Biobutanol: a Green Energy Biofuel

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International Journal of Advanced Engineering Research and Technology (IJAERVolume 2 Issue 1, April 2014, ISSN No.: 23488

www.ijaert.org

Haruna Ibrahim1*

and Oluwole Joshua Okunola2

1&2National 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 ofethanol. 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 newproduction 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 toits 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. Theseadvantages include; low volatility, high energy density,

eases separation from water mixture. Biobutanol can be

used in internal combustion engines as blend, additiv

wholly. This might be due to its closeness in chem

similarity to petroleum gasoline. The production

consumption of biobutanol is expected to reduce

consumption of oil and natural gas by automo

industry [2] and also reduce emission of greenho

gases that are harmful to environment.

1.1 Isomers of Butanol

Butanol has four isomers with slightly diffeproperties. They are;

1. n-butanol or butan-1-ol (CH3CH2CH2CH2OH)

colourless, odouless and flammable liquid w

banana smell. It is found useful as solvent in pai

coatings and varnishes, in plasticizers, in textileswelling agent for coated fabrics, in cosmetics

makeup, nail care, and shaving, in drugs

antibiotics, hormones and vitamins and as fue

gasoline additive and brake fluid.

2. iso-butanol or 2-methyl propan-(OHCH2(CH3)2CCH3), is a colourless liquid w

characteristic sweet smell immiscible in water miscible in most organic solvents. It is found us

as solvent for coatings and adhesives, manufactur

other chemicals, as dispersing agent for cleaning

floor polishing, as flavor and fragrance andpharmaceuticals as pesticides and gasoline additiv

3. Sec-butanol or butan-2-ol (CH3(OH)CHCH2CH3a colourless, flammable liquid, slightly miscible

water but miscible in organic solvents. It is fo

useful as solvent, domestic cleaning in paremover and as perfumes and flavours.

4. Tert-butanol or 2-methyl propan-2

(CH3(CH3)2OH), is a clear liquid with charactericamphor smell very miscible in water and etha

and forms solid at 250C. It is used in dena

ethanol, as paint removal, octane booster in gaso

and for synthesis of other chemicals.Table 1 below summarizes the physical propertie

the four isomers of butanol as claimed by Mach

[4].

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Table 1: Physical properties of isomers of butanol [4]

Property n-butanol Iso-butanol Sec-butanol Tert-butanol

Density @ 200C (g/cm

3) 0.810 0.802 0.806 0.781

Boiling point (0C) 118 108 99 82

Water solubility (g/100ml) 7.7 8.0 12.5 MiscibleFlash point (0C) 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% higherconsumption but lower emissions of carbon mono oxide,

hydrocarbons and nitrogen oxides (NOx). It was

reported that, biobutanol production via anaerobic

fermentation has been observed since 1861, when it waswitnessed by Pasteur [6]. During the anaerobic bacteriafermentation process, butanol is a single product among

many. In 1905, Schardinger produced acetone by similar

process. Kaminiskiet al [2] claimed that the interest in

biobutanol in 20th

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 neededfor 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 materialshortage 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 thefermentation production of biobutanol process.

According to Jones [9], the industrial production ofbutanol byClostridium spp. of Acetone-Butanol-Ethanol

(ABE) fermentation process flourished during the first

half of 20th century and continued into second half ofthe 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, in1912. He isolated a bacterium later known asClostrium

Acetobutylicum which he used to ferment starch i

Acetone, Butanol and Ethanol. Acetone was in h

demand then during the First World War for

production of cordite, cartridges and propellant. Ano

report [6], claimed that between 1912 and 1914 Ch

Weizmann performed one of his first microorgan

screenings to study microbiology in hopes to be

understand the fermentation process. During the WoWar 1, the need for production of the smokeless

powder in large quantities as cannot be imported

British to seek for the assistance of Weizmann to des

a system to increase acetone production by fermentat

Acetone was used to produce smokeless gun powder

cordite. The British Army later adopted

implemented it at the loyal Naval Cordite FactoIndustrial fermentation of starchy raw materials

feedstock using Clostridium acetobutylicum as bact

fermentation agent was first commercialized in 1914

When the U.S joined the war, Britain and U.S starte

joint project for production of acetone.At the end of the World War 1, large stockpiles

butanol a by-product of acetone had built up [5].

stockpiles of the butanol were employed by E.I. du p

de Nemours and co which used the butanol as solvent

cellulose lacquer, which was a quick-drying automofinish [4&5]. It was reported [5] that Weizm

demanded for a home for Jews in the Palestine a

reward from Great Britain which lead to the Balf

declaration of 1917 which formed the foundation of

State of Israel. Weizmann became the first presidafter the establishment of the state of Israel. After

expiration of Weizmanns patent in 1936, the anaerofermentation plants were left opened for production

acetone and butanol. It was reported [6] that ev

company had its own patent microorganism, which w

able to produce acetone and butanol in large amou

from molasses.

Later again during the Second World War, acetone

needed for munitions, this spike off production

acetone and butanol [6]. Great Britain had to im

molasses and U.S. used corn mash to produce acetone

was reported that, India, Australia, South Africa


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Japan joined in the production of acetone. After the

Second World War in 1960s, fermentation process ofbutanol 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 ofmolasses had increased, hence the fermentation processfor acetone and butanol production became inefficient

and not economical. Kopkeet 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 than100,000 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 BIOBUTANO

Butanol is a high quality liquid fuel and a widely u

industrial chemical [10]. Biobutanol suits inte

combustion engine more than bioethanol and can

used as a direct replacement for gasoline. It was recen

used as a fuel in an unmodified car that was dri

across U.S [9]. Butanol is superior to ethanol in alm

every way convertible to jet fuel and gasoline, a valua

established chemical and solvent and gate way molec

to a wide range of chemical derivatives [3]. Accordin

kaminiskiet al, [2], researches have shown that the

of butanol as fuel additive is better than ethanol beca

it has high calorific value, 29.2MJ/dm3, higher mel

point, -89.50C high boiling point, 117.20C high fl

point, 360C and high self-ignition at 3400C. Butanol

higher energy density, lower water adsorption, and be

blending ability with gasoline than ethanol [

Biobutanol is less flammable, less soluble, in water,

less corrosive [11]. Table 2 compares the propertie

butanol, ethanol and gasoline. It is expected

production of biobutanol can reduce consumption of

and natural gas by the automobile industry and red

emissions of harmful gasses into the atmosphere [2].

Table2: Comparison of fuel properties of butanol and others [2 &5].

Fuels Energy density

(MJ/dm3)

Mileage (%)] Air-fuel

ratio

Boiling point

(0C)

Flash point

(0C)

Octane

RatingGasoline 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 offlame 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 gasothan ethanol. The drawback that biobutanol has over

gasoline is lower octane rating as shown in tabl

above. This implies that switching from gasoline

biobutanol would result in larger fuel consumption [

However, biobutanol has bigger energy content t

ethanol because of the larger number of carbon atom

the molecule (four for biobutanol and two for ethanol

Biobutanol Bioethanol


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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 theexisting infrastructure the same cannot be achieved with

ethanol for the fear of contamination. Butanol can betransported 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 stableon long time storage and highly combustible but not

explosive [4]. Butanol can be catalytically converted to

jet fuel [7].

4. PRODUCTION OF BIOBUTANOLBiobutanol 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 aldoprocess 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 biomassfrom substrates such as corn grain, corn stovers and

other feedstocks. Microbes, especially the Clostridiumacetobylicum 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


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of biomass sugars into butanol. Cobalt's proprietary

bacterial strain development technology improves the

fermentation performance of a variety of naturallyoccurring 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. Thisinnovative technology makes it possible to utilize arange 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 higherboiling 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 ofadsorbents for butanol [2]. Another method is the use of

membrane reactor which increases the concentration of

butanol from 0.39 g/dm3/h to 15.8 g/dm

3/h.

Pervaporation, is one of the membrane separat

technologies, which has high selectivity and low ene

consumption compared to other separation techniq[11]. Pervaporation can be used to separate azeotro

mixtures and other kind of mixtures, which are usu

difficult to separate by conventional techniques

distillation [19]. Pervaporation involves the selectransport by diffusion of some components throa membrane. Due to their low vapour pressure and

solubility in water, ionic liquids are solvents

extraction of organic compounds in water. Pervapora

is effective for removal of organic compounds fr

water and separation of mixtures of two or more orga

compounds [13]. According Marszaek et al, [another constrain is the use for the fermentation c

products which is not very economical; prima

because of high price due to demand for these cr

by food industries.

However, by optimizing fermentation productivyield, and titer, Cobalt is making biobutanol a viable

economic transportation fuel. Cobalt's distilla

process for butanol recovery uses approximately half

energy and half the equipment compared to conventio

butanol distillation [16]. In addition Cobalts technolplatform offers a continuous process to efficien

convert diverse non-food feedstocks into biobutanol.

5. CONCLUSIONBiobutanol is a green fuel; its use in transport sector

contribute to reduction in environmental degrada

associated with the use of fossil fuels. It has all it tato replace ethanol as fuel additive with gasoline beca

its physicochemical properties are closer to thatgasoline than ethanol; higher energy density,

solubility in water, less corrosive and lower vap

pressure that makes it less polluting than ethanol. It

be used as direct replacement for gasoline in inte

combustion engine. With cobalt advance technology

biobutanol production, the agricultural residues

were known to be wastes are going to be turned to us

raw materials for biobutanol production. The product

of biobutanol from agricultural residues will gene

employment opportunities and provide econoempowerment to ma

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