What is biobutanol?

Butanol can be produced from biomass (as "biobutanol")as well as fossil fuels (as
"petrobutanol"); but biobutanol and petrobutanol have the same chemical properties.
Butanol may be used as a fuel in an internal combustion engine. Because its longer
hydrocarbon chain causes it to be fairly non-polar, it is more similar to gasoline than it is
to ethanol. Butanol has been demonstrated to work in vehicles designed for use with
gasoline without modification, and is thus often claimed to provide a direct replacement
for gasoline (in a similar way to biodiesel in diesel engines). Biobutanol has the
advantage in combustion engines in that its energy density is closer to gasoline than the
simpler alcohols (while still retaining over 25% higher octane rating); however,
biobutanol is currently more difficult to produce than ethanol or methanol.
http://www.newworldencyclopedia.org/entry/Alternative_energy#Bioalcohols

Biobutanol is a four-carbon alcohol produced by the fermentation of biomass. It

has a long hydrocarbon chain which renders it fairly non-polar. The production of
biobutanol can be carried out in ethanol production facilities. The primary use of
biobutanol is a fuel in an internal combustion engine.

Its properties are similar to that of gasoline. Some gasoline-powered vehicles can even
use biobutanol without being modified. It can be blended with gasoline in concentrations
up to 11.5% by volume. However, it has a lower energy content, on average 10-20%,
than that of gasoline, which is a major disadvantage of biobutanol.

Biobutanol exhibits the potential to reduce carbon emissions by 85% when compared to
gasoline, thus making it a viable and suitable alternative to gasoline and gasoline-
ethanol blended fuels.

Advantages of Biobutanol

At high concentrations, biobutanol be blended with conventional petrol rather than

ethanol for use in unmodified engines. Experiments have also proved that biobutanol
can be used in unmodified conventional engines at 100%. However, no manufacturers
have guaranteed use of blends greater than 15%.

Biobutanol has a higher energy content than ethanol. With an energy content of about
105,000 BTUs/gallon, biobutanol is close to the energy content of gasoline, which is
roughly 114,000 BTUs/gallon.
Less corrosive and explosive than ethanol, biobutanol is also less susceptible to
separation in the presence of water than ethanol. It can be produced domestically from
a variety of feedstocks, which can also help drive the economy via the generation of
jobs.

Carbon dioxide captured by growing feedstocks minimizes overall greenhouse gas

emissions by balancing carbon dioxide released from burning biobutanol. Environmental
Protection Agency (EPA) test results show that biobutanol reduces hydrocarbon, carbon
monoxide and nitrogen oxide emissions.

http://www.azocleantech.com/article.aspx?ArticleID=408

What are biobutanol advantages?

One of the most important biobutanol advantage is the fact that its will reduce carbon
emissions. The EPA has released data showing that hydrocarbon, carbon monoxide,
and nitrogen oxide releases can be greatly reduced by use of biobutanol. Another
advantage is that biobutanol has a higher energy content than ethanol, almost 20%
more by density. Due to its similarities to conventional gasoline, it is able to blend much
better than ethanol with gasoline. It has even shown promise when using 100%
biobutanol in a conventional gasoline engine. Besides these, biobutanol experiences a
lower chance of separation and corrosion than ethanol. Biobutanol also resists water
absorption, allowing it to be transported in pipes and carriers used by gasoline. A very
exciting advantage of biobutanol is that vehicles require no modifications to use it. This
means that with effective pumping systems, it can be implemented immediately.
Currently, funds are quickly rising for biobutanol production and the only requirement is
a cheap and fast modification to the ethanol plants which already exist. As yield
efficiencies rise, the cost of biobutanol will continue to drop from its already reasonable
price.
 http://www.biobutanol.com/Resources.html

Several breakthroughs in biobutanol processing methods and the development of

genetically modified microorganisms have set the stage for biobutanol to topple ethanol
as the best renewable fuel. Biobutanol shows great potential as a motor fuel, industrial
solvent and chemical feedstock, owing to its higher energy density and better fuel
economy when compared to ethanol.

Apart from the increasing popularity of biobutanol due to its advantages, its yield
percentage and production speed are based on the organisms that process the
substrates. Efforts are currently in progress to enhance the metabolism of the existing
microbes used for fermentation. Another major drawback is the cost of separation of
butanol from the fermentation broth. However, several membrane-based separation
methods are currently under research, which are likely to reduce costs of biobutanol by
40-50%. Biobutanol seemingly has a promising future through the integration of genetic
engineering and membrane separation.

http://www.azocleantech.com/article.aspx?ArticleID=408

Benefits
Biobutanol is an alternative to conventional transportation fuels. The benefits of
biobutanol include:

 Higher energy content—Biobutanol's energy density is 10%–20% lower than

gasoline's energy density. However, biobutanol's energy content is relatively high
among gasoline alternatives.

 Lower reid vapor pressure—When compared with ethanol, biobutanol has a

lower vapor pressure, which means lower volatility and evaporative emissions.

 Increased energy security—Biobutanol can be produced domestically from a

variety of feedstocks, while creating U.S. jobs.
  Fewer emissions—Carbon dioxide captured by growing feedstocks reduces
overall greenhouse gas emissions by balancing carbon dioxide released from
burning biobutanol.

http://www.afdc.energy.gov/fuels/emerging_biobutanol.html
What is Biobutanol?

biobutanol structure
Biobutanol, which is also sometimes called biogasoline, is an alcohol that is produced
from biomass feedstocks. Butanol is a 4-carbon alcohol that is currently used as an
industrial solvent in many wood finishing products. Biobutanol can be utilized in internal
combustion engines as both a gasoline additive and or a fuel blend with gasoline. The
energy content of biobutanol is 10% less than that of regular gasoline. This is not as
bad as energy density of ethanol is 40% lower. Since biobutanol is more chemically
similar to gasoline than ethanol, it can be integrated into regular internal combustion
engines easier than ethanol. Its bioproduction route was halted in the 1960s due to high
production price with respect to production from petroeum. New technology
advancements and an increase in petroleum prices are making bioproduction of butanol
more competitive and safer. Biobutanol has displayed the potential to reduce the carbon
emissions by 85 percent when compared to gasoline, making it a superior alternative to
gasoline and a gasoline-ethanol blended fuel.
http://www.biobutanol.com/

Biobutanol
Raw materials of Biobutanol
3. Raw Materials for Butanol Production
Butyl alcohol (butanol) likewise ethyl alcohol (ethanol) can be produced by:
• processing sugar or starch of agricultural crops (biobutanol of the 1st generation);
• processing plant cellulose (biobutanol of the 2nd generation);
• synthesizing chemical source products (butanol).
Butanol made of biomass is commonly named as biobutanol, although its
characteristics are absolutely the same as those of butanol made of oil (chemical raw
materials).
http://www.abercade.ru/en/materials/analytics/339.html
However, it can also be blended with gasoline and used as a transportation fuel.
Butanol is commonly produced using fossil fuels, but it can also be produced from
biomass, in which case it is called biobutanol. Biobutanol is produced from the same
feedstocks as ethanol—corn, sugar beets, and other types of biomass. Biobutanol is a
renewable fuel and qualifies under the Renewable Fuel Standard; the category depends
on the feedstock used for production.
http://www.afdc.energy.gov/fuels/emerging_biobutanol.html
Process of making Biobutanol
Production
The first biobutanol plants are retrofits of existing corn ethanol plants. The fuel is
produced through fermentation of corn feedstock and the process is nearly identical
to fuel ethanol production from corn. Biobutanol companies produce a range of high-
value products, including transportation fuel. Primary co-products of biobutanol plants
may include solvents/coatings, plastics, and fibers. Production of these co-products
helps biobutanol companies improve economic performance through diversification of
product offerings. A challenge for biobutanol is that more ethanol than biobutanol can
be produced from a bushel of corn.

http://www.afdc.energy.gov/fuels/emerging_biobutanol.html

Traditional materials for the production of butanol are starchy crops (cereals, maize,
potatoes) and molasses from sugar cane or sugar beet.
http://agronomy.emu.ee/vol122/2014_2_4_b5.pdf

How is biobutanol made?

Biobutanol is made via fermentation of biomasses from substrates ranging

from corn grain, corn stovers and other feedstocks. Microbes, specifically of the
Clostridium acetobutylicum, are introduced to the sugars produced from the biomass.
These sugars are broken down into various alcohols, which include ethanol and
butanol. Unfortunately, a rise in alcohol concentration causes the butanol to be toxic to
the microorganisms, killing them off after a period of time. This made the fermentation
process expensive and unrealistic when compared to the petroleum costs of the late
50’s. Luckily, new technological advances and the discovery of new microbes have
improved the efficiency and cost of the fermentation process tremendously. Through
genetic engineering, researchers have been able to modify the most efficient microbes
to be able to withstand high alcohol concentrations. New modifications are constantly
being researched, including the modification to enzymes and genes involved in butanol
formation from biomass fermentation.
A promising trend is a slew of recent ethanol fermentation plants purchases by
biobutanol companies. These ethanol plants are being retrofitted with advanced
separation systems to allow them to produce biobutanol. Since biobutanol has
inherently higher value vs. bioethanol, the trend of the plant conversions is likely to
continue.
Aside from fermentation, a handful of companies are pursuing pyrolysis biobutanol.
This route can convert waste biomass or crop waste into biobutanol.

What are some recent developments for biobutanol?

Aside from the increasing popularity of biobutanol due to its advantages, the
percent yield and speed of its production are dependant partially on the organisms
which process the substrates. Efforts are currently underway to improve the existing
microbes used for fermentation. Next major cost hurdle is separation costs of butanol
from fermentation broth--several membrane based separation methods are under
investigation which can reduce costs of biobutanl by 40-50%. Through a mixture of
genetic engineering and membrane separation, biobutanol has a promising future.
http://www.biobutanol.com/

How is biobutanol being used in energy production?

5. Butanol as a Motor Fuel
Butanol can replace gasoline as a fuel even to a larger extent than ethanol due to its
physical properties, cost effectiveness, safety and because its application does not
require any automobile engine adjustments.
The main reason why nobody has considered butanol as an alternative fuel is that its
production has never been deemed cost effective. As mentioned above, this product is
applied mostly as an industrial solvent and its price is almost three times higher than the
gas price. When the traditional fermentation process is used, from a bushel of grain (35
pounds of sugar) it is possible to get only 1.3 gal of butanol, 0.7 gal of acetone, 0.33 gal
of ethanol and 0.62 pound of hydrogen. Such butanol production will not be competitive
with ethanol production with the product yield of 2.85 gal per bushel. Biotech progress
enabled to transform corn and other types of biomass into a rather cost effective source
of biobutanol. However, the introduction of industrial-scale production depends on some
other factors.
In contrast to ethanol, butanol can be mixed in higher proportions with gasoline and
used in the existing automobiles without any modification in air-fuel mixture formation
system.
Butanol is generating a larger amount of clean energy per operating cycle than ethanol
or methanol and approximately by 10% more than gasoline.

Since new highly effective technologies of biobutanol production have been developed,
experts have put emphasis on butanol made of grain considering it as a potential fuel.
There is a chance that in the next 10-15 years ethanol will be displaced from its top
position.

The success is based on a number of butanol advantages over ethanol, including:

1. Energy content in butanol is 25% higher than in ethanol: 110.000 BTU per gallon of
butanol vs. 84.000 BTU per gallon of ethanol. Gasoline contains about 115.000 BTU per
gallon.
2. Butanol is safer for use since its evaporation is six times less than that of ethanol and
its volatility is 13.5 times lower than that of gasoline. Reid vapor pressure of butanol is
0.33 pounds per square inch (psi), gasoline – 4.5 psi and ethanol – 2.0 psi. As a result,
it is more safe to use butanol as oxygenate and no significant variations of proportions
in the mixture are required in the summer and winter season. It is used now as
oxygenate in the states of Arizona and California and other places.
3. Butanol is a significantly less aggressive substance than ethanol. Thus, it can be
transported through the existing fuel pipelines, while for ethanol transportation it is
necessary to involve rail or water transport.
4. Butanol can be mixed with gasoline;
5. Butanol can replace gasoline completely, while it is possible to use ethanol only as an
additive to gasoline with the maximum share of 85% and only after major engine
adjustments. Currently, most of the mixtures contain 10% of ethanol.
6. Butanol production is helpful for resolving issues related to hydrogen supply
infrastructure.
7. Modified butanol is characterized by higher energy output (10 watt-hour/g) than
ethanol (8 watt-hour/g);
8. No sulfur or nitrogen oxides are released through butanol combustion and it is
considered as an additional ecological benefit. Thus, biobutanol is more cost effective
vs. ethanol and gasoline mixture, it improves automobile fuel efficiency and increases
distance run per unit of the consumed fuel. Biobutanol is produced from the same
source products as ethanol – corn, sugar beet, sorgho, manioc, sugar cane, corn stems
and other types of biomass, but it can replace gasoline in the equal volume.

http://www.abercade.ru/en/materials/analytics/339.html
Butanol

Butanol is more similar to gasoline than ethanol or methanol. This similarity is a

consequence of its longer hydrocarbon chain, which means there is more carbon in
relation to the single oxygen and thus the molecule is less polar. The diagram below
shows only one version of butanol. Because there are four carbons, there are four
possible structures to butanol.

image of a butane molecule

Butane

image

n-Butanol

The similarity of butanol to gasoline means that it can be used in a standard vehicle
without the need for modifications. Also, because of its size, butanol has an energy
density similar to that of gasoline. In fact, butanol is so close to gasoline in energy
content that its octane rating nearly makes up for the difference in energy density. In
other words, a liter of butanol will get your car about as far as a liter of gasoline, with the
difference only being about 10%. It is also true that butanol only produces about 2.03 kg
of carbon dioxide per kilogram of butanol while gasoline produces 3.3 kg of carbon
dioxide per kilogram of gasoline.

With all of these advantages the natural question is “why has butanol not replaced
gasoline?” The answer is three-fold. First, butanol actually produces more carbon
dioxide than what arises just from burning it. The reason for this discrepancy is that
producing the biomass, harvesting it, and processing it all requires energy which
releases CO2. This input of energy needed just to produce butanol as raises questions
about how efficient biofuels are, a topic addressed in detail in another article. Right now
there is a great deal of research into using algae to produce butanol. Tulane University
is leading the charge in this are as well as in the use of bacteria to produce butanol from
cellulose.

The second reason that butanol has not replaced gasoline is that its health effects are
not well understood. It is thought to behave similar to ethanol in the human body, but
further research into its effects, especially when burned as a fuel, are required before it
is considered safe.

Finally, butanol has not replaced gasoline because it is very difficult to produce. Until
recently, butanol was not considered a viable biofuels because it tended to kill the
organisms that produce it before they were able to create it in any great quantity. In
order to prevent this, butanol has to be removed from solution as it is made. Until 2012,
the removal of butanol away from the organisms producing it was an energy intensive
and expensive process. Research out of the University of Illinois, however, may make
the process simpler and allow for the efficient production of larger quantities of butanol.
It remains to be seen how effective this process is on larger scales, but it may pave the
way for butnaol to replace gasoline in the near future.
http://biofuel.org.uk/bioalcohols.html
Biobutanol can be utilized in internal combustion engines as both a gasoline additive
and or a fuel blend with gasoline.
http://www.biobutanol.com/
Butanol may be the most practical advanced biofuel on the horizon.

What makes butanol such a great biofuel?

Here is the rundown.

1) Butanol has a higher fuel value than ethanol, offering about 85% of the fuel value of
gasoline on a gallon-for-gallon basis compared to only about 60% for ethanol. Thus,
one gallon of butanol can displace about 1.25 gallons of ethanol. This also means better
fuel economy for vehicles running on butanol and butanol blends.
2) Butanol can be blended with gasoline in higher amounts. While ethanol is currently
limited to 10% by volume mixed with gasoline, butanol can be blended up to 16% under
current US regulations. Higher blends are likely possible without requiring any
modifications to engines running on butanol blends. As such, butanol is a much better
drop-in fuel and can displace a larger amount of petroleum-derived gasoline or diesel.

3) Butanol can be transported via existing fuel infrastructure and blended directly at
existing refineries.

4) Butanol can be produced using the same fermentation plants and same sugar and
cellulosic feedstocks as ethanol. It can also be produced from cellulosic feedstocks in
the same way that ethanol can.

5) Biobutanol also has a higher theoretical yield from glucose or glucose equivalents
compared to an advanced biofuel alternative such as a terpene.

Butamax, a joint venture between DuPont and BP, has announced plans to produce
biobutanol by 2012-2013. Butamax does not plan to produce butanol for the world by
itself. The company is also planning to offer licenses to other interested producers.
Gevo has focused on isobutanol, which has similar properties as a fuel, and has started
work in its demonstration plant in St. Joseph, Missouri, with annual output of 1 million
gallons announced for later this year unless legal barriers stop them. Other players
appear to be further from commercialization, but they all bear watching as advanced
biofuels, and butanol in particular, approach the marketplace.
http://www.bio-catalyst.com/we-need-advanced-biofuels-is-butanol-the-best-choice/

4. The use of biobutanol in road transport

4.1 Perspectives of biobutanol use in road transport The preferred use of biobutanol is
the production of motor fuels for spark ignition engines by mixing with conventional
gasoline; therefore biobutanol could become an option to bioethanol due to better
potential in terms of its physico-chemical properties. Biobutanol concentration in fuel
can reach up to 30% v/v without the need for engine modification. Since the butanol fuel
contains oxygen atoms, the stoichiometric air/fuel ratio is smaller than for gasoline and
more fuel could be injected to increase the engine power for the same amount of air
induced. The oxygen content is supposed to improve combustion, therefore lower CO
and HC emissions can be expected. Biobutanol and its mixtures can be used directly in
the current gasoline supply system, such as transportation tanks and re-fuelling
infrastructure. Biobutanol can be blended with gasoline without additional large-scale
supply infrastructure, which is a big benefit as opposed to the bioethanol use. Finally
biobutanol is non-poisonous and non-corrosive and it is easily biodegradable and does
not cause risk of soil and water pollution.
Biobutanol/17484.pdf

The basic problem of wider use of biobutanol depends on its production with sufficient
efficiency and this in turn is limited by separation of butanol from fermentation broth.
The distillation process is not applicable. The classical extraction requires the use of a
flammable or toxic liquid. For separation and purification of biobutanol it is proposed to
apply ionic liquids. Use of ionic liquids for the extraction of butanol (to remove from the
fermentation environment) can be achieved either through direct application of the liquid
in the bioreactor and separation of butanol outside of bioreactor or directing
fermentation broth outside the bioreactor and separation of butanol in the membrane
contractor.
Keywords: biobutanol, renewable energy sources, ionic liquids
Production of butanol by the anaerobic fermentation is one of the oldest industrial
method for obtaining this organic solvent [1]. In the early 20th century interest in butanol
resulted from an inadequate level of supply of natural rubber and increase of its market
price. At that time, butanol was used as one of raw material for the production of
butadiene being a raw material for synthetic rubber production. Currently, butanol is
considered as an alternative biofuel. Butanol is a colourless, flammable alcohol. It is
widely used in industry, among others, applied as a solvent. It arouses particular
interest due to the role it can play in the future as a biofuel. It is expected that
production biobutanol can reduce consumption of oil and natural gas by the automobile
industry and reduce emissions of harmful gases into the atmosphere
The process of biobutanol production Butanol can be obtained using several chemical
technologies. It is also possible to produce butanol in the process of fermentation by
means of bacteria of the genus Clostridium. This process occurs under anaerobic
conditions, and butanol as one of the products - called biobutanol [2, 6]. The most
popular bacteria species used for fermentation is Clostridium acetobutylicum. Such
fermentation is so called ABE (acetone-butanol-ethanol), due to the names of the main
products of this process, the typical ratio of these compounds being 3:6:1. The final
concentration of butanol is about 3% [2, 7]. In the course of industrial production of
biobutanol, using a fermentation process one must take into account three factors,
evaluation of the process profitability: the cost of raw material and its pretreatment, a
relatively small amount of product obtained, its significant toxicity, cost of product
recovery from fermentation broth. Clostridium acetobutylicum belongs to the amylolytic
bacteria; therefore a good substrate for production of butanol for these bacteria is
starch. Nevertheless, the use for the fermentation crop products is not very economical;
primarily because of too high price due to demand for these products from food
industries. Therefore, for the production of butanol there are commonly used agricultural
wastes for example: straw, leaves, grass, spoiled grain and fruits etc which are much
more profitable from an economic point of view. One looks for other sources of plant
biomass, which production does not require a lot of work and costs (eg algae culture)
Modern research on the production process of biobutanol focuses on finding the best
kind of substrate for fermentation process and for efficient strain of bacteria. Potentially,
one can use all the waste containing monosaccharide, and polysaccharides and waste
glycerol. Analogously, the biomass of algae is one example of such a substrate. Algae
culture does not require intensive labour and high costs. Some of the micro-algae
contain relatively high percentage of sugars in dry matter, such as Chlorella contains
about 30÷40% of sugars, which greatly increases their usefulness in the production of
biobutanol. There is also carried out research on the genetic modification the bacteria
Clostridium acetobutylicum and Clostridium beijerinckii in order to increase the
resistance of bacteria to the concentration of butanol in the fermentation broth.
Methods for removal of butanol from the broth
The method eliminates the toxic effect of butanol on bacterial cells is a systematic
removal of this compound from the fermentation broth. The traditional method of
product recovery is distillation. As butanol has a higher boiling point than water,
therefore, this process consumes much energy, and therefore it increases the cost of
the whole process, especially at low concentration of butanol in the broth. Distillation is
a process energetically and economically unfeasible, as the boiling point of water is
lower than the maximum concentration of butanol and butanol fermentation broth is 3%
by weight. This leads to low productivity and high costs of separation and purification of
butanol [10, 11]. Therefore, currently other methods are used such as adsorption,
membrane pertraction, extraction, pervaporation, reverse osmosis or "gas stripping"
[12]. Particularly, much attention is paid to the method of pervaporation, which is
potentially promising way to recover butanol from fermentation broth, as it allows
separation and concentration of the product during a single process.
Kaminski_18(S1).pdf

The production of biobutanol by fermentation for use as a biofuel is generating

considerable interest as it offers certain advantages in comparison with bioethanol.
These include higher energy content, lower water adsorption and corrosive properties,
better blending abilities and the ability to be used in conventional internal combustion
engines without the need for modification. Biobutanol can be produced from starch or
sugar based substrates by fermentation utilizing various species of solvent-producing
anaerobic bacteria belonging the genus Clostridium (see also– Basic Strategies of Cell
Metabolism). The industrial production of butanol by Clostridium spp. in the
AcetoneButanol-Ethanol (ABE) fermentation process flourished during the first half of
the last century and continued into the second half until the availability of cheap crude
oil made petrochemical synthesis more economically competitive.
Renewed interest in the production of biobutanol from biomass has lead to the
reexamination of the ABE fermentation. Currently a number of companies and scientific
institutions are investigating the possible revival of the conventional ABE process or the
development of new bio-processes. Two major companies recently announced that they
have committed themselves to the production of biobutanol as a biofuel additive.
The ABE process, however, has a number of limitations which render it uneconomic, at
present, as compared with the ethanol fermentation. Key problems associated with the
bio-production of butanol are the cost of the substrate, along with toxic inhibition of the
fermentation by butanol limiting the yields and concentration of solvent that can be
produced. Research involving genetic engineering, metabolic engineering, process
engineering and alternative methods of solvent extraction and recovery is being
undertaken to improve the production of biobutanol by fermentation. Strategies include
reducing butanol toxicity and manipulation of the fermentation and the cultures to
achieve better product specificity and yields along with improved substrate utilization.
The most intensively studied solvent-producing species is Clostridium acetobutylicum.
Its genome has been sequenced and the regulation and genetic manipulation of solvent
formation is being extensively investigated. Molecular biology has provided a detailed
understanding of genes and enzymes involved in solvent production and the
engineering of recombinant strains with superior biobutanol–producing ability is now fast
becoming a reality. Advances in continuous culture technology, integrated fermentation
processes, in situ product removal and improved downstream processing are providing
new approaches to improving substrate utilization, reducing butanol toxicity, reducing
process stream volumes and obtaining overall improved bioreactor performance.
The medium to long term future for biofuels is likely to be dependent on the ability to
ferment lignocellulose substrates. Current technologies for the degradation of plant
biomass tend to be slow, inefficient and only marginally economic. Solvent-producing
Clostridium strains offer a number of advantages in that they can produce a variety of
hemicellulase and cellulase enzymes naturally, although they are not able to ferment
crystalline cellulose. Another plus is that it they able to ferment both hexose and
pentose sugars whereas industrial yeast is only able to ferment hexose sugars. Certain
Clostridial strains have a powerful complex of cellulase enzymes known as a
cellulosome. Genetic engineering research is aimed at transferring this complex to
butanol producing strains to improve the efficiency of cellulose degradation.
Both the current price of crude oil, and the environmental aspects relating to carbon
dioxide emissions, could speed up a swing back to fermentation processes using
renewable plant biomass. The high price of crude oil had made the biotechnological
route for butanol production economically competitive once again. Thus the future of the
industrial processes for the production of butanol by fermentation can be predicted to be
on the increase.
Compatibility with Existing Internal Combustion Engines
Butanol is well suited to current vehicle and engine technologies. It does not require
automakers to compromise on performance to meet environmental regulations. Butanol
uses fuel to air ratios which are closer to that of gasoline than ethanol and butanol does
not attack the piping of internal combustion engines. One distinct advantage of
biobutanol over bioethanol is it can be used as a direct one for one replacement for
gasoline without making any vehicle modifications.. Butanol’s performance as a
transportation fuel has long been recognized. It was, for example, used to fuel vehicles
during World War II. Recently it was used as the fuel it in an unmodified car that was
driven across the USA. Ethanol is limited to around a 10% mixture before internal
combustion engine modifications are required. To use higher concentrations of ethanol,
car engines have to be modified to flexi fuel vehicles. Due to its low vapour pressure,
butanol can be blended into gasoline at higher concentrations than existing biofuels
without the need to retrofit vehicles or require specially adapted vehicles.
Biobutanol/E6-58-05-11.pdf

Feedstock
Sugars can be fermented into alcohols. Sugars are obtained from sugar crops, starch
crops and lignocellulose.
Sugar crops
Among sugar crops, the most extended are sugarcane and sugar beet, and to a lesser
extent, sweet sorghum. The sugar is extracted via milling (sugarcane, sweet sorghum)
or via heat extraction and vaporisation (sugar beet).
Starch crops
Starch crops are mainly maize, wheat, other cereals and potatoes. Starch is a
polysaccharide and needs to be hydrolized into monosaccharides (sugars) for
fermentation. For this saccharification the techniques commonly applied is enzymatic
hydrolysis, generally associated to ”jet cooking”.
In the enzymatic hydrolysis, the starch crops are crushed and mashed; then enzymes
(e.g. amylases) are added to the mash which dissolve the starch into sugar.
nol/EIBI-6-sugar-to-hydrocarbons.pdf
 saccharification
play

Definition of SACCHARIFICATION
1. : the process of breaking a complex carbohydrate (as starch or
cellulose) into its monosaccharide components
https://www.merriam-webster.com/dictionary/saccharification

VOLATILITY AND ENGINE OPERATION

The ability of a liquid to change to vapor is known as VOLATILITY. All liquids tend
to vaporize at atmospheric temperatures, but their rates of vaporization vary. The rate
of vaporiza-tion increases as the temperature increases and as the pressure decreases.
(Temperature is more important than pressure.) In general, for a given temperature, a
highly volatile fuel will vaporize more readily and at a faster rate than a fuel with a
lower volatility.

The volatility of fuel affects engine starting, length of warmup period, fuel
distribution, and engine performance. (When compared to diesel fuel (F-76), gasoline
is much more volatile.) High volatility, however, can also result in fuel dilution of the
lube oil in the crankcase. The ways in which volatility can affect engine operation are
discussed in the sections that follow.

http://www.tpub.com/engine3/en32-59.htm

h2SO4
Sulfuric acid

Molasses,[1] or black treacle (British, for human consumption; known as molasses otherwise), is
a viscous by-product of refiningsugarcane or sugar beets into sugar

anaerobic
relating to, involving, or requiring an absence of free oxygen.
Flashpoint

the temperature at which a particular organic compound gives off sufficient vapor to ignite in air.

hydrophilic
having a strong affinity for water.

hy·gro·scop·ic
tending to absorb moisture from the air.

corrosive
having the quality of corroding or eating away; erosive.

2.

harmful or destructive; deleterious:

Corrosion is a natural process, which converts a refined metal to a more chemically-stable
form, such as its oxide, hydroxide, or sulfide. It is the gradual destruction of materials (usually
metals) by chemical and/or electrochemical reaction with their environment.

Enzymes
Enzymes are very efficient catalysts for biochemical reactions. They speed up reactions by providing an
alternative reaction pathway of lower activation energy.

http://www.rsc.org/Education/Teachers/Resources/cfb/enzymes.htm

Hydrolysis
hydrolysis of cellulose in the lignocellulosic materials to fermentable reducing sugars

lignin
a complex organic polymer deposited in the cell walls of many plants, making them rigid and
woody
lignin is a phenyl propane polymer which forms a complex network cross-linking the cellulose and
hemicellulose together

1-Butanol, which is also known as n-butanol or 1-butanol or butyl

alcohol (sometimes also called biobutanol when produced biologically), is an alcohol with a
4 carbon structure and the molecular formula of C4H10O. It is primarily used as a solvent, as
an intermediate in chemical synthesis, and as a fuel. There are four isomeric structures
for butanol. The straight chain isomer with the alcohol at an internal carbon is sec-
butanol or 2-butanol. The branched isomer with the alcohol at a
terminal carbon is isobutanol, and the branched isomer with the alcohol at the
internal carbon is tert-butanol. 1-Butanol is produced in small amounts by gut microbial
fermenetation through the butanoate metabolic pathway.

https://pubchem.ncbi.nlm.nih.gov/compound/1-butanol#section=Names-and-Identifiers

The five steps are: 1) grinding, 2) cooking and liquefaction, 3) saccharification, 4) fermentation, and
5) distillation.

Enzymes are NOT alive. They are complex chemicals produced by bacteria. They cannot
reproduce, or actually consume waste. They speed up chemical reactions without getting used
themselves.

The solventogenic Clostridium species can metabolize both hexose and pentose sugars, which are
released by cellulose and hemicellulose in wood and agricultural wastes; this is an advantage over
other cultures used to produce biofuels. If all the residues available were converted into acetone-
butanol (AB), the result would produce 22.1 x 109 gallons of AB. In 2009, 10.6 x 109 gallons of
ethanol was produced, but that was only equivalent to 7.42 x 109 gallons of butanol on an equal
energy basis.

There are several issues that are a challenge to producing AB in a traditional batch process: 1)
product (butanol) concentration is low 13-20 g/L, 2) incomplete sugar utilization (<60 g/L), and 3) the
process streams are large. These issues are due to severe product inhibition. Other issues include:
1) butanol glucose yield low, 22-26%, 2) butanol concentration in fermentation is low, 1.5%, 3)
butanol concentration of 1% inhibits microbial cell growth, 4) butanol fermentation is in two phases,
and 5) feedstock cost is high.
One of the more important considerations of butanol production is limiting the microbial inhibitory
compounds. These compounds include some compounds related to lignin degradation, including
syringaldehyde, courmaric acid, ferulic acid, and hydroxymethylfurfural.

As an example of one particular process, wheat straw was processed using a separate hydrolysis,
fermentation, and recovery process. The following conditions were used: 1) wheat straw milled to 1-
2 mm size particles, 2) dilute sulfuric acid (1% v/v) pretreatment at 160 C for 20 min., 3) mixture
cooled to 45 C and hydrolyzed with cellulase, xylanase, and β-glucosidase enzymes for 72 h,
followed by centrifugation and removal of sendiments, 4) fermentation with C. beijerinckii P260
(fermentation gases CO2 and H2 were released to the environment, but could be captured, separated
and used in other processes, and 5) butanol removed by distillation. For this particular process, the
production of ABE was relatively high, with butanol and acetone being the major products. The
reaction was done in a batch reactor and no treatment was used to remove inhibitor chemicals.
Table 7.7 shows the process with wheat straw, barley straw, corn stover and switchgrass. Wheat
straw did not need to be detoxified, but the others did. Detoxification can be done with adding lime (a
weak base) or using a resin column to separate out the components.

Figure 7.20: A schematic diagram of acetone butanol ethanol (ABE) production.

Credit: Pryor, Scott; Li, Yebo; Liao, Wei; Hodge, David; “Sugar-based and Starch-based Ethanol,” BEEMS Module B5

So, what can be done to overcome butanol toxicity? What kind of downstream processing needs to
be done to separate out the wanted components? The butanol level in the reactor has to be kept to a
certain threshold in order to reduce toxicity to the culture and utilize all the sugar reactants.

First of all, these are the typical processing steps that must be utilized in some form for most refining
units (the upstream processing includes pretreating the raw material, similar to what we discussed in
Lesson 5): 1) sorting, 2) sieving, 3) communition (size reduction by milling), 4) hydrolysis, and 5)
sterilization. The next main stage is the bioreaction stage: metabolite biosynthesis and
biotransformations. The final aspect of processing is downstream processing, and the methods used
depend on the products made. To separate solids, filtration, precipitation, and centrifugation take
place. Flocculation can also be done. To separate liquids, several processes can be done: 1)
diffusion, 2) evaporation, 3) distillation, and 4) solvent-liquid extraction.

For butanol processing, there have been several processes developed to reduce the level of toxicity.
These include: 1) simultaneous saccharification, fermentation, and recovery (SSFR), 2) gas stripping
(using N2and/or fermentation gases – CO2 and H2), 3) cell recycle, 4) pervaporation (combination
process of permeation/evaporation using selective membranes), 5) vacuum fermentation, 6) liquid-
liquid extraction, and 6) perstraction (combination of solvent extraction and membranes for
permeation). The goal is to convert all the sugars to acetone and butanol, but remove the products
as they are produced to decrease toxicity. We’ll discuss more about liquid-liquid extraction (or
solvent extraction) when we get to the lesson on biodiesel.
https://www.e-education.psu.edu/egee439/node/648
Substrates
The prices of substrates for biobutanol production influence the economic competition
with the petrochemical industry [34]. The cost of feedstock represents over 70% of the
total production costs of biobutanol [63]. At the beginning of butanol fermentation,
substrates based on sugars and starch were used, but these are expensive and the
process becomes unfeasible. One of the strategies to decrease the production cost is to
use cheap and renewable feedstocks, such as lignocellulosic materials (e.g. agricultural
waste, paper waste, wood chips), which are abundant. The production of alcohol using
lignocelluloses follows an integrated process involving basically three steps: pre-
treatment, hydrolysis and fermentation [7]. The main substrates used for biobutanol
production are reported in Table 1.

The molasses are used for biobutanol production. However, these kinds of substrate
are more expensive than agricultural residues. On the other hand, molasses can be
used directly in the fermentation. Thus, it is not possible to assert that the cellulosic
residues will be cheaper than molasses. Van der Merwe et al. [64] reported analyses of
the energy efficiency and economics of biobutanol production using sugarcane
molasses. Another important point to be analyzed related to the choice of substrate and
its availability throughout the year. The major sources of this kind of raw material are
agricultural residues and wastes, such as rice straw, wheat straw, wood (hardwood),
byproducts left over from the corn milling process (corn fiber), annual and perennial
crops, waste paper [14] and sweet sorghum [65]. These raw materials consist of three
types of polymers: cellulose, hemicellulose, and lignin. Cellulose has strong physical-
chemical interaction with hemicelluloses and lignin. Cellulose, a linear glucose polymer
(that is broken in the hydrolysis), is a highly ordered polymer formed of glucose
representing about 50% of the wood mass. Hemicellulose is a short, highly branched
heteropolymer formed mainly of xylose, plus glucose, mannose, galactose and
arabinose and sometimes uronic acids. Lignin consists of phenylpropanoid units derived
from the corresponding p-hydroxycinnapyl alcohols. Lignin is hydrophobic and highly
resistant to chemical and biological degradation [66]. Clostridium beijerinckiii is being
explored as a promising strain to produce biobutanol from cellulosic materials [26].
https://sustainablechemicalprocesses.springeropen.com/articles/10.1186/2043-7129-2-
15
ACID HYDROLYSIS
ENZYMATIC HYDROLYSIS

Another basic method of hydrolysis is enzymatic hydrolysis. Enzymes are naturally

occurring plant proteins that cause certain chemical reactions to occur. However, for
enzymes to work, they must obtain access to the molecules to be hydrolyzed. For
enzymatic processes to be effective, some kind of pretreatment process is thus needed
to break the crystalline structure of the lignocellulose and remove the lignin to expose
the cellulose and hemicellulose molecules. Depending on the biomass material, either
physical or chemical pretreatment methods may be used.
Physical methods may use high temperature and pressure, milling, radiation, or
freezing—all of which require high-energy consumption. The chemical method uses a
solvent to break apart and dissolve the crystalline structure.

An example of an enzymatic hydrolysis-based process is under development by the

National Renewable Energy Laboratory (NREL). After a dilute acid pretreatment, the
slurry is detoxified to remove materials that would be poisonous to the microorganisms
used in the process. A small part of this slurry is sent to a separate vessel that is used
to grow microorganisms that produce the cellulase enzyme for the process. Another
part of the slurry is sent to another vessel to maintain and grow a yeast culture for
fermentation. In the NREL process, both enzymes and the fermentation microorganisms
are added at the same time to the slurry, and sugar conversion and fermentation occur
simultaneously in a process called simultaneous saccharification and co-fermentation
(SSCF).

Due to the tough crystalline structure, the enzymes currently available require several
days to achieve good results. Since long process times tie up reactor vessels for long
periods, these vessels have to either be quite large or many of them must be used.
Either option is expensive. Currently the cost of enzymes is also too high and research
is continuing to bring down the cost of enzymes.

However, if less expensive enzymes can be developed enzymatic processes hold

several advantages: (1) their efficiency is quite high and their byproduct production can
be controlled; (2) their mild process conditions do not require expensive materials of
construction; and (3) their process energy requirements are relatively low.
https://hort.purdue.edu/newcrop/ncnu02/v5-017.html