OF BIOBUTANOL
Biobutanol can be made from a variety of biomass types
which include corn, wheat, sugar cane, sugar beet and, in
the future, non-food lignocellulosic materials. According
to Jones [9], virtually all butanol is produced chemically
using either the oxo process from propylene or aldo
process from acetaldehyde. However, it can also be
produced by fermentation just like ethanol. Biobutanol
can be adapted ethanol plants from corn and other grains
or sugar cane and from cellulose [3]. It was reported [15]
that biobutanol was made via fermentation of biomass
from substrates such as corn grain, corn stovers and
other feedstocks. Microbes, especially the Clostridium
acetobylicum are introduced to the sugars produced from
biomass. The sugars are broken into acetone, butanol
and ethanol in the ratio 3:6:1 [2]. But unfortunately, a
rise in butanol concentration causes butanol to be toxic
to the microoganisms, kill them off after a short while.
Ezeji et al [16] claimed that anaerobic bacteria;
Solventogenic clostridia are capable of secreting
numerous enzymes that facilitate the decomposition of
polymeric carbohydrate into monomers. These bacteria
are capable of converting simple sugars such as glucose,
galactose, mannose, xylose etc. into acetone, butanol and
ethanol but the toxicity of the butanol kills these
microorganisms. Ramney and Yang [8] reported that,
ABE fermentation reaction goes through the production
of acetic, butyric and propionic acids by Clostridium
acetobylicum, then the metabolic shift of the culture
produces solvents; acetone, butanol and ethanol.
By increasing butyric acid concentration to >2g/l
and decreasing the pH <5 are usual require conditions
for the induction of metabolic shift from acidogenesis to
solventogenesis (conversion from acids to solvents) but
this reaction is difficult to control [8]. Genetically
modified versions of the Clostridium to improve butanol
tolerance and yield technology is being developed in the
US, Europe and Asia [15]. This will eliminate the
bacteria poisoned challenge faced by biobutanol
developers as these bacteria get poisoned by the butanol
they produce once its concentration rises above around
6%. A microbiologist in the College of Agricultural,
Consumer and Environmental Sciences at the University
of Illinois, Hans Blaschek, is working on strains of the
soil bacterium Clostridium beijerinckii, which he
himself developed 10 years ago at the Illinois laboratory
[15].
An alternative non-fermentative method has been
established by metabolic engineering of the amino acid
biosynthesis pathways, which allows for production of
1-butanol and also iso-butanol [12]. As the raw materials
are expensive due to their demand for food, cellulose
waste materials are used to process biobutanol. Straw
from crops, wood residues, and other sources of plant
biomass are investigated that would be more cost
effective [16].
4.1 Advance Techniques in Biobutanol production
It has been reported [4] that Clostrida secrete numerous
enzymes that can break down polymeric carbohydrates
into monomers. This process utilizes inexpensive
agricultural residues as fermentation substrates which is
capable of reducing the production cost. Ezeji et al, [16]
reported that a lot of Engineering attempts have been
employed to increase the ABE fermentation yield such
as cell recycle and cell immobilize to increase cell
density and reactor productivity and using extractive
fermentation to minimize product inhibition. Despite all
the efforts employed with ABE fermentation has never
produced up to 20g/l glucose of butanol concentration
[8]. Colorado based company used genetically modified
yeast that produces only iso-butanol from glucose. A
biofuel based in California used non-modified Clostrium
to break down celluloses, hemicelluloses and starch in
plants. It was reported [17] that Cobalts dilute acid
hydrolysis pretreatment process, which extracts sugars
from ligno-cellulosic biomass, was validated on woody
biomass, bagasse and agricultural residues. To convert
the cellulose and hemicellulose in lignocellulosic
biomass, Cobalt has developed a process that
simultaneously extracts and converts the
carbohydrates into simple sugars. It was reported [18]
that Cobalt production technologies are designed to
process a broad range of non -food feedstocks, avoiding
the risks associated with reliance on a single crop.
Cobalt's technology is based on a bacterial fermentation
International Journal of Advanced Engineering Research and Technology (IJAERT)
Volume 2 Issue 1, April 2014, ISSN No.: 2348 8190
18
www.ijaert.org
of biomass sugars into butanol. Cobalt's proprietary
bacterial strain development technology improves the
fermentation performance of a variety of naturally
occurring feedstocks. These feedstocks are specifically
selected for their ability to utilize all five of the sugars
found in plant materials, including the 5-carbon sugars
that cannot be fermented by common yeast. This
innovative technology makes it possible to utilize a
range of residual biomass feedstocks. cobalt technology
has improved the resistance of the microorganism to
the by-products of biomass conversion. The Cobalt
uses continuous bioreactor system which dramatically
increases production rate as much as 11-fold over
traditional batch fermentation processes [19]. This
results in a more capital efficient production process as
well as lower input costs, resulting in a more economic
process.
4.2 Characterization of Biobutanol
Biobutanol properties are more similar to gasoline than
bioethanol [11]. Biobutanol does not form azeotropic
mixture with water as ethanol does. It tolerates water
contamination unlike ethanol and biodiesel indicating
that it has less affinity to water than ethanol [4]. Tables 1
and 2 provide the properties of quality butanol.
4.3 Drawbacks Associate with Production of
Biobutanol
Distillation of biobutanol from the fermentation broth is
very energy consuming [11]. As butanol has a higher
boiling point than water, process consumes much
energy, and therefore it increases the cost of the
whole process, especially at low concentration of
butanol in the broth. Therefore, currently other methods
are used such as adsorption, membrane perstraction,
extraction, pervaporation, reverse osmosis or "gas
stripping with more emphasis on pervaporation. The
adsorption method of removing butanol from broth is
done with silicalite which selectively adsorb small
alcohol molecules of methanol to pentanol from aqueous
solution. This method is not favourably feasible for
industrial scale. This follows from the small-capacity of
adsorbents for butanol [2]. Another method is the use of
membrane reactor which increases the concentration of
butanol from 0.39 g/dm
3
/h to 15.8 g/dm
3
/h.
Pervaporation, is one of the membrane separation
technologies, which has high selectivity and low energy
consumption compared to other separation techniques
[11]. Pervaporation can be used to separate azeotropic
mixtures and other kind of mixtures, which are usually
difficult to separate by conventional techniques like
distillation [19]. Pervaporation involves the selective
transport by diffusion of some components through
a membrane. Due to their low vapour pressure and low
solubility in water, ionic liquids are solvents for
extraction of organic compounds in water. Pervaporation
is effective for removal of organic compounds from
water and separation of mixtures of two or more organic
compounds [13]. According Marszaek et al, [14],
another constrain is the use for the fermentation crop
products which is not very economical; primarily
because of high price due to demand for these crops
by food industries.
However, by optimizing fermentation productivity,
yield, and titer, Cobalt is making biobutanol a viable and
economic transportation fuel. Cobalt's distillation
process for butanol recovery uses approximately half the
energy and half the equipment compared to conventional
butanol distillation [16]. In addition Cobalts technology
platform offers a continuous process to efficiently
convert diverse non-food feedstocks into biobutanol.
5. CONCLUSION
Biobutanol is a green fuel; its use in transport sector will
contribute to reduction in environmental degradation
associated with the use of fossil fuels. It has all it takes
to replace ethanol as fuel additive with gasoline because
its physicochemical properties are closer to that of
gasoline than ethanol; higher energy density, low
solubility in water, less corrosive and lower vapour
pressure that makes it less polluting than ethanol. It can
be used as direct replacement for gasoline in internal
combustion engine. With cobalt advance technology in
biobutanol production, the agricultural residues that
were known to be wastes are going to be turned to useful
raw materials for biobutanol production. The production
of biobutanol from agricultural residues will generate
employment opportunities and provide economic
empowerment to many.
REFERENCES
1. Internet (a), (Access: 06/10/2013).Biobutanol:
Important biofuel and byproduct, Available at:
http://www.biobutanol.com.
2. Kamniniski W. Tomcrak E. Gorak A. (2011).
Biobutanol-Production and purification Methods.
Ecological Chemistry and Engineering. Vol. 18, No
1 Pp31-37
International Journal of Advanced Engineering Research and Technology (IJAERT)
Volume 2 Issue 1, April 2014, ISSN No.: 2348 8190
19
www.ijaert.org
3. Internet (b, accessed 10/06/2013), Biobutanol: A
game changer. State of biobutanol-study detailing
producers, their technology and the market.
Available at: http://www.biobutanol.com
4. C. Machado (2010).Technical characteristics and
current status of butanol properties and uses as
biofuel, BIO 2010 biocombustibles.
5. Ko pke Michael, Noack Steffi and Du rre Peter
(2011). The Past, Present, and Future of Biofuels
Biobutanol as Promising Alternative, Biofuel
Production-Recent Developments and Prospects,
Dr. Marco Aurelio Dos Santos Bernardes (Ed.),
ISBN: 978-953-307-478-8, InTech.
6. Internet (c, accessed 10/06/2013). History-
biobutanol and butanol fermentation. Available at:
http://www.biobutanol.com.
7. Bryan P. Tracy (2012). Improving Butanol
Fermentation To Enter the Advanced Biofuel
Market, mBio 3(6) doi: 10, 1128/mBio. 00578-12.
8. David Ramey, And Shang-Tian Yang (2004).
Production of Butyric Acid and Butanol from
Biomass Final Report, Work Performed Under:
Contract No.: DE-F-G02-00ER86106 For: U.S.
Department of Energy Morgantown, WV .
9. Jones D. T. (2011). Buthanol. Encyclopedia of Life
Support System, Biotechnolgy, Vol. VI. Available
at: http://www.eolss.net/Eolss-sampleAllChapter-
aspe
10. Ibrahim H. Biofuel for Sustainable (and eco-
friendly) Energy Development. International
Journal Of Engineering And Computer Science
ISSN:2319-7242 olume 2 Issue 5 May, 2013 Page
No. 1584-1594.
11. Niloofar Abdehagh, Aida Sharif, Handen Tezel and
Jules Thibault (2013). In Situ Removal of
Biobutanol from fermentation Broth.
12. Prospectus. Biobutanol: The Next Big Biofuel, A
Techno Economic and Market Evaluation, 2009,
Nexant with Chemical Strategy, 44 South broad
way, White plains, New york city 10601 USA
13. Ned Haluzan (2012). Biobutanol production and
properties, Bioenergy Talk: Discussing biomass &
biofuels. Available at:
http://bioenergytalk.blogsport.com/.
14. Joanna Marszaek and Wadysaw L. Kamiski
(2012). Efficiency of acetone-butanol-ethanol-
water system Separation by pervaporation.
Chemical and Process Engineering 2012, 33 (1),
131-140 DOI: 10.2478/v10176-012-0012-3.
15. Internet (d, accessed 10/06/2013). Biobutanol
development made headway. How economic and
policy affect players in Asian. Available at:
http://www.icis.com/staticpages/magazines.htm
16. Thaddeus Chukwuemeka Ezeji, Nasib Qureshi and
Hans Peter Blaschek. Bioproduction of butanol
from biomass: from genes to bioreactors,
ELSEVIER, ScienceDirect.
17. Cobalt (a) Cobalt Technologies Hits Key
Commercial Milestone With Pretreatment Process
Demonstration. Available at:
http://www.vpcp.com/cobalt_technologies.
18. Cobalt (b) (2014). Building a sustainable future.
Available at:
http://www.vpcp.com/cobalt_technologies.
19. Liu F., Xiao K. and Yang S.T. (2012). Separation
of n-butanol from Dilute Solution by Pervaporation
Using Composite PDMS Membrane, Separation
Division 12 AIChE Conference Proceedings