CHAPTER 1

1.0. INTRODUCTION
Fusel oil production is increasing directly proportionally to the increase in the production of
ethanol in sugar milling companies. Much fusel oil is produced annually as a waste product
from the distillation sections of the sugar mills during the sugar milling season.

The sugar industry is one of the leading foreign currency earners in many countries. An
example is Swaziland whose sugar industry is the top foreign currency earner in the country.
Therefore the sugar industry is a pivotal sector of the economies of many countries,
particularly the developing countries like Zimbabwe. Much employment is provided by the
sugar industry. For an instance, Triangle and Hippo Valley sugar estates collectively employ
a maximum of around fourteen thousand workers during the sugar cane crushing season.

Therefore this demonstrated importance of the sugar industry calls for maximum value
extraction from the sugar mill industrial waste to enable increased economic viability in
operation and to create more employment for the nations.

Consequently, various research efforts have been done in order to assess the feasibility of
commercially utilising fusel oil, one of the waste products from the sugar mills. These
research efforts have led to the use of fusel oil in manufacturing food flavours and perfumes
in some countries. However, in the majority of countries (including Zimbabwe), fusel oil has
not yet been beneficially utilised and is therefore just burnt in open air at the sugar mills.

Disposing of fusel oil by burning in open air comes with its own disadvantages. There is so
much loss in combustible fluid that is lost when fusel oil is burnt in open air. Fusel oil is also
harmful to organisms if spilt into the environment. The aforementioned facts therefore make
it worthwhile investigating an alternative method of effectively utilising fusel oil in our local
sugar industry. This is the work that will be embarked on in this research project.

1.0. GENERAL OBJECTIVE

To develop an efficient separation system that enables the beneficial utilisation of fusel oil
through producing fuel for boilers.

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1.1. SPECIFIC OBJECTIVES

The specific objectives to be fulfilled in this work are:

1. To characterise fusel oil (its chemical and physical composition).

2. To investigate the physical and chemical properties of fusel oil.
3. To investigate the effects of fusel oil on the environment.
4. To investigate the production of fusel oil.
5. To develop an efficient separation procedure and equipment for separating water and
other contaminating components from fusel oil, and hence obtain a fuel that can be
used in boilers for electricity generation.
6. To empirically determine the heating value of the fuel that is expected to be produced
from the developed separation system.
7. To assess the economic viability of the production of the fuel.

1.2. PROBLEM STATEMENT

Zimbabwe has got a big sugar industry and this industry is still expanding [1]. Each year,
thousands of litres of fusel oil are produced as a by-product of ethanol distillation in the sugar
industries. Moreover, global demand for sugar is increasing at an average of about 2% per
annum [1] and this translates to a further projected increase in the fusel oil production since
fusel oil production is directly proportional to the amount of sugar produced.

Despite these large volumes of fusel oil being produced, no revenue is being realised out of
the fusel oil. For example, Triangle Sugar Estates alone produce approximately 40 000 to 200
000 [1] litres of fusel oil in a 48-week sugar production season but all of this oil is just
disposed of by burning in open air within the industrial site, as is the case with Triangle
Limited. This is because no initiative has been undertaken so far in Zimbabwe to establish a
process to utilise this seemingly “waste” product within the sugar factories. A lot of value is
being lost in this burning of fusel oil, hence the need to undertake this project.

1.3. PROJECT JUSTIFICATION

This project serves to develop a separation system and procedure for removing water and
other contaminating agents from fusel oil in order to produce a fuel with a high calorific
value. The fuel so produced will be burnt in the boilers in order to generate electricity for use
within the plant.

With the current rising of costs of water, electricity, agricultural inputs and other raw
materials, it is fundamental for the sugar industry to extract the maximum possible value out
of sugar cane. No valuable component must be lost as industrial waste. Fusel oil is one such
industrial effluent which predominantly consists of alcohols whose mixture can be used as
boiler fuel.

Fusel oil production is 0.5% of the ethanol production by volume [2]. This is a large quantity
considering that millions of litres of ethanol are produced per year. The distillation stage of
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ethanol production consumes the greatest amount of energy, and this energy must be
compensated for by generating electricity from the fuel processed from the waste product,
fusel oil. It is therefore worthwhile doing this research to enable beneficial utilisation of this
industrial effluent and thus economise ethanol plant operations.

The electricity generated from the fuel from fusel oil will significantly add to the amount of
electrical power available for use in the industrial operations. Therefore, in monetary terms,
utilisation of fusel oil will significantly pay off the ethanol plant operational costs. This also
means that the cost of ethanol production will be reduced.

Processing of industrial waste like fusel oil contributes a lot in keeping our environment clean
and healthy. For example, if spilt into the environment, fusel oil has detrimental effects to
organisms. Tests on animals indicates that spilled fusel oil may be absorbed through the skin
of animals and cause central nervous system disturbances [3]. Ingestion of fusel oil also
causes irritation to the digestive tract and it also has a narcotic effect. Therefore fusel oil is a
harmful pollutant if spilt into the environment.

Burning fusel oil in open air can easily lead to spills into the environment. This kind of
disposal has to be stopped and the fusel oil has to be used for a beneficial application within
the plant. Therefore utilising fusel oil is a great effort towards environmental stewardship as
well as economising plant operations.

Complete utilisation of by-products produced from agricultural and food industrial

manufactures is one of the most important part in economical reserves and our substantial
task in environmental protection at the same time. The successful application of this project
contributes a lot to achieving the seventh Millennium Development Goal which calls for
ensuring environmental sustainability [4]. Ensuring environmental sustainability entails the
prevention of spilling harmful chemicals into the environment, whether intentionally or
accidentally.

1.4. THEORETICAL BACKGROUND

Fusel oil is formed as a by-product during the fermentation of molasses to produce ethanol.
Fusel oil is a mixture of higher alcohols (C3 to C5). Fusel oil is produced in the following
manner. When amino acids are sufficient (early in fermentation) fusel oils originate from the
catabolic pathway (Ehrlich pathway)[5]:

amino acid α-ketoacid higher alcohol

When amino acids are deficient (later in fermentation) they originate from the anabolic
pathway from pyruvate:
amino acid

carbohydrate pyruvate α-ketoacid

higher alcohol

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The higher alcohols produced constitute the fusel oil. During the distillation process, fusel oil,
having higher boiling point than ethanol, is drawn off the column at a tray below the ethanol
tray.

Various researches have been done with the goal of utilising fusel oil for profitable means
rather than just burning it in open air. Fusel oil is not yet utilised widely in industry.
Utilisation of fusel oil is mostly in experimental stages. The following descriptions give a
brief account of each research experiment on a probable way of utilising fusel oil.

1.4.1. Esterification Of Fusel Oil Using Reactive Distillation [6]

In this research paper the potential utilization of fusel oil was studied by reacting it with
acetic acid to form different esters. Using reactive distillation, the researchers have compared
different process alternatives which react and separate the mixture of alcohols into different
esters. Based on simple cost analysis the best possible configurations have been identified.

Acetic acid esters of its major alcohol components have economic value as chemicals for the
production of flavours and fragrances. Different strategies of obtaining the esters from
mixture of alcohols were investigated. The different schemes were simulated in commercial
simulator, Aspen Plus. The objective was to arrive at a process that consumes minimum
energy.

Reactive distillation was investigated first, whereby fusel oil was reacted with acetic acid.
Then another alternative was also explored. The alternative was to first separate the alcohols
in fusel oil into individual components, and then react them with the acid. This second option
proved to be better because there was no separation of products after reaction. The
researchers came to a conclusion that fusel oil can be used to produce esters of commercial
value.

1.4.2. Application of fusel oil in sugarcane and its effects on the soil
Azania (2003) tested fusel oil and its impacts on soil fertility in sugarcane plants and weeds.
Sugarcane plants treated with fusel oil at four concentrations (12.5, 25.0, 50.0 and 100.0 %
volume/volume) applied at a volume corresponding to 150 m3/ ha wilted in a progressive and
irreversible process of drying of the leaves and branches in the first 24 hours after
application.

One of the conclusions of this study pointed to a possible desiccant potential of the by-
product toward the plants because the drying and death of the sugarcane plant was observed a
short time after application of the fusel oil. In the soil, the chemical attributes were altered
with increased levels of calcium, acid potential and aluminium. The conclusion reached at
was that fusel oil can therefore be used as a herbicide in clearing sugar cane plants in
preparation for new planting.

1.4.3. Esterification of iso-amyl alcohol and oleic acid by candida antarctica Lipase B
In this research, the esterification of iso-amyl alcohol and oleic acid by candida lipase B was
studied. Iso-amyl alcohol is a product of the separation of fusel oil into its components.

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Kinetic model for description of the enzymatic esterification of oleic acid and iso-amyl
alcohol has been elaborated and presented for the first time in literature. The model is based
on the ping-pong bi-bi mechanism and not only the product, but substrate inhibition is taken
into account, as well. The model fitted well to the experimental data (checked by R2 values),
though the measurements covered an extremely wide concentration range. The kinetic model
containing the determined parameters can be used in a particular enzymatic esterification
reaction for calculations of the optimal conditions of various aspects, like highest yield,
lowest acid residue, lowest amount of enzyme and shortest reaction time.

In conclusion, the researchers are planning to apply the model for bioreactor design to realise
continuous enzymatic iso-amyl oleate synthesis by lipase B.

1.5. SCOPE OF THE PROJECT

This project will be limited to the production of fusel oil in the Zimbabwe sugar industries.
The project is localised on the development of an efficient separation procedure and
equipment for recycling fusel oil, and the determination of the heating value of the fuel from
fusel oil.

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CHAPTER 2

2.0. LITERATURE REVIEW

2.1. FUSEL OIL

Whenever a sugar containing substrate is fermented in the presence of a suitable diet, the
fermented mashes contain ethanol and also a small amount of a considerable variety of other
substances arising out of cell metabolism. The major among these substances found in the
fermented mash are higher alcohols, inorganic salts and acids, essential oils, and gases like
carbon dioxide. The mash also contains solid substances like yeast cells, yeast gums,
albuminoids, pectic substances, complex organic phosphates and glycogen.

The term fusel oil originated from Germany and means inferior or bad spirits[7]. Nowadays
the term fusel oil is used to designate the collective mixture of higher alcohols by-product
stream in the distillation of ethanol. Fusel oil is a colourless to yellow, oily liquid by-product
of ethanol distillation. Fusel oil is originally produced as a congener in the fermentation of
molasses to produce ethanol.[1]

The quality and quantity of fusel oil generated during ethanol production depends on the type
and method of preparation of the mash used for fermentation, condition and environment
under which fermentation proceeds and the method of removal of fusel oil from the
distillation column.

Since the presence of fusel oil in the final ethanol product greatly deteriorates the product
quality, fusel oil must be removed during the rectification phase of the ethanol production.
However, removal of fusel oil is always accompanied by losses of ethanol into the fusel oil
phase.

2.2 COMPOSITION OF FUSEL OIL

Fusel oil is not a compound but it is a mixture of mainly higher alcohols and water, with a
negligible amount of esters. The approximate composition of fusel oil is shown in Table 2.0
below:

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Table 2.0: Approximate composition of fusel oil [3]

Constituent Mass Percentage (%)

Iso-amyl alcohol ((CH3)2CHCH2CH2OH) 44 – 80
Iso-butanol ((CH3)2CHCH2OH) 0 – 14
1-butanol (CH3CH2CH2CH2OH) 0–2
1-propanol (CH3CH2CH2OH) 0–6
Ethanol (CH3CH2OH) 1 – 17
Water (H2O) 8 – 21

The composition of fusel oil can also be conveniently reported as:

(i). Low boiling fraction, LBF (boiling below 132 oC at atmospheric pressure)

(ii). High boiling fraction, HBF (boiling above 132 oC at atmospheric pressure)

LBF constitutes the major portion in fusel oil, about 95-98 % volume/volume of fusel oil
(v/v). The composition of LBF is determined accurately by chromatographic technique.
Amyl, propyl and butyl alcohols make up the LBF.

The constituents of HBF are classified into three groups which are:

1. Acidic (10-25 % v/v of HBF)

2. Basic (5-10 % v/v of HBF)

3. Neutral (60-80 % v/v of HBF)

The acidic fraction consists of fatty acids like caproic, caprylic, pelagonic, capric, lauric and
their ethyl esters. The basic fraction consists chiefly of tri- and tetramethyl pyrazines.
Presence of diethyl and triethyl methyl pyrazines is also noted. The neutral unsaponifiable
substances are high boiling alcohols and terpens, whilst the non-volatile residue contain
higher hydrocarbons like C15H26, C15H28 and also C30H60 (from the waxes in cane). However,
HBF is in such a minute quantity that it is usually neglected in quoting the composition of
fusel oil.

2.3. PROPERTIES OF FUSEL OIL

2.3.1 PHYSICAL PROPERTIES

The physical properties are best represented in a table as shown below (Table 2.1).

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Table 2.1: Physical Properties of Fusel oil [2,8]

Property Value

Appearance Colourless to pale yellow liquid (pure)

Odour Mild choking alcoholic odour

Boiling point Range (1 atm) 123 – 133 oC

Flash point ±42 oC (open cup)

Flammability 1 – 10 % v/v

Autoflammability 350 oC

Density (25 oC) 837 kg/m3 approx.

Refractive Index (20 oC) 1.405 – 1.41

Vapour pressure (25 oC) 5mm Hg

Solubility in Water Slight

Solubility in most organic solvents Miscible

The melting point range of fusel oil is -117.2 oC to 0 oC. Under room temperature and
pressure (20 oC and 1 atmosphere), all the components of fusel oil are in the liquid state.

2.3.2 Definition of terms in Table 2.1 above:

2.3.2.1 Flash Point

The flash point of a volatile material is the lowest temperature at which it can vaporize to
form an ignitable mixture in air. Vapour/air mixtures become explosive at the flash point.
Measuring a flash point requires an ignition source. At the flash point, the vapour may cease
to burn when the source of ignition is removed.

2.3.2.2 Flammability

Flammability is defined as how easily something will burn or ignite,

causing fire or combustion. The degree of difficulty required to cause the combustion of a
substance is quantified through fire testing. Internationally, a variety of test protocols exist to
quantify flammability.

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2.3.2.3 Autoflammability

The autoflammability (autoignition) temperature or kindling point of a substance is the

lowest temperature at which it will spontaneously ignite in a normal atmosphere without an
external source of ignition, such as a flame or spark. This temperature is required to supply
the activation energy needed for combustion. The temperature at which a chemical will ignite
decreases as the pressure increases or oxygen concentration increases.

2.3.3 CHEMICAL PROPERTIES

2.3.3.1 pH

The pH of fusel oil is approximately neutral. This is because fusel oil is composed mainly of
C3 to C5 alcohols which have relatively large alkyl groups, compared to ethanol. The large
alkyl groups donate a high electron density to the oxygen atom in the hydroxyl anion (OH-),
thus reducing the tendency of the H+ cation from breaking away from the oxygen atom.
Therefore the acidity of the fusel oil is greatly reduced by this effect leading to the pH being
approximately 7 (neutral pH). Thus the pH of fusel oil is lower than that of ethanol.

2.3.3.2 Reaction with Water

Fusel oil is stable in a water environment. It does not react with water.

2.3.3.3 Stability in presence of oxidising agents

The oxidising agents include nitrates, perchlorates and peroxides. Fusel oil is unstable in the
presence of oxidising agents. It will easily react with these chemicals.

2.3.3.4 Products of reaction with air or oxygen

Incomplete combustion with air or oxygen liberates the hazardous carbon monoxide gas.
Complete combustion of fusel oil in oxygen or air liberates carbon dioxide gas, water vapour
and energy.

2.3.3.5 Polymerisation ability

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Fusel oil does not polymerise under any conditions, whether self-polymerisation or
polymerisation with other monomer substances. Self-polymerisation is a process whereby the
fusel oil components will be polymerising between themselves.

A prerequisite for polymerisation is that there must be monomers with unsaturated bonds
(like double or triple bonds). But all the components of fusel oil have saturated bonds.
Therefore polymerisation between fusel oil components is impossible.

2.4. ENVIRONMENTAL EFFECTS OF FUSEL OIL

Most of the effects of fusel oil in the environment are biological. The following account gives
the biological effects of fusel oil.

2.4.1 INHALATION

Concentrations of fusel oil vapour of 150 parts per million (ppm) can cause irritation to the
nose and throat. High concentrations of Fusel Oil vapours can cause severe irritation to the
nose, throat, and respiratory tract, cough and difficult breathing as well as central nervous
system depression effects such as nausea, vomiting, headache, dizziness, and eventually
unconsciousness.

This shows that when handling liquid fusel oil, one needs to have proper personal protection
against the vapours. This also shows that fusel oil must always be kept in a closed container.
If the fusel oil container has to be opened for some reason or the other, then the time for
which the container is open has to be very short in order to avoid the effect of the vapour on
people.

2.4.2 EYES

Vapour or liquid fusel oil may cause severe corneal irritation if it comes into contact with the
eyes.

2.4.3 SKIN

Liquid fusel oil may cause mild irritation to the skin. Tests on animals indicates that iso-amyl
alcohol (the major component of fusel oil) may be absorbed through the skin and cause
central nervous system effects. Repeated or prolonged exposure can cause redness, drying
and cracking of the skin (dermatitis).

Hence handling of fusel oil must be done with proper personal protection equipment to avoid
contact with the skin.
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2.4.4 INGESTION

Ingestion of Fusel Oil can cause central nervous effects such as nausea , vomiting, stomach
and chest pain , headache, weakness, dizziness, and at higher doses: collapse, coma and
death.

This is also the reason why beer and wine breweries have to keep the fusel oil content of their
liquor products to the minimum, otherwise the fusel oil would badly affect the people who
consume the liquor.

2.4.5 POTENTIAL FOR ACCUMULATION IN THE BODY

Fusel oil does not accumulate in the body. Once absorbed into the body, the fusel oil is
broken down and excreted. But if much fusel oil is absorbed, the body takes a long time to
break down the chemical, so the victim suffers the effects of the presence of fusel oil in the
body.

2.5 STORAGE OF FUSEL OIL

Fusel oil must be stored in a cool, dry, well-ventilated area, out of direct sunlight. Storage
must be away from heat and ignition sources. Incompatible materials such as oxidizing
materials are kept away from fusel oil storage tanks. Grounded, non-sparking ventilation
systems and electrical equipment that does not provide a source of ignition are used in fusel
oil storage. Fusel oil containers are well labelled and are kept tightly closed when not in use.

Suitable, approved storage cabinets, tanks, rooms and buildings are used in fusel oil storage.
If storing small quantities under refrigeration, an approved, explosion-proof refrigerator is
used. Due to the explosion potentiality of fusel, the quantity of material in storage is limited
to the safe amounts that can be handled by the plant safety system in preparation for burning
in open air. Access to storage area is restricted. Storage area is kept separate from populated
work areas. Damage or leaks are inspected periodically. Appropriate fire extinguishers are
always made available in and near the storage area. All applicable regulations for the storage
and handling of flammable materials must always be followed.

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CHAPTER 3.

3.0 PRODUCTION OF FUSEL OIL

Fusel oil is initially produced in the fermentation of molasses and then it is liberated in the
distillation stage, whereby ethanol (the required product) is produced as the tops product. For
every 100 litres of ethanol distilled, approximately 0.5 litres of fusel oil are produced [7].
Since fusel oil is a by-product of ethanol production, the quantity of fusel oil produced is
directly proportional to the amount of ethanol distilled.

Molasses is the liquid residue that is left left after condensing the sap of sugar cane or sugar
beets until sugar crystals precipitate. This is the crystallisation stage. When all the crystals
that can be formed have been centrifuged off, the syrup can be as high as 85% dry matter and
90o brix. It is too viscous to be handled by ordinary mill equipment and is referred to as high-
brix molasses. It is therefore diluted down to (in the U.S.) a standard of 79.5o brix, which is
still quite thick, but which is possible to handle in many mills.[7]

The ASFCO (American Society of Feed Control Officials) definition of cane molasses is:
“A63.7:S Cane molasses is a by-product of the manufacture of sucrose from sugar cane. It
must contain not less than 43% total sugars expressed as invert. If its moisture content
exceeds 27%, its density determined by double dilution must not be less than 79.5o brix.”
Brix is a measure of the sugar content of a solution. 1o brix is 1 gram of sucrose in 100 grams
of the sugar solution.

The kind of molasses fermented in ethanol production is blackstrap molasses which is the
resultant liquid after centrifugation of C-massecuite. A brief account of the production of C-
massecuite is given below.

Crystallization of the sugar starts in the vacuum pans, whose function is to produce sugar
crystals from the syrup. In the pan boiling process, the syrup is evaporated until it reaches the
supersaturation stage. At this point, the crystallization process is initiated by “seeding” or
“shocking” the solution. When the volume of the mixture of liquor and crystals, known as
massecuite, reaches the capacity of the pan, the evaporation is allowed to proceed until the
final massecuite is formed. At this point, the contents of the vacuum pans (called “strike”) are
discharged to the crystallizer, whose function is to maximize the sugar crystal removal from
the massecuite. Some mills seed the vacuum pans with isopropyl alcohol and ground sugar
(or other similar seeding agent) rather than with crystals from the process. From the
crystallizer, the massecuite (A massecuite) is transferred to high-speed centrifugal machines

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(centrifugals), in which the mother liquor (termed “molasses”) is centrifuged to the outer
shell and the crystals remain in the inner centrifugal basket. The crystals are washed with
water and the wash water centrifuged from the crystals.

The liquor (A molasses) from the first centrifugal is returned to a vacuum pan and reboiled to
yield a second massecuite (B massecuite), that in turn yields a second batch of crystals. The B
massecuite is transferred to the crystallizer and then to the centrifugal, and the raw sugar is
separated from the molasses. This raw sugar is combined with the first crop of crystals. The
molasses from the second boiling (B molasses) is of much lower purity than the first
molasses. It is reboiled to form a low grade massecuite (C massecuite), which goes to a
crystallizer and then to a centrifugal. This low-grade cane sugar produced from C massecuite
is mingled with syrup and is sometimes used in the vacuum pans as a “seeding” solution. The
cane sugar from the combined A and B massecuites is dried in fluidized bed or spouted bed
driers and cooled, then sent for storage. This stored sugar is the common brown sugar we
know. The C-molasses is the blackstrap molasses which is then sent to the fermenters for
ethanol production.

3.1 UNIT OPERATIONS INVOLVED IN PRODUCTION OF FUSEL OIL

3.1.1 FERMENTATION OF MOLASSES

Fermentation in food processing typically is the conversion of carbohydrates to alcohols

and carbon dioxide or organic acids using yeasts, bacteria or a combination of them,
under anaerobic conditions.

Anaerobic conditions are conditions whereby air will be excluded from the system.
Fermentation is an exothermic process.

The microorganism which is most effective for use in fermentation is yeast, preferably of the
genus Saccharomyces or of the genus Torulaspora. It is particularly desired that the
microorganism to be used be a mutant form of a commercial fermentation yeast strain so that
the ethanol content in the final mash is at least 7 to 8%. The yeasts which can be particularly
useful are Saccharomyces cerevisiae, Saccharomyces cerevisiae varieties: elliopesoideus,
Saccharomyces beticus, Saccharomyces bayanus, Saccharomyces carlsbergensis,
Saccharomyces uravum, Saccharomyces vini, Saccharomyces oviformis, Saccharomyces
chevaleri, Saccharomyces fermentati and Saccharomyces rosei. According to yeast
nomenclature, all of these yeast species, except for the last two, are classified as species of
Saccharomyces cerevisiae, and the last two are classified as Torulaspora delbrueckii. [9].

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Of these different types of yeast in existence, saccharomyces cerevisiae is the industrially
important yeast for alcohol fermentation. Saccharomyces cerevisiae consists of different
strains and varieties, which are used for different applications. Yeast which is used in beer
making are called “Brewing strains”, and for wine making the yeast strain is called “wine
strains”. However, for the purpose of ethanol production, the yeast strain used is called
“Bakers strains”. The differentiation is based on specific properties of yeast required by the
particular industry.

The process of molasses fermentation is as follows. The C-molasses is first diluted with water
to form a mash with the ratio of 1:5 (molasses to water) by volume. This brings the sucrose
content of the molasses solution to 10-20 weight per cent (wt%). If nitrogen content of
molasses is small, the solution is fortified with ammonium sulphate to provide adequate
supply of nitrogen to yeast. For growth and multiplication, yeast requires utilisable organic
carbon (sugars), nitrogen source, various organic and inorganic trace growth factors.
Therefore enough nitrogen for yeast growth is needed.

The fortified solution of molasses is then acidified with a small quantity of sulphuric acid.
This adjusts the pH of the mash to a range of about 4 to 5. Addition of this mineral acid
favours the growth of yeast but simultaneously inhibits the growth of useless bacteria.

Fermentation is carried out as a either a batch or a continuous process. In the batch

fermentation process, the solution from the acidification stage is received in a large
fermentation tank and inoculated with yeast at 20 - 30oC and kept for about one to three days.
During this period, enzymes sucrase and zymase which are present in the yeast, convert the
sucrose in molasses into ethanol. During all stages of fermentation, care must be taken to
ensure no infection (other organisms which compete with the yeast for the glucose) occurs.
The fermented beer contains 6 – 10 wt % ethanol. Some other by-products are also produced
in this molasses fermentation process. The by-products include higher alcohols (fusel oil) and
aldehydes.

However, batch fermentation presents problems with it. These problems are:

(a). There is low fermentation efficiency

(b). There is more by-product formation

(c). There is higher residence time for the fermentation reaction to reach completion

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(d). There is a requirement of yeast for each batch.

These problems can be solved in continuous fermentation.

In continuous fermentation, feed is continuously pumped into fermenters and an equal

volume of fermented mash flows out continuously, for recovery of alcohol, into distillation.
Yeast is inoculated only at the beginning of the fermentation cycle. The process continues for
long periods without stopping. A cascade system of continuous fermentation is used where 3
to 7 fermenters are used in series. Concentration of alcohol in the first fermenter is at 5 to 6
per cent volume/volume (v/v), while it is around 7 to 9 % v/v in the last fermenter. This kind
of profile helps in two ways. Productivity of yeast is higher in the initial fermenters at lower
concentration of alcohol. The latter fermenters ensure higher level of concentration as well as
completion of the reaction of conversion of sugar to alcohol. Yeast becomes inactive as the
alcohol content rises too high. The threshold of yeast inactivity is around 12% ethanol
content. In both batch and continuous fermentation, the fusel oil production rate is 0.5 % of
the volume of ethanol that is produced.

Higher concentration of alcohol helps in lower consumption of steam in distillation. When

the system is used with granulating yeast , this yeast forms granules at the end of
fermentation and, thus, can be separated from the fermented mash simply by gravitational
settling. This settled yeast, then, is reactivated with additives like nutrients and then recycled
to fermentation. Recycle of yeast builds up a higher population of yeast in the fermenting
mash, thus giving higher productivity as well as robustness of operation.

The diagram (Figure 2.0) below shows a typical block diagram of the continuous
fermentation process.

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Figure 3.0: Block diagram of the continuous fermentation process

Another diagram (Figure 2.1) below shows the relative positioning of equipment in a
fermentation process.

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Figure 3.1: Relative positioning of equipment in fermentation.

3.1.1.1 MECHANISM OF FERMENTATION

The sucrose is first converted to glucose then fermented. Sucrose is a disaccharide and
glucose is a monosaccharide.

The chemical reaction for conversion to glucose is:

C12H22O11 + H2O 2C6H12O6 ………..2.1

(sucrose) (water) (glucose)

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This conversion is a hydrolysis reaction.

The chemical reaction for fermentation is:

Yeast
C6H12O6 2CH3CH2OH + 2CO2 + energy …..2.2

(glucose) (ethanol) (carbon dioxide)

The main yeast type used in fermentation is saccharomyces cerevisiae.

This type of yeast is used because:

(a). it grows vigorously

(b). it has high tolerance for alcohol and

(c). it has a high capacity for producing a large yield of alcohol.

The yeast acts as a catalyst. Only monosaccharides can be directly converted to ethanol. All
polysaccharides have to be hydrolysed to monosaccharides before conversion to ethanol.

Along with ethanol, some side reactions occur which produce higher alcohols (fusel oil) with
three carbon atoms and up to five carbon atoms per molecule, together with aldehydes and a
small amounts of esters.

The formation of fusel oils is as follows:

When amino acids are sufficient (early in fermentation) fusel oils originate from the catabolic
pathway (Ehrlich pathway) [5] , which is:

amino acid α-ketoacid higher alcohol.

The higher alcohols in a fermented liquor are the small aliphatic alcohols other than ethanol
(C3 to C5 alcohols). They are formed by decarboxylation and reduction of the α-keto acid
arising from deamination of the amino acid. After deamination of the amino acid to obtain
ammonium the yeast needs to deal with the α-keto acids and it can only excrete them after
decarboxylation and reduction. This process involves the degradation of amino acids.

An illustration of the above Ehrlich pathway is:

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The RCHOH is the higher alcohol produced. The amino acids are synthesised by the yeast
from the nitrogen source and the carbohydrates present in the reaction mixture. The yeast use
these amino acids to build essential proteins for yeast growth.

The reduction of the aldehyde is catalysed by the same enzyme family that converts
acetaldehyde to ethanol. Under some conditions, the aldehyde is oxidized to an acid rather
than being reduced to an alcohol. Aldehydes are more toxic than alcohols or acids so the
yeast would prefer to make one or the other of these compounds from the amino acid
skeleton.

Different higher alcohols have different amino acid precursors. For example, leucine is the
amino acid precursor for 3-methylbutan-1-ol or isoamyl alcohol, and isoleucine is the amino
acid precursor for 2-methylbutan-2-ol or active amyl alcohol. 2-methylpropan-1-ol or
isobutyl alcohol is derived from valine.

Propan-1-ol is not derived from an amino acid but from α-ketobutanoic acid which can be
formed from pyruvate and acetyl CoA. Acetyl coenzyme A (acetyl CoA) is an important
molecule in metabolism, used in many biochemical reactions. Its main function is to convey
the carbon atoms within the acetyl group to the citric acid cycle to be oxidized for energy
production.
Molecular formula of acetyl CoA is:

When amino acids are deficient (later in fermentation) fusel oil originates from the anabolic
pathway from pyruvate.
amino acid

carbohydrate pyruvate α-ketoacid

(glucose) higher alcohol
All these higher alcohols that are produced make up the fusel oil. Hence fusel oil is produced
via these afore-explained pathways. The fermented liquor is transferred to the distillation
column for separation of the fractions. This fermented liquor is called the beer.

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3.1.1.2 FACTORS WHICH GOVERN THE FORMATION OF FUSEL OIL

(i). Condition of yeast utilised in regard to nitrogen

The condition of yeast utilised in regard to nitrogen is important. Nitrogen-poor medium

causes the yeast to produce higher quantities of fusel oil than normal. The form in which the
nitrogen is supplied also affects the yield of fusel oil.

(ii). Temperature of the system.

For a specific yeast strain, there is an optimum temperature limit which gives higher
selectivity of ethanol relative to fusel oil. This optimum temperature produces high yields of
ethanol and correspondingly low yields of fusel oil.

(iii). Residence time in the fermenter

The amount of fusel oil produced increases with longer fermentation times. In the case of
cane molasses it reaches to a maximum and then remains constant thereafter.

(iv). Amount of fusel oil already produced

Fusel oil strongly retards fermentation at 0.4% and inhibits it completely at 0.7 to 0.8% in
relation to the volume of ethanol. Therefore, for high ethanol yields at an economic costs,
there should be an optimum or maximum allowable fusel oil concentration in the
fermentation broth.

(v). Longer time interval between fermentation and distillation

Longer time interval between fermentation and distillation tends to increase the amount of
higher aliphatic alcohols formed. These alcohols constitute the fusel oil.

(vi). Type of microorganism used in the fermentation

Certain leucine and valine requiring mutant microorganisms can significantly reduce the
content of the fusel oils. However there is a maximum limit of ethanol content in the
fermented mashachieved by using them. The general microorganism used is a yeast,
Saccharomyces cerevisiae.

3.1.1.2 EQUIPMENT FOR FERMENTATION

Fermentation of molasses is done using either the batch or continuous fermentation process.
Different equipment is used for each of these processes.

The bioreactor configurations are as follows:

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Stirred tank reactor (STR)

Mixing and bubble dispersion are achieved by mechanical agitation; this requires a relatively
high input of energy per unit volume. A wide variety of impeller sizes and shapes are
available to produce different flow patterns inside the vessel. Baffles are used in STR to
reduce vortexing.

Only 70-80% of the volume of the reactor is filled with liquid- allowing headspace for the
disengagement of droplets from exhaust gas and accommodates any foam which may
develop. A supplementary impeller can also be installed to avert excessive foam or
alternatively, antifoams are used.

Diagram of the STR:

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Figure 3.2: Continuous stirred tank bioreactor

Temperature of the broth is regulated using internal coils as a heat exchanger surface. This
configuration presents the largest surface area for heat exchange with no extra costs of
pumping.

The STR has the advantages that: (i). It has high heat and mass transfer performance

(ii). It has quicker and more efficient mixing.

The disadvantage is that it requires high input of energy for mixing.

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3.1.2 DISTILLATION

The fermented beer from the fermentation stage is transferred to the distillation stage to
increase the concentration of ethanol. High grade hydrous industrial ethanol is generally
produced at a strength of 96o GL (192o US proof), where (oGL = degress Gay Lussac = % by
volume ethanol; US proof = 2 × % by volume ethanol). This hydrous ethanol product cannot
be further enriched by ordinary distillation because of azeotrope formation, but must be
dehydrated by other means. [10]

The beer feed is preheated from the normal fermentation temperature in several stages,
recovering low level and intermediate level heat from effluent streams and vapours in the
process. This preheated beer is degassed and fed to the beer stripper, which has stripping
trays below the beer feed point and several rectifying trays above it.

The condensed high wines from the top of this tower are then fed to the extractive distillation
tower, which may operate at a pressure of 6-7 bars (87-101.5 psi). In this tower, most of the
impurities are removed and carried overhead to be condensed as a low grade ethanol stream,
from which a small purge of heads (acetaldehyde and other low boiling impurities) may be
taken.

The partially purified, diluted ethanol from the bottom of the extractive distillation tower is
fed to the rectifying tower, which has an integral stripping section. In this tower, the high
grade ethanol product, whether industrial or potable, is taken as a side draw from one of the
upper trays. A small heads cut is removed from the overhead condensate.

Fusel oil is drawn off at two points above the feed tray but below the product draw tray to
avoid a build-up of fusel oil impurities in the rectifying tower. Fusel oil is also drawn below
the ethanol product tray because of its greater density than the ethanol-rich liquid product.
The rectifying tower is heated by vapours from both the pressurized extractive distillation
tower and the pressurized concentrating tower.

In the concentrating tower, the overhead condensate from the rectifying column is
concentrated. The partially purified ethanol stream recovered from this concentration stage is
fed back to the extractive distillation tower for re-purification and recovery of its ethanol
content. The acetaldehyde fraction obtained from the concentrating tower can be sold or used
as a fuel.

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The diagram below shows a typical flow diagram for the distillation of ethanol.

Figure 3.3: Flow sheet for the distillation of ethanol. [10]

The diagram below shows the more pictorial view of the distillation system shown above

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Figure 3.4: Pictorial flow sheet of the ethanol distillation process

3.1.3 EQUIPMENT FOR DISTILLATION

In the early version of distillation systems, all the towers were operated at atmospheric
pressure. However, installations made within the past 40 years utilize the multistage pressure
system to reduce energy consumption to a level of about 50% of the all-atmospheric system.
The commercial installations utilizing the multistage pressure, or ‘pressure cascading’
technique operate with a steam consumption of 3.0-4.2 kg of steam/litre (25-35 lb/gallon) of
96o GL ethanol. This is double the efficiency of about 6 kg of steam/litre for earlier
conventional distillation systems.

The most common distillation contactors are perforated trays. Trays provide intensive mixing
of the vapour and liquid phases and at the same time allowing easy movement of vapour up
and liquid down the column.

Side view of a perforated tray contactor:

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Figure 3.5: Side view of the perforated tray contactor

The plan view of the tray is:

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Figure 3.6: Plan view of the perforated tray contactor

The image below (Figure 2.5) shows the picture of the actual perforated tray contactor:

Figure 3.7: Actual picture of the perforated tray contactor [11]

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The other distillation equipment that also used is a packed column. The packed column
provides the necessary large interfacial area for diffusion. The packed column consists of a
cylindrical shell filled with some form of packing. The packing may consist of rings, saddles
or other shaped particles, all of which are designed to provide a high interfacial area for mass
transfer. In packed columns the vapour flows steadily up and the reflux steadily down the
column, giving a true countercurrent system in contrast to the conditions in bubble cap
columns, where the process of enrichment is stagewise.

A diagram of the packed column is shown below (figure 2.6).

Figure 3.8: Packed column for distillation.

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REFERENCES

1. Tongaat Hulett, (2012), Integrated Annual Report, South Africa, Tongaat Hulett, p4.

2. M. Garcia-perez, Biomass Conversion to Bio-fuels, ChE 481, Lecture 2, (2010)

3. NCP Alcohols (2009), Material Safety Data Sheet: Fusel Oil, South Africa, NCP
Alcohols, p2

4. http://www.un.org/millenium goals

5. Lucie A. Hazelwood, Jean-Marc Daran, Antonius J. A van Maris, Jack T. Pronk and
J. Richard Dicknson. (2003). The Erlich Pathway for Fusel oil Production. American
Society for Microbiology and Environmental Microbiology.

6. Z. Kucuk, K. Ceylan, Turk J. Chem. (1998), Potential Utilization of Fusel Oil: A

Kinetic Approach for Production of Fusel Oil Esters through Chemical Reaction,
Issue 22. Pp. 289-300

7. D. Caldwell, Molasses in Feeds, Indiana, Westway Trading Corporation.

8. J. Godbole, Ethanol From Cane Molasses, Hawaii Ethanol Workshop,

Honolulu,(2002)

9. A. G Patil, S. M Koolwal and H. D Butala, (2002), Fusel oil: Composition, removal

and potential utilisation, International Sugar Journal, Volume 104, Issue 1238, p1-8.

10. P. W. Madson, Ethanol distillation: the fundamentals, p281-285.

11. J. F. Richardson, J. H. Harker, J. R. Backhurst, (2002), Coulson and Richardson’s

Chemical Engineering Volume 2: Particle Technology and Separation Processes, Fifth
Edition, Oxford, Butterworth Heinemann. p627.

12. http://www.parchem.com/chemical-supplier-distributor/fusel-oil-010103.aspx

13. http;//www.scihub.org/AJSIR.

14. J. McMurry, (2008), Organic Chemistry, Seventh Edition, Australia, Thompson

Books/Cole

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