Various Types of Fractional Distillation Process used in Process Plants

What is Fractional Distillation?

Fractional Distillation or Distillation or Fractionation is the process of separation of components

from a product or mixture (Crude Oil) by heating the mixture to a temperature at which several
fractions of the compound will vaporize.

Normally when the mixture is heated, the component with the lowest boiling point will vaporize
first and will separate out from the mixture. With further increase in temperature, other
components will start to vaporize and separate. The component parts have boiling points that differ by
less than 25 °C (45 °F) from each other under a pressure of one atmosphere. If the difference in boiling points is
greater than 25 °C, a simple distillation is typically used.

Fractional Distillation is the most widely used form of separation technology and finds uses in
petroleum refineries, petrochemical, and chemical plants, natural gas processing and cryogenic air
separation plants. It is one of the most important separation processes.

Fractionation Towers or Distillation Columns in Process Plants

What are the alternatives to the fractional distillation process?

There are a few alternatives to distillation as mentioned below but require higher investment
costs. This is the main reason that distillation remains the main choice in the hydrocarbon industry,
especially in large-scale applications.

1. Liquid-Liquid Extraction or Solvent Extraction.

2. Hydrophilic Pervaporation
3. Multi-membrane Permeation Separation
4. Adsorption process.

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1. Liquid-Liquid Extraction or Solvent Extraction.

Liquid–liquid extraction (LLE), also known as solvent extraction and partitioning, is a method to
separate compounds or metal complexes, based on their relative solubilities in two different
immiscible liquids, usually water (polar) and an organic solvent (non-polar). There is a net transfer
of one or more species from one liquid into another liquid phase, generally from aqueous to
organic. The transfer is driven by chemical potential, i.e. once the transfer is complete, the overall
system of chemical components that make up the solutes and the solvents are in a more stable
configuration (lower free energy). The solvent that is enriched in solute(s) is called extract. The
feed solution that is depleted in solute(s) is called the raffinate. LLE is a basic technique in chemical
laboratories, where it is performed using a variety of apparatus, from separatory
funnels to countercurrent distribution equipment called as mixer settlers.[not verified in
body] This type of process is commonly performed after a chemical reaction as part of the work-
up, often including an acidic work-up.
The term partitioning is commonly used to refer to the underlying chemical and physical processes
involved in liquid–liquid extraction, but on another reading may be synonymous with it. The
term solvent extraction can also refer to the separation of a substance from a mixture by
preferentially dissolving that substance in a suitable solvent. In that case, a soluble compound is
separated from an insoluble compound or a complex matrix
From a hydrometallurgical perspective, solvent extraction is exclusively used in separation and
purification of uranium and plutonium, zirconium and hafnium, separation of cobalt and nickel,
separation and purification of rare earth elements etc., its greatest advantage being its ability to
selectively separate out even very similar metals. One obtains high-purity single metal streams on
'stripping' out the metal value from the 'loaded' organic wherein one can precipitate or deposit
the metal value. Stripping is the opposite of extraction: Transfer of mass from organic to aqueous
phase.
LLE is also widely used in the production of fine organic compounds, the processing of perfumes,
the production of vegetable oils and biodiesel, and other industries.[not verified in body] It is
among the most common initial separation techniques, though some difficulties result in
extracting out closely related functional groups.
Liquid–liquid extraction is possible in non-aqueous systems: In a system consisting of a molten
metal in contact with molten salts, metals can be extracted from one phase to the other. This is
related to a mercury electrode where a metal can be reduced, the metal will often then dissolve
in the mercury to form an amalgam that modifies its electrochemistry greatly. For example, it is
possible for sodium cations to be reduced at a mercury cathode to form sodium amalgam, while
at an inert electrode (such as platinum) the sodium cations are not reduced. Instead, water is
reduced to hydrogen. A detergent or fine solid can be used to stabilize an emulsion, or third phase.

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 Liquid-liquid solvent extraction method

Liquid-Liquid Extraction Column Types - Agitated and Static

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2. Hydrophilic Pervaporation

Pervaporation (or pervaporative separation) is a processing method for the separation

of mixtures of liquids by partial vaporization through a non-porous or porous membrane.

The term pervaporation is a portmanteau of the two steps of the process: (a) permeation through
the membrane by the permeate, then (b) its evaporation into the vapor phase. This process is used
by a number of industries for several different processes, including purification and analysis, due
to its simplicity and in-line nature.
The membrane acts as a selective barrier between the two phases: the liquid-phase feed and the
vapor-phase permeate. It allows the desired component(s) of the liquid feed to transfer through it
by vaporization. Separation of components is based on a difference in transport rate of individual
components through the membrane.
Typically, the upstream side of the membrane is at ambient pressure and the downstream side is
under vacuum to allow the evaporation of the selective component after permeation through the
membrane. Driving force for the separation is the difference in the partial pressures of the
components on the two sides and not the volatility difference of the components in the feed
The driving force for transport of different components is provided by a chemical potential
difference between the liquid feed/retentate and vapor permeate at each side of the membrane.
The retentate is the remainder of the feed leaving the membrane feed chamber, which is not
permeated through the membrane. The chemical potential can be expressed in terms of fugacity,
given by Raoult's law for a liquid and by Dalton's law for (an ideal) gas. During operation, due to
removal of the vapor-phase permeate, the actual fugacity of the vapor is lower than anticipated
on basis of the collected (condensed) permeate.
Separation of components (e.g. water and ethanol) is based on a difference in transport rate of
individual components through the membrane. This transport mechanism can be described using
the solution-diffusion model, based on the rate/ degree of dissolution of a component into the
membrane and its velocity of transport (expressed in terms of diffusivity) through the membrane,
which will be different for each component and membrane type leading to separation.

pervaporation of hydrophilic zeolite

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3. Adsorption process

What is adsorption?
The use of solids for removing substances from either gaseous or liquid solutions has been widely
used since biblical times. This process, known as adsorption, involves nothing more than the
preferential partitioning of substances from the gaseous or liquid phase onto the surface of a
solid substrate. From the early days of using bone char for decolonization of sugar solutions and
other foods, to the later implementation of activated carbon for removing nerve gases from the
battlefield, to today’s thousands of applications, the adsorption phenomenon has become a useful
tool for purification and separation.
Adsorption phenomena are operative in most natural physical, biological, and chemical systems,
and adsorption operations employing solids such as activated carbon and synthetic resins are used
widely in industrial applications and for purification of waters and wastewaters.

The process of adsorption involves separation of a substance from one phase accompanied by its
accumulation or concentration at the surface of another. The adsorbing phase is the adsorbent,
and the material concentrated or adsorbed at the surface of that phase is the adsorbate.
Adsorption is thus different from absorption, a process in which material transferred from one
phase to another (e.g. liquid) interpenetrates the second phase to form a “solution”. The term
sorption is a general expression encompassing both processes.

Physical adsorption is caused mainly by van der Waals forces and electrostatic forces between
adsorbate molecules and the atoms, which compose the adsorbent surface. Thus adsorbents are
characterized first by surface properties such as surface area and polarity.

A large specific surface area is preferable for providing large adsorption capacity, but the creation
of a large internal surface area in a limited volume inevitably gives rise to large numbers of small
sized pores between adsorption surfaces. The size of the micropores determines the accessibility
of adsorbate molecules to the internal adsorption surface, so the pore size distribution of
micropores is another important property for characterizing adsorptivity of adsorbents. Especially
materials such as zeolite and carbon molecular sieves can be specifically engineered with precise
pore size distributions and hence tuned for a particular separation.

Surface polarity corresponds to affinity with polar substances such as water or alcohols. Polar
adsorbents are thus called “hydrophilic” and aluminosilicates such as zeolites, porous alumina,
silica gel or silica-alumina are examples of adsorbents of this type. On the other hand, nopolar
adsorbents are generally “hydrophobic”. Carbonaceous adsorbents, polymer adsorbents and
silicalite are typical nonpolar adsorbents. These adsorbents have more affinity with oil or
hydrocarbons than water.

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Types of Distillation Processes
There are various types of distillation processes that are popularly used in various industries for
separating different products. Those are

Fractional Distillation
Extractive Distillation
Reactive Distillation Simple
distillation.
Steam distillation.
Vacuum distillation.
Air-sensitive vacuum distillation.
Short path distillation.
Zone distillation
Azeotropic Distillation
Distillation under Reduced Pressure
Destructive Distillation
Industrial Distillation

When the physical properties (mainly boiling point) of the components in a mixture are very close to
one another (Example: an azeotropic mixture), the separation method becomes difficult.

Out of the above types, Fractional, Extractive, Reactive and Industrial distillation are the most
frequently used ones.

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1. Fractional Distillation

Fractional distillation is the separation of a mixture into its component parts,

or fractions. Chemical compounds are separated by heating them to a temperature at
which one or more fractions of the mixture will vaporize. It uses distillation to fractionate.
Generally, the component parts have boiling points that differ by less than 25 °C (45 °F)
from each other under a pressure of one atmosphere. If the difference in boiling points is
greater than 25 °C, a simple distillation is typically used.

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 2. Extractive Distillation
Extractive distillation is defined as distillation in the presence of a miscible, high-boiling,
relatively non-volatile component, the solvent that forms no azeotrope with the other
components in the mixture. The method is used for mixtures having a low value of relative
volatility, nearing unity. Such mixtures cannot be separated by simple distillation, because
the volatility of the two components in the mixture is nearly the same, causing them to
evaporate at nearly the same temperature at a similar rate, making normal distillation
impractical.
The method of extractive distillation uses a separation solvent, which is generally non-
volatile, has a high boiling point and is miscible with the mixture, but doesn't form an
azeotropic mixture. The solvent interacts differently with the components of the mixture
thereby causing their relative volatilities to change. This enables the new three-part
mixture to be separated by normal distillation. The original component with the greatest
volatility separates out as the top product. The bottom product consists of a mixture of the
solvent and the other component, which can again be separated easily because the solvent
does not form an azeotrope with it. The bottom product can be separated by any of the
methods available.
It is important to select a suitable separation solvent for this type of distillation. The solvent
must alter the relative volatility by a wide enough margin for a successful result. The
quantity, cost and availability of the solvent should be considered. The solvent should be
easily separable from the bottom product, and should not react chemically with the
components or the mixture, or cause corrosion in the equipment. A classic example to be
cited here is the separation of an azeotropic mixture of benzene and cyclohexane,
where aniline is one suitable solvent.

Process flow diagram showing an extractive distillation apparatus. In this case, the mixture components A and B
are separated in the first column through the solvent E (recovered in the second column).

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 Extractive Distillation-Separate

3. Reactive Distillation Simple

Reactive distillation is a process where the chemical reactor is also the still. Separation of
the product from the reaction mixture does not need a separate distillation step which
saves energy (for heating) and materials. This technique can be useful for equilibrium-
limited reactions such as esterification and ester hydrolysis reactions. Conversion can be
increased beyond what is expected by the equilibrium due to the continuous removal of
reaction products from the reactive zone. This approach can also reduce capital and
investment costs.
The conditions in the reactive column are suboptimal both as a chemical reactor and as
a distillation column, since the reactive column combines these. The introduction of an in
situ separation process in the reaction zone or vice versa leads to complex interactions
between vapor–liquid equilibrium, mass transfer rates, diffusion and chemical kinetics,
which poses a great challenge for design and synthesis of these systems. Side reactors,
where a separate column feeds a reactor and vice versa, are better for some reactions, if
the optimal conditions of distillation and reaction differ too much.

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 Reactive Distillation Unit Manufacturer

Scheme of a simple reactive distillation setup

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 4. Steam distillation

Steam distillation is a special type of distillation (a separation process) for temperature

sensitive materials like natural aromatic compounds. It once was a popular laboratory
method for purification of organic compounds, but has become less common due to the
proliferation of vacuum distillation. Steam distillation remains important in certain
industrial sectors.

Many organic compounds tend to decompose at high-sustained temperatures. Separation

by distillation at the normal (1-atmosphere) boiling points is not an option, so water
or steam is introduced into the distillation apparatus. The water vapor carries small
amounts of the vaporized compounds to the condensation flask, where the condensed
liquid phase separates, and allowing easy collection. This process effectively enables
distillation at lower temperatures, reducing the deterioration of the desired products. If the
substances to be distilled are very sensitive to heat, steam distillation may be applied under
reduced pressure, thereby reducing the operating temperature further.

After distillation, the vapors are condensed. Usually the immediate product is a two-phase
system of water and the organic distillate, allowing separation of the components
by decantation, partitioning or other suitable methods.

Diagram of how to economically clean up plant wastewater streams. Steam is use as a stripping gas to remove
hydrocarbons from the wastewater. This method is effective when the volatile organic compounds have lower
boiling points than water or have limited solubility in water.

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5. Vacuum distillation

Vacuum distillation is distillation performed under reduced pressure, which allows the
purification of compounds not readily distilled at ambient pressures or simply to save time
or energy. This technique separates compounds based on differences in boiling points. This
technique is used when the boiling point of the desired compound is difficult to achieve or
will cause the compound to decompose. A reduced pressure decreases the boiling point of
compounds. The reduction in boiling point can be calculated using a temperature-
pressure nomograph using the Clausius–Clapeyron relation.

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6. Air-sensitive vacuum distillation

Some compounds have high boiling points as well as being air sensitive. A simple vacuum
distillation system as exemplified above can be used, whereby the vacuum is replaced
with an inert gas after the distillation is complete. However, this is a less satisfactory
system if one desires to collect fractions under a reduced pressure. To do this a "pig"
adaptor can be added to the end of the condenser, or for better results or for very air
sensitive compounds a Perkin triangle apparatus can be used.

The Perkin triangle, has means via a series of glass or Teflon taps to allows fractions to be
isolated from the rest of the still, without the main body of the distillation being removed
from either the vacuum or heat source, and thus can remain in a state of reflux. To do
this, the sample is first isolated from the vacuum by means of the taps, the vacuum over
the sample is then replaced with an inert gas (such as nitrogen or argon) and can then be
stoppered and removed. A fresh collection vessel can then be added to the system,
evacuated and linked back into the distillation system via the taps to collect a second
fraction, and so on, until all fractions have been collected.

Molecular Distillation Mass Transfer Operations

Molecular distillation is vacuum distillation below the pressure of 0.01 torr. 0.01 torr is
one order of magnitude above high vacuum, where fluids are in the free molecular flow
regime, i.e. the mean free path of molecules is comparable to the size of the equipment.
The gaseous phase no longer exerts significant pressure on the substance to be
evaporated, and consequently, rate of evaporation no longer depends on pressure. That
is, because the continuum assumptions of fluid dynamics no longer apply, mass transport
is governed by molecular dynamics rather than fluid dynamics. Thus, a short path
between the hot surface and the cold surface is necessary, typically by suspending a hot
plate covered with a film of feed next to a cold plate with a clear line of sight in between.
Molecular distillation is used industrially for purification of oils.

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 7. Short path distillation

Short-path distillation is a distillation technique that involves the distillate travelling a

short distance, often only a few centimeters, and is normally done at reduced pressure. A
classic example would be a distillation involving the distillate travelling from one glass bulb
to another, without the need for a condenser separating the two chambers. This technique
is often used for compounds, which are unstable at high temperatures or to purify small
amounts of compound. The advantage is that the heating temperature can be considerably
lower (at reduced pressure) than the boiling point of the liquid at standard pressure, and
the distillate only has to travel a short distance before condensing. A short path ensures
that little compound is lost on the sides of the apparatus. The Kugel Rohr is a kind of a short
path distillation apparatus which often contain multiple chambers to collect distillate
fractions.

Short-path vacuum distillation apparatus with vertical condenser (cold finger), to minimize the distillation path; 1: Still
pot with stirrer bar/anti-bumping granules 2: Cold finger – bent to direct condensate 3: Cooling water out 4: cooling
water in 5: Vacuum/gas inlet 6: Distillate flask/distillate.

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8. Zone distillation

Zone distillation is a distillation process in long container with partial melting of refined
matter in moving liquid zone and condensation of vapor in the solid phase at condensate
pulling in cold area. The process is worked in theory. When zone heater is moving from the
top to the bottom of the container then solid condensate with irregular impurity
distribution is forming. Then most pure part of the condensate may be extracted as
product. The process may be iterated many times by moving (without turnover) the
received condensate to the bottom part of the container on the place of refined matter.
The irregular impurity distribution in the condensate (that is efficiency of purification)
increases with the number of iterations. Zone distillation is the distillation analog of zone
recrystallization. Impurity distribution in the condensate is described by known equations
of zone recrystallization – with the replacement of the distribution co-efficient k of
crystallization - for the separation factor α of distillation.

9. Azeotropic Distillation

In chemistry, azeotropic distillation is any of a range of techniques used to break

an azeotrope in distillation. In chemical engineering, azeotropic distillation usually refers to
the specific technique of adding another component to generate a new, lower-boiling
azeotrope that is heterogeneous (e.g. producing two, immiscible liquid phases), such as the
example below with the addition of benzene to water and ethanol. This practice of adding
an entrainer which forms a separate phase is a specific sub-set of (industrial) azeotropic
distillation methods, or combination thereof. In some senses, adding an entrainer is similar
to extractive distillation.

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 Phase diagram(left) and process flow diagram (right) of an apparatus for the azeotropic distillation with "material
separation agent". In this case the phase diagram includes a zone where components are not miscible, so
following the condensation of the azeotrope, it is possible to separate the liquid components through decantation.

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10. Destructive Distillation

Destructive distillation is the chemical process of the decomposition of unprocessed

material by heating it to a high temperature; the term generally applies to processing
of organic material in the absence of air or in the presence of limited amounts of oxygen or
other reagents, catalysts, or solvents, such as steam or phenols. It is an application
of pyrolysis. The process breaks up or 'cracks' large molecules. Coke, coal gas, gas
carbon, coal tar, ammonia liquor, and coal oil are examples of commercial products
historically produced by the destructive distillation of coal.

Destructive distillation of any particular inorganic feedstock produces only a small range of
products as a rule, but destructive distillation of organic materials commonly produces very
many compounds, often hundreds, although not all products of any particular process are
of commercial importance. The distillate are generally lower molecular weight. Some
fractions however polymerise or condense small molecules into larger molecules, including
heat-stable tarry substances and chars. Cracking feedstock into liquid and volatile
compounds, and polymerising, or the forming of chars and solids, may both occur in the
same process, and any class of the products might be of commercial interest.

Currently the major industrial application of destructive distillation is to coal.

Historically the process of destructive distillation and other forms of pyrolysis led to the
discovery of many chemical compounds or elucidation of their structures before
contemporary organic chemists had developed the processes to synthesis or specifically
investigate the parent molecules. It was especially in the early days that investigation of the
products of destructive distillation, like those of other destructive processes, played parts
in enabling chemists to deduce the chemical nature of many natural materials. Well known
examples include the deduction of the structures of pyranoses and furanoses.

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Many early experiments used retorts for destructive distillation.

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 11. Industrial distillation

Industrial distillation is performed inside a large, vertical, tall cylindrical column. These columns are
popularly known as “fractionation towers” or “distillation columns” or “Distillation Towers” and can
be found in most of the process plants. The diameter of such Columns can range from about 65
centimeters to 6 meters and heights can range from about 6 meters to 60 meters or more.

Other types[edit]

 Catalytic distillation is the process by which the reactants are catalyzed while being
distilled to continuously separate the products from the reactants. This method is used
to assist equilibrium reactions reach completion.
 Flash evaporation (or partial evaporation) is the partial vaporization that occurs when
a saturated liquid stream undergoes a reduction in pressure by passing through a
throttling valve or other throttling device. This process is one of the simplest unit
operations, being equivalent to a distillation with only one equilibrium stage.
 Codistillation is distillation, which is performed on mixtures in which the two
compounds are not miscible. In the laboratory, the Dean-Stark apparatus is used for
this purpose to remove water from synthesis products. The Bleidner is another example
with two refluxing solvents.
 Membrane distillation is a type of distillation in which vapors of a mixture to be
separated are passed through a membrane, which selectively permeates one
component of mixture. Vapor pressure difference is the driving force. It has potential
applications in seawater desalination and in removal of organic and inorganic
components.
The unit process of evaporation may also be called "distillation":

 In rotary evaporation a vacuum distillation apparatus is used to remove

bulk solvents from a sample. Typically the vacuum is generated by a water aspirator or
a membrane pump.
 In a kugelrohr a short path distillation apparatus is typically used (generally in
combination with a (high) vacuum) to distill high boiling (> 300 °C) compounds. The
apparatus consists of an oven in which the compound to be distilled is placed, a
receiving portion which is outside of the oven, and a means of rotating the sample. The
vacuum is normally generated by using a high vacuum pump.
Other uses:

 Dry distillation or destructive distillation, despite the name, is not truly distillation, but
rather a chemical reaction known as pyrolysis in which solid substances are heated in
an inert or reducing atmosphere and any volatile fractions, containing high-boiling
liquids and products of pyrolysis, are collected. The destructive distillation of wood to
give methanol is the root of its common name – wood alcohol.
 Freeze distillation is an analogous method of purification using freezing instead of
evaporation. It is not truly distillation, but a recrystallization where the product is
the mother liquor, and does not produce products equivalent to distillation. This
process is used in the production of ice beer and ice wine to increase ethanol
and sugar content, respectively. It is also used to produce applejack. Unlike distillation,
freeze distillation concentrates poisonous congeners rather than removing them; As a
result, many countries prohibit such applejack as a health measure. However, reducing
methanol with the absorption of 4A molecular sieve is a practical method for

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production. Also, distillation by evaporation can separate these since they have
different boiling points.

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